anellated calix[4]arenes - ruhr-universit¤t bochum

Anellated Calix[4]arenes

Dissertation

for the Degree of

Doctor of Natural Sciences (Dr. rer. nat.)

by

Wiebke Hüggenberg

from Witten

Faculty of Chemistry and Biochemistry

Bochum 2011

Referent: Prof. Dr. Gerald Dyker

Koreferent: Prof. Dr. Martin Feigel

Tag der Abgabe: 16.5.2011

Tag der Disputation: 8.7.2011

Die vorliegende Arbeit wurde von Januar 2007 bis Mai 2011 am Lehrstuhl für

Organische Chemie II der Fakultät für Chemie und Biochemie der Ruhr-Universität

Bochum in dem Arbeitskreis Organische/Metallorganische Chemie von Herrn Prof. Dr.

Gerald Dyker angefertigt.

Herrn Prof. Dr. Gerald Dyker danke ich für die Überlassung des interessanten Themas,

die Diskussionsbereitschaft bei theoretischen und praktischen Problemen sowie den

gegebenen Freiraum zur Forschung.

Herrn Prof. Dr. Martin Feigel danke ich für die freundliche Übernahme des Koreferats.

Meinen Laborkollegen Marcus Pillekamp, Dr. Matthias Kanthak, Erik Schwake,

Stephan Schöler, Christian Dietz, Dr. Hebert Estevez Rivera, Dr. Lertnarong Sripanom

und Dr. Thomas Meyer-Gall danke ich für das angenehme Arbeitsklima, die zahlreichen

kleineren und größeren Gefallen und die Unterstützung während der gesamten Zeit.

Annamaria Seper und Christian Wagner danke ich für ihre Beiträge zu dieser Arbeit im

Rahmen von Vertiefungspraktika.

Den ehemaligen Masterstudenenten Sebastian Klimczyk, Simon Trosien und Saskia

Neukirchen möchte ich ebenfalls für ihre Unterstützung und das angenehme

Arbeitsklima danken.

Besonderer Dank gilt den Mitgliedern der analytischen Abteilungen der Fakultät: Herrn

Gregor Barchan und Herrn Martin Gartman möchte ich ganz besonders für die

Aufnahme zahlreicher NMR-Spektren danken. Frau Sabine Bendix und Frau Jutta

Schäfer danke ich für die Aufnahme zahlreicher Massenspektren. Frau Karin

Bartholomäus möchte ich für die Durchführung der Elementaranalysen danken.

Frau Prof. Dr. Iris M. Oppel danke ich für die Aufnahme und besonders die

Verfeinerung der Röntgenstrukturanalysen. Ebenfalls möchte ich Frau Manuela Winter

für die Aufnahme der Röntgenstukturanalysen danken.

Tobias Plöger danke ich für die Aufnahme der ATR-IR Spektren.

Dem Lehrstuhl für Organische Chemie I von Herrn Prof. Kiedrowski möchte ich für die

Nutzung der Feinwaage danken.

Allen Mitarbeiterinnen und Mitarbeitern des Lehrstuhls Organische Chemie II, Frau

Heidemarie Joppich, Frau Barbara Schröder, Frau Ulrike Steger und Herrn Torsten

Haenschke der Ruhr-Universität Bochum danke ich für die vielfältige Unterstützung

und die freundliche Aufnahme. Besonderer Dank gebührt Herrn Klaus Gomann für die

technische Unterstützung bei Problemen mit der HPLC-Anlage.

Meinen Eltern danke ich für die Unterstützung und Geduld während dieser Arbeit,

besonders in den letzten Monaten.

Meinen Freunden möchte ich ebenfalls für ihre Hilfsbereitschaft, Geduld und

Unterstützung danken.

Besonderen Dank möchte ich Stephan Schöler und Christian Dietz für das kurzfristige

Korrekturlesen dieser Arbeit aussprechen.

Für finanzielle Unterstützung möchte ich der Deutschen Forschungsgemeinschaft

(DFG) danken (Projekt Dy 12/9-2).

i

Table of contents

I. Theoretical Part 1

1 Introduction 1

1.1 General 1

1.1.1 Syntheses of calixarenes 7

1.1.2 Conformational Isomerism 8

1.1.3 Inherently chiral calixarenes 11

1.1.4 Nomenclature 12

1.2 Goal of Research 12

2 Multifold Photocyclizations of Styrylcalix[4]arenes 15

2.1 Calix[4]arenes with anellated subunits and [2+2] cycloaddition products 15

2.2 Synthesis and photocyclization of a proximal distyrylcalix[4]arene 18

2.3 Prevention of the [2+2] cycloaddition by steric hindrance 25

2.4 Conclusion 30

3 Anellated calixarenes by dehydrohalogenation 31

3.1 Introduction 31

3.2 Phenanthrene model compounds 36

3.3 Syntheses of calix[4]phenanthrene derivatives 41

3.4 Synthesis of a fluorenone model compound 50

3.5 Syntheses of calix[4]fluorenones 57

3.6 Previous studies on calix[4]triphenylenes 70

3.7 Synthesis of a triphenylene model compound 74

3.8 Syntheses of calix[4]triphenylenes 76

3.9 Conclusion 84

4 Syntheses of unsymmetrical tetrazines 89

4.1 Introduction 89

4.2 Syntheses of tetrazine model compounds 92

4.3 Synthesis of tetrazine moieties at calix[4]arenes 100

4.4 Conclusion 105

Table of Contents

ii

5 Conclusion and Outlook 109

II. Experimental Part 113

1 Methods and Materials 113

1.1 Reaction control and separation methods 113

1.2 Analytical chemistry: apparatus, instruments, acquisition methods and

comments on analytical data 114

1.3 Solvents and reagents 116

2 Syntheses 121

2.1 Syntheses of reagents and model compounds 121

2.1.1 Triphenyl(1-phenylethyl)phosphonium bromide (84) 121

2.1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118) 123

2.1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124) 126

2.1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethyl-

silane (125) 129

2.1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-

phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-

3,5-dimethylphenyl)methanone) (120b) 132

2.1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and

1-(4-hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128) 137

2.1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) 141

2.1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130) 144

2.1.9 (2-Bromophenylethynyl)trimethylsilane (144) 147

2.1.10 1-Bromo-2-ethynylbenzene (140) 149

2.1.11 2-Chlorobenzoyl chloride (148a), 2-Bromobenzoyl chloride (148b),

2-Iodobenzoyl chloride (148c) 151

2.1.12 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) 154

2.1.13 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) 157

2.1.14 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c) 160

2.1.15 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151) 163

2.1.16 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154) 166

2.1.17 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161) 169

Table of Contents

iii

2.1.18 4-Bromo-2,6-dimethylphenol (208) 172

2.1.19 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209) 174

2.1.20 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210) 177

2.1.21 1,3-Dimethyltriphenylen-2-yl acetate (211) 180

2.1.22 4-Methoxy-3,5-dimethylbenzaldehyde (250) 183

2.1.23 4-Methoxy-3,5-dimethylbenzoic acid (251) 185

2.1.24 4-Methoxy-3,5-dimethylbenzoyl chloride (245) 187

2.1.25 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246) 189

2.1.26 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydra-

zonoyl chloride (247) 192

2.1.27 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole

(253) 195

2.1.28 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine

(249) 198

2.1.29 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258) 201

2.1.30 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzohydrazonoyl

chloride (259) and 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-

oxadiazole (260) 203

2.1.31 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine

(261) 208

2.1.32 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262) 210

2.2 Syntheses at the upper rim of calixarenes 213

2.2.1 Transannular cyclization-product (cone) (60) 213

2.2.2 cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]arene (73) 216

2.2.3 cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene (74) 218

2.2.4 cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]arene (75) 220

2.2.5 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-

arene (65) 222

2.2.6 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c) 226

2.2.7 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-

propoxycalix[4]arene (85) 233

2.2.8 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene

(86a and 86b) 236

Table of Contents

iv

2.2.9 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-

tetra-n-propoxycalix[4]arene (88) 240

2.2.10 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-

calix[4]arene (132) 243

2.2.11 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(133) and 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]arene (134) 245

2.2.12 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-

propoxycalixarene (136) 249

2.2.13 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a) 252

2.2.14 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b) 255

2.2.15 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(141a) 257

2.2.16 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxy-

calix[4]arene (141b) 260

2.2.17 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a)263

2.2.18 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(137b) 266

2.2.19 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and

5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166) 269

2.2.20 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and

5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172) 274

2.2.21 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) and

5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) 279

2.2.22 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),

5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and

paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180) 282

2.2.23 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),

paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (175) and

5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176) 289

2.2.24 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165) 296

2.2.25 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and

5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174) 297

Table of Contents

v

2.2.26 cone-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163),

5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181) and

paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182) 302

2.2.27 cone-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (166),

paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) and

5,17-Bis(2-chloro-benzoyl)-25,26,27-tri-n-propoxcalix[4]arene (178) 306

2.2.28 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184) 309

2.2.29 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene

(212) 314

2.2.30 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene

(214) 317

2.2.31 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218) 320

2.2.32 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]-

arene (220) 322

2.2.33 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes

(217a and 217b) 325

2.2.34 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b) 329

2.2.35 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263) 332

2.2.36 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-dicarbonyl chloride

(264) 334

III. Appendix 335

1 Cross-peak tables 335

1.1 General Remarks 335

1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118) 336

1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124) 337

1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)-trimethyl-

silane (125) 338

1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-

phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-3,5-

dimethylphenyl)methanone) (120b) 340

1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and 1-(4-

Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128) 342

Table of Contents

vi

1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) 344

1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130) 345

1.9 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) 346

1.10 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) 347

1.11 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c) 348

1.12 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151) 349

1.13 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154) 350

1.14 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161) 351

1.15 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209) 352

1.16 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210) 353

1.17 1,3-Dimethyltriphenylen-2-yl acetate (211) 354

1.18 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246) 355

1.19 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydra-

zonoyl chloride (247) 356

1.20 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole

(253) 357

1.21 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine

(249) 358

1.22 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258) 359

1.23 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzohydrazonoyl

chloride (259) and 2-(4-Methoxy-3,5-dimethyl-phenyl)-5-phenyl-1,3,4-

oxadiazole (260) 360

1.24 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine

(261) 362

1.25 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262) 363

1.26 Transannular cyclization product (cone) (60) 364

1.27 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene

(65) 366

1.28 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c) 369

1.28.1 proximal cone-Calix[4]diphenanthrene (81a) 369

1.28.2 proximal cone-Calix[4]diphenanthrene (81b) 373

1.28.3 proximal cone-Calix[4]diphenanthrene (81c) 375

1.29 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxy-

calix[4]arene (85) 377

Table of Contents

vii

1.30 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene

(86a and 86b) 380

1.31 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-

tetra-n-propoxycalix[4]arene (88) 383

1.32 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(133) 385

1.33 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-

propoxycalixarene (136) 387

1.34 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a) 389

1.35 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(141a) 391

1.36 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(141b) 393

1.37 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a) 395

1.38 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(137b) 397

1.39 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and

5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166) 399

1.40 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and

5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172) 403

1.41 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) 407

1.42 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),

5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and

paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180) 409

1.43 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),


5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176) 415

1.44 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and

5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174) 421

1.45 paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182) 425

1.46 paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) 427

1.47 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184) 430

Table of Contents

viii

1.48 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene

(212) 435

1.49 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene

(214) 437

1.50 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(220) 439

1.51 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes

(217a and 217b) 441

1.52 29,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b) 444

1.53 Structure (157) 448

2 Crystal Structure Data 449

2.1 Transannular cyclization-product (cone) (60) 449

2.2 proximal cone-Calix[4]diphenanthrenes (81a) 463

2.3 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene

(86a) 475

3 Abbreviations 489

4 References 493

1

I. Theoretical Part

1 Introduction

1.1 General

Calixarenes are basket-shaped cyclic oligomers of phenol units, bridged by methylene

groups ortho to the hydroxyl groups.1 Their three-dimensional structure makes them

attractive building blocks for supramolecular chemistry2 and they are predestined to act

as host molecules because of their electron-rich, hydrophobic cavity. Moreover, they are

readily available and can easily be functionalized as required. Their ability to complex

cations3, anions4 or small neutral5 molecules makes them useful for separations and

applicable as sensors, selective receptors or extractants.6 Especially interesting is their

potential for enantioselective recognition and asymmetric catalysis utilizing inherently

chiral calixarenes (see Chapter 1.1.3 for inherent chirality).7 Furthermore, they can be

used as modifiers to improve selectivity in separations by HPLC or when bound to

silica gel they can serve as the stationary phase themselves.8

Calixarenes 1 and 2 are examples of fluorescent molecules able to detect toxic metals

(Figure 1.1). The 1,3-alternate calixarene 1, water-soluble due to the sulfonyl groups at

the upper rim, detects Cs+ selectively over other ions and could therefore find

application in extracting Cs+ from nuclear waste.9

Figure 1.1. Fluorescent sensors for Cs+ and Cd2+.

2 Theoretical Part

Functionalization of the calixarene scaffold with 1,2,3-triazole-containing systems, as

in calixarene 2, has been reported to be promising for the detection of Cd2+ and Zn2+

cations in organic solvents.10

Ion-selective electrodes based on calixarene 3, containing soft sulfur binding sites,

exhibit a high selectivity towards Ag+ over other ions, except Hg2+.11

Calixarene 4 contains pyrene units as chromphores, which are linked via amide

functionalities to the calixarene skeleton, and is an anionic receptor (Figure 1.2). It can

selectively detect fluoride, while no complex formation is observed with other halide

ions.12 The complex formation with F- ions causes a 54 nm red-shift of the UV

absorption band and a 12 nm blue-shift of the excimer emission as well as enhanced

fluorescence.

Figure 1.2. Fluorescent receptor for fluoride ions (4) and calixarene 5 , R = propyl, capable of

ion-pair recognition.

Calixcrown 5 is a ditopic receptor, which can complex a carboxylate ion by hydrogen

bonding with its upper rim hydroxytrifluoroethyl substituents and also bind a sodium

cation at the bridging polyether chain.13 Moreover, the presence of a sodium cation

enhances the ability to complex the anion at the upper rim. While the free ligand 5

adopts a flattened cone conformation with the trifluoroethanol groups sticking out and

the free phenolic units parallel to each other, the sodium complex has a more open

cavity. This probably enables the acetate ion to enter the cavity with the carboxylate

oxygen in proximity to the bound sodium cation, instead of forming hydrogen bonds to

the hydroxyl group.

Calixarenes also have a great potential in studying biomolecular functions like

recognition, catalysis and transport or acting as multivalent ligands for bio-

Introduction 3

macromolecules.14 One of the first examples was a vancomycin mimic based on the

calix[4]arene scaffold reported by Ungaro and et al.15

The transfer of chloride ions through lipid bilayer membranes has been studied using

calixarene like 6 bearing butylamide substituents at the lower rim.16 One molecule of 6

is, however, too small to span the membrane. Apparently, ion channels are formed by

HCl-mediated self-assembly to aggregates as observed for a comparable structure with

tetramethylamide chains. The proximally 1,5,9-triazacyclododecane substituted

calixarene 7 is a phospodiesterase mimic, efficiently catalyzing the cleavage of

phosphodiester bonds.17 Interestingly, it was observed that the metal centers act

cooperatively in the cleavage when they are on adjacent phenol units, while they act

independently from each other in the distally substituted analogue. The catalytic

efficiency was not further enhanced when three metal centers were placed at adjacent

positions.

HN

OO

OO

HN

O

NH

O

O ONH

6

OO OO

N N

N

N N

NH

H H

H

O O OO

Cu2+ Cu2+

7

Figure 1.3. Examples of calixarenes with the ability to mimic biological functions: ion

transporter 6 and the artificial phosphodiesterase 7.

Chiral recognition and asymmetric catalysis are important in biological systems.

Accordingly, chiral and especially inherently chiral calixarenes are of great interest

since artificial chiral receptors based on calixarenes could help in the study and

understanding of biological systems. Calixarene 8 contains a chiral side chain and

reveals enantioselective recognition towards N-Boc-protected alanine anion 9 (Figure

1.4).18 The (+)-enantiomer of calixarene 10 was reported by Shimizu et al. to show

recognition towards (R)- and (S)-mandelic acid and could be used to determine

enantiopurity of the acid by NMR.19

4 Theoretical Part

Figure 1.4. Enantioselective anionic receptor 8 for alanine anion 9 and inherently chiral

calixarene 10 that can distinguish between enantiomers of mandelic acid.

Moreover, 10 was the first inherently chiral calixarene to be used for asymmetric

catalysis. Although the observed enantioselectivy was poor, the asymmetric Michael-

type addition of thiophenol and cyclohexanone catalyzed by 10 showed chiral

induction.

The enantiomeric palladium complex 11 is the first example of a metal complex based

on an inherently chiral calixarene used in asymmetric catalysis (Figure 1.5).20,21 It

shows good activity as a catalyst for allylic alkylation and hydrogenation. The

alkylation of 1,3-diphenylprop-2-enyl acetate 12 with dimethyl malonate in the presence

of Me3SiOC(NSiMe3)CH3 proceeded with 100 % conversion. After three hours 67 % ee

were achieved with R = H, while R = SiMe3 afforded only 45 % ee.

Figure 1.5. First example of a metal complex based on an inherently chiral calixarene and its

application in the alkylation of 1,3-diphenylprop-2-enyl acetate 12.

When 11 was synthesized with two identical chiral side chains, and thus being not

inherently chiral, no chiral induction was observed. The complementary distally

Introduction 5

substituted ligand showed only poor enantioselectivity, giving 16 % ee. These findings

suggest that the selectivity is little influenced by introduction of asymmetric carbons

alone.

n n n n

Figure 1.6. Calixarenes and calixarene metal complexes used in catalysis.

Calixarenes like 14 can act as phase-transfer catalysts or be used for the extraction of

alkali-metal ions (Figure 1.6).22 While the lipophilic tert-octyl group enhanced the

catalytic activity as well as the extraction ability, the length of the polyether chain,

where the ions bind, has no significant effect.

Biscalix[4]arene-dirhodium complex 15 has been used for the cyclopropanation of

olefins. For example, employing 1 mol% at 20 °C in dichloromethane successfully

converted styrene (17) in 98 % (E/Z 72:28) in the presence of methyl diazoacetate

(MDA) (Scheme 1.1, example a)).23

Furthermore, calixarene 16, formed in situ from its chloromethyl precursor and

Pd(OAc)2, has been applied in the Suzuki cross-coupling of 4-chlorotoluene (19) with

phenylboronic acid (Scheme 1.1, example b)).24

Scheme 1.1. Applications of calixarene metal complexes 15 and 16: a) cyclopropenation of

olefins and b) Suzuki cross-coupling.

6 Theoretical Part

When 16 itself was used as ligand, 4-methylbiphenyl (20) was obtained in only 16 %

yield. Exchanging the isopropyl groups for mesityl groups improved the yield to 50 %,

which could be further increased to 60 % by introducing tert-butyl groups in para-

position of the other two phenol units.

Lately, the interest in hetera- and heterocalixarenes or mixtures of both as a new

generation of supramolecular host molecules has increased (Figure 1.7).25 In

heteracalixarenes phenol units are bridged by heteroatoms―such as oxygen, nitrogen or

sulfur―while in heterocalixarenes phenol units are substituted for hetero-

aromatics.25b,26,27

Figure 1.7. General structures of hetera- and heterocalixarenes.

Although oxa-,28 aza-29 and thiacalixarenes28c have been known for a while, the low

yields in which they were obtained prevented them from becoming more generally used.

Meanwhile, Miyano et al.30 introduced a one-pot procedure similar to conventional

calixarene synthesis to yield thiacalix[4]arene 21 in 54 % as well as a two-step

procedure yielding 21 in 83 % and the corresponding calix[6]- and calix[8]arenes as by-

products in significantly lower yields of about 5 % (Figure 1.8). Both lower and upper

rim derivatization have been successfully employed with this class of calix[4]arenes as

well as derivatization of the bridging sulfur atoms.31

Figure 1.8. Heteracalixarenes.

Several oxacalix[4]arenes27 were synthesized by Katz et al.32 in one step by

nucleophilic aromatic substitution (SNAr) of resorcinols with 1,5-difluoro-2,5-

Introduction 7

dinitrobenzene in yields between 80–90 %. Calixarene 22, for example, was obtained in

88 % yield and shown by X-ray diffraction analysis to adopt a distorted 1,3-alternate

conformation in the solid state.

Azacalixarenes, however, have been only obtained in low yields so far. Compound 23

was synthesized by Tsue et al.33 in a stepwise procedure yielding only 9 % overall,

while 24 was obtained in 19 % in one-step by Yamamoto et al.34,35

Figure 1.9. Heterocalixarenes.

Among heterocalixarenes (Figure 1.9), calixpyrroles like 25a, first synthesized by

Baeyer in 1886,36 have been studied extensively regarding their ability to act as

receptors for anions or neutral molecules and their transition metal coordination

chemistry.37,38

Calix[4]pyrroles have been converted to chlorocalix[4]pyridines 26, with chlorine in

one of the indicated positions, by reaction with dichlorocarbene.39 Jurczak et al.

reported the synthesis of calixfuran 25b in 71 % yield by condensation of furan with

acetone in the presence of concentrated sulfuric acid.40 Research by Wang et al. has

concentrated on stepwise fragment coupling to yield various heterocalixarenes with

mixed aromatic subunits bridged by heteroatoms. Examples are the oxacalix[2]-

arene[2]triazene 27 and azacalix[4]pyridines like 28, of which the azacalix[4]-

arene[4]pyridine shows high complexation ability towards C60 and C70.25d,41

1.1.1 Syntheses of calixarenes

Calixarenes are synthesized by base-catalyzed condensation of para-substituted

phenols, usually p-tert-butylphenol (29), with formaldehyde (30) (Scheme 1.2).

The ring size depends on the base used and its concentration as the cations have a

template effect.1a,42 Symmetrically substituted calixarenes with four, six or eight

8 Theoretical Part

subunits are available in good yields by one-pot procedures.43 Calix[5]arenes as well as

larger ring sizes have also been synthesized in low yields.44

Scheme 1.2. Synthesis of calix[4]arene 32.

Calixarenes consisting of nine to twenty phenol subunits, for example, were obtained

through acid-catalyzed condensation by Gutsche et al.44c Stepwise syntheses can yield

unsymmetrically substituted calixarenes, but are often tedious and give low overall

yields, which is improved by convergent multi-step syntheses.45,46

In para position unsubstituted calixarenes are obtained by lewis acid catalyzed

dealkylation47 of the corresponding p-alkylcalixarenes.48 A wide range of calix[4]arenes

is available by functionalization of calix[4]arene 32 at the hydroxyl groups49 (lower rim

or narrow rim) and the para position of the phenyl rings50 (upper rim or wide rim).

Although less common, meta-substituted calixarenes are also available either by the less

attractive fragment condensation51 or direct functionalization,52 usually assisted by

ortho-directing groups. Thus, not only tetrasubstituted calixarenes can be obtained, but

mono-, 1,2-di- or 1,3-di- and trisubstituted calixarenes, both at the upper as well as the

lower rim, can be also selectively synthesized.53

1.1.2 Conformational Isomerism

Calix[4]arenes can adopt the four different conformations depicted in Figure 1.10: cone,

partial-cone (paco), 1,2-alternate and 1,3-alternate.54 These conformations can

interchange through ring inversion, whereby either the hydroxyl groups or the

para-substituent passes through the ring. However, the latter only matters when

hydrogen is in para-position.

In most cases the cone conformation is favoured both in solution and in the solid state

for calixarenes with free hydroxyl groups. This is confirmed by crystal structure data as

well as the stretching vibrations of the hydroxyl groups, which appear at unusually low

frequencies, in IR spectra.5a-b,55 The reason is stabilization of the cone conformation by

intramolecular hydrogen bonding between the phenolic hydroxyl groups.

Introduction 9

Figure 1.10. Conformational isomerism of calix[4]arenes substituted at the upper rim.

Due to the ring inversion, 1H NMR spectra show only two broad singlets for the

bridging methylene groups at higher temperatures. At lower temperatures, when the ring

inversion is slow on the NMR time scale, these signals appear as two doublets.

Inversion barriers and coalescence temperatures were investigated in dependence from

various solvents by temperature-dependent 1H NMR spectroscopy.56

Alkylation of the hydroxyl groups can fix the calix[4]arene in one of the four

conformations when the alkyl groups are larger than ethyl.57 The conformation adopted

upon alkylation can be influenced by the choice of solvent and alkylating agent as well

as the base used for the deprotonation of the hydroxyl groups, since a metal template

effect of the cations plays a crucial role.57b,58

The different conformations can be distinguished by the characteristic signal pattern

of the methylene protons (Table 1.1). For symmetrical cone calixarenes a highfield

doublet at about 3.2–3.5 ppm and one at lower field around 4.2–4.5 ppm can be usually

observed. The first is assigned to the equatorial protons (in proximity to the aromatic

ring), while the latter belongs to the axial protons (closer to the hydroxyl group).

Figure 1.11. Phenol rings in syn and anti orientation.

10 Theoretical Part

Table 1.1. Characteristic NMR signals of the methylene groups in the different conformations.

signals for the methylene protons conformation

1H NMR

13C NMR

cone two doublets

(each 4 H, J ≈ 12 Hz) one signal: 30–32 ppm

partial-cone

four doublets

(each 2 H, J ≈ 12 Hz) or

two doublets (each 2 H,

J ≈ 12 Hz) and one singlet (4 H)

two signals: 31 ppm and 37 ppm

1,2-alternate two doublets (each 2 H,

J ≈ 12 Hz) and one singlet (4 H) two signals: 31 ppm and 37 ppm

1,3-alternate one singlet (8 H) one signal: 37–38 ppm

13C NMR spectra also give information about the conformation since the shift of the

methylene carbons is little influenced by functionalization in para position or at the

hydroxyl groups.59 Methylene carbons between phenol units with anti orientation are

shifted by about 6 ppm downfield compared to their syn equivalents (Figure 1.11).

Tetra-O-alkylated calix[4]arenes usually do not adopt C4v symmetry, as would be

expected from NMR data. Crystal structure analyses as well as temperature-dependent

NMR experiments in solution60 have shown that the C2v-symmetric conformation,

pinchend cone or flattened cone, is favoured (Figure 1.12). In the pinched cone

conformation two phenol units are coplanar to each other, while the other units are tilted

outwards. The meta and para aryl protons of the subunits that are parallel to each other,

experience an upfield shift caused by the ring current of the opposite phenol ring.61

Figure 1.12. Inversion of calix[4]arenes in cone conformation between C2v-C4v symmetries.

Computational studies confirm that the C2v-symmetric conformation is the

energetically more stable conformation.62 Thus, the C4v symmetry observed in NMR

Introduction 11

spectra is considered to be a transition state between the pinched cone conformers, the

rate of interconversion between these being faster than the NMR timescale.

1.1.3 Inherently chiral calixarenes

The easiest way to synthesize chiral calixarenes is functionalization with chiral

substituents.63 However, due to their three-dimensional structure calixarenes can be

chiral although consisting of achiral phenol units.64 This inherent chirality, first

mentioned by Böhmer,64a was defined by Schiaffino et al.65 as arising “from the

introduction of a curvature in an ideal planar structure that is devoid of symmetry axes

in its bidimensional representation”, or to be more exact “is devoid of perpendicular

symmetry planes in its bidimensional representation” as described by Szumna.66 The

first example of an inherently chiral calixarene was reported by Gutsche et al. (33,

Figure 1.13).46

OAcOAc AcOOAc

OO

O

33

OH

O

O O

OO OO

35

37

OHOH HOOH

O OEt

34

OOH HOO

Br Br

PO

OO

36

OO OO

EtO EtO OEt OEt

38

OO OO

EtO EtO OEt OEt

39

O

Br

HN O

Figure 1.13. Examples of inherently chiral calixarenes.

12 Theoretical Part

One way to introduce inherent chirality in calixarenes in the cone conformation is

asymmetric funtionalization at either the upper67 or lower rim68, or both.69 In addition

asymmetric functionalization can be combined with conformational variation of the

calixarene ring as in calixarene 37.70 Another approach is meta functionalization,

usually achieved by prior functionalization of the para position with an ortho-directing

group,52a as described for calixarene 38 by Reinhoudt et al., or involving intramolecular

ring closure, as reported by Shinkai for calixarene 39.71

1.1.4 Nomenclature

It is common to designate cyclic tetramers of phenol units like 31 and 32 as

calix[n]arenes, with the number in brackets describing the ring size.1a,55 When the

hydroxyl groups are not functionalized the name of the para-substituent is used as a

prefix. With more complex substitution patterns the numbering system according to

IUPAC (Figure 1.14) is used to specify the positions of substituents.

When necessary the conformation of the calixarene is added as a prefix to its name.

Regioisomers of disubstituted calixarenes can be distinguished by the terms proximal or

distal.53 The first means that adjacent phenol units are functionalized, while the latter

means that the substituents are at phenol units opposite each other.

22

21

25

1

24

23

13

12

11

10

9

2716 15

26

1918

17

7 6

5

43

28

20 2

814

OH

OH HOOH

A

B

C

D

Figure 1.14. Numbering of the parent calix[4]arene.

1.2 Goal of Research

This thesis deals with the synthesis and functionalization of calixarenes and can be

divided into two main topics.

Introduction 13

The first objective is the synthesis of inherently chiral calixarenes that consist of

phenol units being part of anellated ring systems. Extending and functionalizing the

electron-rich calixarene cavity should provide access to tailor-made hosts for molecular

recognition. The calix[4]monophenanthrene 40 has previously been synthesized in our

group by oxidative photocyclization of strylcalix[4]arenes (Figure 1.15).72 Preliminary

studies have shown that polysubstituted styrylcalix[4]arenes undergo transannular

[2+2] cycloaddition yielding the cyclobutane-bridged calix[4]diphenanthrene 41.73

Figure 1.15. Previously synthesized calix[4]monophenanthrene 40 and [2+2] cycloaddition

product 41.

This competing reaction has to be suppressed in order to synthesize higher

homologues of the calixphenanthrenes. Furthermore, it will be investigated if the first

cyclization influences the orientation of the successively formed phenanthrene units.

As an alternative approach to calixphenanthrenes and its derivatives as well as

calix[4]arenefluorenones, palladium-catalyzed cyclizations are going to be investigated

(Figure 1.16).

Additionally, calix[4]triphenylenes should be available from acid-catalyzed

rearrangement of spirocalixarenes 46 (Scheme 1.3). The latter as well as biphenylcalix-

arene 45 have been synthesized by our group with R being pyridyl substituents.72a,74

Figure 1.16. Envisaged anellated calixarenes.

14 Theoretical Part

Scheme 1.3. Acid-catalyzed rearrangement of spirocalixarene 46 to calix[4]triphenylene 47.

Preliminary studies have been made to replace the basic pyridyl with benzyl or benzoyl

groups, resulting in loss of the substituents upon Suzuki reaction to biphenylcalixarene

45.73 Therefore, the reaction conditions of the Suzuki reaction are to be adjusted and

suitable reaction conditions for the formation of the spiro-compound and its subsequent

rearrangement to the triphenylenes to be established.

The second objective is to enlarge the calixarene cavity at the upper rim with

N-heteroarenes. Sterically demanding substituents at the heteroarene should lead to the

orientation of the nitrogens towards the inside of the cavity, acting as endo-oriented

coordination sites in addition to the π-cavity. Molecules like that should be able to

complex transition metals in the cavity. The tetrazinecalix[4]arene 48 and its subsequent

Diels–Alder reaction to calixarene 49, containing eight endo-oriented nitrogens, is the

primary goal (Scheme 1.4).

Scheme 1.4. Synthesis of calixarene 49 with endo-oriented N-coordination sites.

15

2 Multifold Photocyclizations of Styrylcalix[4]arenes

2.1 Calix[4]arenes with anellated subunits and [2+2] cycloaddition

products

Calix[4]arenes containing anellated subunits are rare and often inherently chiral due to

their functionalization in meta position of the phenolic unit (Chapter 1.1.3).

Calix[4]naphthalenes are probably the best-known examples, which are usually

prepared by stepwise procedures from suitable fragments (Figure 2.1).51,75,76 The

indenol derivative 52 was also obtained via a stepwise synthesis by Böhmer et al., while

tetrahydronaphtol derivative 51 was isolated in 20 % yield by condensation of the

starting material with formaldehyde in alkaline solution.51 Gutsche et al. reported the

calixarenes 53-55, which were synthesized by 1,4-conjugate additions to

calix[4]monoquinones.52c

Figure 2.1. Examples of calix[4]arenes with anellated subunits.

Figure 2.2. Calix[4]arenes with anellated subunits obtained by intramolecular reactions.

16 Theoretical Part

Calix[4]naphthalene 56 and the cyclic ether 57 were obtained by intramolecular

reactions of para-substituted tetrapropoxycalixarenes (Figure 2.2).77

Our group successfully prepared the first calix[4]phenanthrene 40 by irradiation of

styrylcalix[4]arene 58 with iodine and potassium carbonate in benzene in 89 % yield

(Scheme 2.1).72 Studies of the mechanism have shown that basic reaction conditions are

crucial to prevent acid-catalyzed cleavage of an intermediary enol ether to the linear

tetramer 59 (39 %) in addition to the formation of 40 (22 %).

Scheme 2.1. Photocyclization of Monostyrylcalix[4]arene 58 in presence of base and without

(route a or b).

Photocyclization of distyryl- 60 and tetrastyrylcalix[4]arene 62 under the optimized

reaction conditions, however, did not yield the desired calixphenanthrenes but the

transannular [2+2] cycloaddition products 61 and 41 (Scheme 2.2).73,78 In fact,

syntheses of ladderanes from functionalized [2.2]paracyclophanes reported by Hopf et

al. are in accordance with these results.79 Mattay et al. also attempted the

photocyclization of 62, concluding from mass spectra that the reaction took place on

only two positions.77

The cyclobutane-bridged calixarene 61 was the only product obtained analytically

pure from the reaction mixture in 37 % yield. Additionally, two only poorly resolved

fractions were isolated by HPLC. The 1H NMR spectra of both compounds showed a

diagnostic signal for the bay-region proton of a phenanthrene unit at around 8.6 ppm.

Based on the integration of the respective NMR signals, the compounds are presumably

calixmonophenanthrene 63, which has a molecular ion peak at m/z = 794 in the FAB

mass spectrum, and the desired calixdiphenanthrene 64 (Figure 2.3).

Multifold Photocyclizations of Styrylcalix[4]arenes 17

Scheme 2.2. [2+2]-cycloaddition products 61 and 41 formed during photolysis of

styrylcalix[4]arenes 60 and 62.

Diphenanthrene 64 was unfortunately only obtained as a minor by-product in about

6 %, while approximately 25 % of the partially cyclized product 64 were formed. The

overall ratio of compounds 61, 63 and 64 was determined to be 6:4:1.

Figure 2.3. Minor products of the photolysis of styrylcalix[4]arene 60.

A crystal structure of calixarene 61 surprisingly showed a partial cone conformation

(Figure 2.4), which would be minimally favoured over the cone conformation by

0.8 kcal mol-1 according to semi-empirical PM3 calculations. However, since the inter-

conversion between these two conformations is prevented by the propoxy groups, the

obtained crystals presumably do not represent the bulk material, but a minor impurity

18 Theoretical Part

not detectable by NMR. Indeed, the 13C NMR spectrum before the crystallization shows

no signals at about 37 ppm, which would indicate an anti orientation of the adjacent

phenol units (Chapter 1.1.2). The 1H NMR spectrum reveals that calixarene 61 is fixed

in a pinched cone conformation due to the bridging cyclobutane. This results in an

extraordinary upfield shift of the m-aryl protons of the substituted phenyl units to

δ = 5.50 and 5.86 ppm.

Figure 2.4. Crystal structure of cyclobutane-bridged calixarene 61 in the partial cone

conformation.

2.2 Synthesis and photocyclization of a proximal distyrylcalix[4]-

arene

Since [2+2] cycloaddition between two adjacent styryl units should not be possible, the

proximal distyrylcalix[4]arene 65 was synthesized (Scheme 2.4). Introducing

functionalities at the lower rim of just two phenyl units of a calixarene, usually to

reduce the reactivity of these rings in order to make substitution at the upper rim of the

unsubstituted units more favourable, is a commonly used method.49a,80

While selective 1,3-functionalization is often easily achieved in good yields, direct

1,2-functionalization at calixarenes is more difficult and often results only in moderate

yields. Several methods for 1,2-functionalization at the lower rim were described in

literature (Scheme 2.3). Reinhoudt et al.,81 for example, observed that the proximal

substituted product is an intermediate in tetrapropylation of calixarenes with sodium


hydride and propyl iodide in DMF. Based on this, Harvey et al.80c reported direct

propylation under the same conditions to result in 45 % of dipropoxycalixarene 66 after

2 h. However, attempts to reproduce this reaction under varying reaction conditions

gave only tetrapropoxycalixarene or no reaction at all.78a

Scheme 2.3. Proximal difunctionalizations at the lower rim known from literature.

Other known lower rim 1,2-functionalized calixarenes are the 25,27-di(3,5-

dinitrobenzoyl)-26,28-dihydroxy-calix[4]arene (70) in the partial cone conformation

and the 25,26-dibenzoylcalixarene 69, both of which were synthesized by

transesterification of the corresponding 1,3-substituted compounds in good yields―81

% and 90%.80c Although first distal substitution is necessary, which adds a reaction

step, especially the benzoylcalixarene proved to be interesting. Indeed the benzoyl

group is easily removable and thus used as protecting group in the synthesis of mono-80b

and dibromated78a,80c calixarenes, respectively. However, the transesterification is

sensitive to the amount of base used, and Harvey et al. reported that it does not occur

when more than one equivalent sodium hydride is used. Accordingly, attempts using

sodium hydride as dispersion in mineral oil (60 %) failed to yield the desired 1,2-

dibenzoylcalixarene 69.

Shimizu et al.82 reported the synthesis of 25,26-dipropoxycalixarene via hydrogenation

of the corresponding allyl ether in 99 % yield as well as the direct preparation of the

25,26-dibenzylcalixarene 71 in 60 %. As reported yields for the 1,2-functionalized allyl

20 Theoretical Part

ether are moderate,81,83 the dibenzylcalixarene was prepared (Scheme 2.4). However,

stirring parent calixarene 32 with sodium hydride and benzyl bromide in acetonitrile

yielded only up to 47 % of the required calixarene 71. Tetrabenzylcalix[4]arene and

monobenzylcalix[4]arene were isolated in varying yields up to 32 % and 6 % along with

traces of the distal substituted calixarene and starting material. The best and fastest

method to isolate the desired proximal dibenzylcalixarene 71 from larger experiments

was found to be dry-column chromatography. Starting with petroleum ether/toluene 1:1

and increasing the ratio of toluene in 10 % steps, pure toluene finally elutes the pure

product. The by-products were usually not completely separated from one another and

have to be purified further.

Scheme 2.4. Synthesis of 5,11-distyrylcalix[4]arene 65.

The dibenzylcalixarene 71 was submitted to bromination with N-bromosuccinimide in

2-butanone as described in literature to yield 86 % of compound 72.82 Subsequent

removal of the benzyl groups was easily achieved by treatment of 72 with aluminium


chloride in toluene at 0 °C to afford 85 % of 5,11-dibromotetrahydroxycalixarene 73.

The 1H NMR spectrum shows two broad signals for the methylene protons at δ = 3.49

and 4.18 ppm, characteristically for calixarenes with free hydroxyl groups (spectrum,

see p. 216).80c

Propyl groups at the lower rim were introduced under standard reaction

conditions81,49b,84 and gave the proximal dibromotetrapropoyxcalixarene 74 in an

excellent 94 % yield. Transformation to the diformylcalixarene 75 in 45 % yield was

achieved by lithiation of the 5,11-dibromo compound and subsequent treatment with

DMF in analogy to the method used for preparation of the 1,3-functionalized

diformylcalixarene.85 Alternatively, synthesis of the proximally substituted

diformylcalixarene was described by Casnati et al.86 using Gross formylation (Scheme

2.5). In that case tetrapropoxycalixarene 76 is treated with SnCl4 and Cl2CHOCH3.

However, the reaction yields a mixture of proximal and distal diformylcalixarenes 75

and 78 from which the 1,2-functionalized compound can be isolated by reduction to the

alcohol, separation of the same and subsequent reoxidization. The detour over the

alcohol is necessary since the diformylated isomers are inseparable by chromatography.

Consequently, this method was not considered to provide a superior route.

Scheme 2.5. Alternative synthesis of proximal diformylcalixarene 75 by Gross formylation.86

Wittig reaction of the diformylated compound with benzyltriphenylphosphonium

chloride yielded 95 % of the distyrylcalixarene 65. Due to the mixture of possible E/Z

isomers the signal pattern for the bridging methylene protons in the 1H NMR spectrum

22 Theoretical Part

Figure 2.5. Partial 1H NMR spectra of 5,11-distyrylcalixarene 65, recorded at 200 MHz in

CDCl3. Top: mixture of E/Z isomers, bottom: sample isomerized with iodine.

is rather complex with six superimposed signals for the equatorial and seven for the

axial protons (Figure 2.5). Isomerization of a NMR sample with iodine in the heat87 led

to a simpler spectrum, especially in the aliphatic region, showing only three doublets for

equatorial protons and one at δ = 4.46 ppm for the axial ones. In the unisomerized 13C NMR spectrum eight different peaks appear between δ = 156.18 and 157.18 ppm for

the tertiary aromatic carbon atoms substituted by propoxy groups, indicating that all

possible isomers were formed. A signal at m/z = 796 in the FAB mass spectrum

unambiguously identified styrylcalixarene 65.

The proximal disubstituted distyrylcalixarene was irradiated according to the standard

photolysis conditions with iodine and potassium carbonate in benzene. Purification by

flash chromatography yielded 67 % of cyclization products. From 235 mg material

subjected to HPLC three different compounds were isolated, which is consistent with

the number of expected diasteroisomers (Scheme 2.6). The molecular ion peak at

Scheme 2.6. Photocyclization of proximal distyrylcalix[4]arene 65.


m/z = 792 present in the FAB mass spectra of all three compounds, confirms that the

calixphenanthrenes have been formed. Semiempirical PM3 calculations revealed that

the diastereoisomer 81c should be favoured compared to structures 81b and 81a with

about 3.4 and 10.6 kcal mol-1, respectively. However, 81a was clearly identified as the

main product by one- and two-dimensional NMR experiments as well as a crystal

structure analysis (Figure 2.6).

Figure 2.6. Crystal structure of proximal calix[4]diphenanthrene 81a.

These findings suggest that attracting π-π interactions predominate steric repulsion in

the first cyclization. Although 81a is a meso compound by its configuration, the steric

demands of the phenanthrene units pointing towards each other result in an asymmetric

conformation of the molecule. Accordingly, the 1H and 13C NMR spectra show a large

number of signals and there are four different sets for each of the propyl groups,

bridging methylene groups and the aryl units. The existence of four different subunits

and the crystal structure confirm the chirality of 81a.

The diagnostic signals for the Phen-5-H appear at δ = 8.70 and 7.61 ppm, respectively

(Figure 2.7). The phenanthrene, tilted towards the cavity, experiences anisotropic

effects from the other phenanthrene unit and exhibits a 1.03 ppm upfield shift for its

Phen-5-H as well as an even stronger paratropic shift for the corresponding Phen-6-H,

which is found as a triplet at δ = 5.71 ppm. Its Phen-1-H is assigned to a singlet at

δ = 6.00 ppm. The upfield shift of this signal and those of an unsubstituted aryl unit

prove that these units are tilted towards each other (rings B and D) and the molecule is

fixed in a pinched cone conformation. The meta proton facing the phenanthrene unit

exhibits the strongest paratropic shift of about 1.3 ppm to δ = 5.30 ppm. Accordingly,

the protons of the adjacent methylene bridge also experience an upfield shift of about

24 Theoretical Part

5.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.6ppm

5.30

5.71

5.76

5.80

6.00

6.16

6.23

8.00

8.70

HmH5

H8

H1'

Hp

HaxHeq

H6'Hm'

Figure 2.7. Partial 1H NMR spectrum of 81a, recorded at 600 MHz in CDCl3.

0.3 ppm to 3.04 and 4.26 ppm. Notably, the two methylene protons at the bridge

between the phenanthrene units exhibit an extremely large downfield shift of about

2 ppm, especially in the case of the equatorial proton, and appear at δ = 5.76 and

5.81 ppm. In addition, they exhibit a somewhat enlarged geminal coupling constant of

J = 15.9 Hz compared to the normal 13.5 Hz.

The number of signals in the NMR spectra exhibited by the second compound isolated

by HPLC indicates a plane of symmetry, which would be only in agreement with

structure 81b. Indeed, there are only two sets of signals each for the propoxy carbons

and the phenyl carbons attached to the oxygen atoms in the 13C NMR spectrum,

confirming two different aryl units. In addition, the three signals for the bridging

methylene carbons at δ = 30.54, 30.89 and 31.33 ppm as well as the three sets of

doublets, identified by coupling in the two-dimensional NMR spectra, are in accord

with the proximal difunctionalization of the calixarene. The diagnostic phenanthrene

signal at δ = 8.78 ppm in the 1H NMR spectrum integrates to two protons, further

evidence that both phenanthrene units have been formed. The relative upfield shift of

the m-aryl protons, δ = 5.84 and 6.26 ppm (∆ ≈ 0.8 and 0.3 ppm), indicates a pinched

cone conformation. Furthermore, these signals as well as the Phen-1-H protons at

δ = 7.06 ppm are broadened, suggesting an equilibrium of the two conformations with

coalescence at room temperature. Again the meta aryl proton and the protons of the

methylene group opposite the phenanthrene unit exhibit the strongest upfield shift to

δ = 5.84 (∆ 0.8) or δ = 2.90 (∆ 0.6) and 4.28 (∆ 0.2) ppm, respectively.

The NMR spectra of the third compound obtained by HPLC shows rather complicated


NMR spectra and the large number of signals again implies high asymmetry. Since the

third expected stereoisomer 81c should exist in a racemic mixture with its enantiomer

this is no surprise. The molecular ion at m/z = 792 and the diagnostic signal for the

phenanthrene-5-H at δ = 8.73 ppm with an integral of two protons, strongly suggest that

it is compound 81c with both phenanthrene units pointing in the same direction. For the

bridging methylene units four sets of doublets appear in the 1H NMR spectrum. The

signals at δ = 4.52 and 4.66 ppm exhibit the large 1.1 ppm downfield shift expected for

the equatorial methylene protons in the bay-region of the phenanthrene units, while their

axial partners appear at δ = 4.94 and 5.31 ppm, ∆ = 0.4 and 0.8 ppm, respectively. The

relative upfield shift of a third set, δ = 3.04 and 4.38 ppm, indicates that this bridge is

opposite one of the phenanthrene units. The fourth set shows no remarkable shift with

peaks at 3.41 and 4.73 ppm. The 13C NMR spectrum shows signals for four different

propyl groups and three signals for the aryl carbons attached to the oxygen, one of

which consists of two superimposed peaks for the PhenC–O. Broad signals at δ = 6.39

and 7.49 ppm again indicate a dynamic process of the different pinched cone

conformations. Due to this as well as the asymmetry of the molecule a complete

assignment of the NMR signals was not possible.

2.3 Prevention of the [2+2] cycloaddition by steric hindrance

In order to suppress the transannular [2+2] cycloaddition of opposite styryl units by

steric hindrance, an additional methyl group at the stilbene moiety was introduced.

First, the modified benzyltriphenylphosphonium bromide 84 had to be prepared as

depicted in Scheme 2.7. The first step involved hydrobromination of styrene (82)

according to a literature method,88 affording (1-bromoethyl)benzene 83 in 88–99 %

yield after distillation in vacuo. Subsequent conversion to compound 84 involving

procedures described in literature89,90 resulted in yields lower than 50 % (Table 2.1).

Scheme 2.7. Synthesis of benzyltriphenylphosphonium bromide 84.

26 Theoretical Part

Table 2.1. Reaction conditions for the synthesis of 1-phenethyltriphenylphosphonium

bromide 84.

Entry Solvent Time Yield

1 benzene 24 h 44 %a

2 ethyl acetate 24 h 45 %b

3 toluene 24 h 62 %

4 toluene 3 d 88 % a yield according to literature 80 %89, b yield according to literature 78 %90

After optimizing the reaction conditions, benzyltriphenylphosphonium bromide 84 was

finally obtained in 88 % yield by refluxing 83 with triphenylphosphane in toluene for

three days in a screw-cap flask.

Diformylcalixarene 7885 was subsequently transformed to the corresponding

distyrylcalixarene 85 in 41 % yield under Wittig conditions (Scheme 2.8). Compound

85 seems to be formed almost exclusively as the E/E isomer. The 1H NMR spectrum is

in fact much less complicated compared to the corresponding distyrylcalixarene 60

without the additional methyl groups at the styryl moiety. Signals of the bridging

methylene protons of the minor isomers exhibit an upfield shift compared to the E/E

isomer, which shows the respective signals at δ = 3.19 and 4.50 ppm. A 1:10 ratio was

determined from the proton NMR. The newly introduced methyl groups give slightly

broadened singlets at δ = 1.89 and 2.12 ppm. Another broad singlet at 6.53 ppm,

assigned to the alkene-H, shows coupling to the singlet of the meta aryl protons of the

substituted subunit at 6.69 ppm. The protons of the unsubstituted ring give a triplet at

δ = 6.64 ppm with J = 7.5 Hz and a doublet at 7.67 ppm with J = 7.4 Hz. A molecular

ion peak at m/z = 824 in the FAB mass spectrum also identifies the product.

Consequently distyrylcalixarene 85 was submitted to photolysis and gave an

inseparable mixture of calix[4]bisphenanthrenes 86a and 86b in 20 % yield after HPLC

(Scheme 2.8). The FAB mass spectrum shows a peak at m/z = 820 which is in

accordance with the molecular ion. The diagnostic signals for the Phen-5-H appear as

doublets at δ = 8.57 and 8.60 ppm in the 1H NMR spectrum. Although the proton NMR

of the mixture is rather complicated, some signals could be assigned to either of the

diastereomers with the help of HMQC and HMBC correlations (Figure 2.8).


OO OO

O O

(E/Z)(E/Z)

OO OO

OO OO OO OO

+

78

86a and 86b(20 %; 1:1.1)

84, -78 °C -> rt, 16 h

nBuLi, THF,45 min, -78 °C;30 min, rt

85 (42 %)

I2, K2CO3,benzene, Ar,hv, 18 h

Scheme 2.8. Synthesis and irradiation of distyrylcalix[4]arene 85.

1.12

1.00

0.54

1.00

1.00

1.68

Figure 2.8. Partial 1H NMR spectrum of a mixture of 86a and 86b in a ratio of 1:1.1, recorded at

400 MHz in CDCl3.

28 Theoretical Part

Isomer 86a has two different subunits while its diastereomer 86b has three.

Accordingly, two different phenanthrene units (A’, A) and three different unsubstituted

units (B’, B and C) are to be expected for the mixture. The 13C NMR spectrum indeed

shows five different peaks each for the carbon atoms of the propoxy groups as well as

the aryl carbons attached to the oxygen. The latter give two different signals at 159.55

and 159.69 ppm assigned to the phenanthrene subunits of the different isomers.

Furthermore, there are three peaks for the corresponding atoms of the unsubstituted aryl

units at δ = 154.57, 154.88 and 155.32 ppm in a 1:2:1 ratio. Therefore, the middle signal

must belong to the two equivalent aryl units (B’) of 86a and the HMBC spectrum shows

coupling to the meta aryl protons of this ring. They appear as doublets at δ = 5.33 and

6.03 ppm with the p-ArH triplet at δ = 5.94 ppm. The signal at 5.33 ppm exhibits the

expected anisotropic upfield shift of about 1.3 ppm caused by the adjacent phenanthrene

unit. The corresponding m-ArH of the diastereomer 86b appear at δ = 5.12 ppm as a

doublet, exhibiting an even larger shift, indicating that both phenanthrene units point

towards one aryl ring. The proton in para position of the aryl unit gives a signal at

δ = 5.64 ppm, while the protons of the opposite aryl ring appear as a multiplet at lower

field between 6.26-6.31 ppm, obviously not influenced by the phenanthrenes.

Integration of the two different sets of signals reveals a ratio of the two diastereomers

86a: 86b of roughly 1:1.1. Crystals of 86a, with both enantiomers in the unit cell, were

obtained from ααα-trifluorotoluene/methanol, confirming the pinched cone

conformation of the molecules (Figure 2.9).

Figure 2.9. Crystal structure of calix[4]diphenanthrene 86a with both enantiomers in the unit

cell.


Scheme 2.9. Synthesis of tetrastyrylcalix[4]arene 88.

Encouraged by the successful suppression of the [2+2] cycloaddition

tetrastyrylcalixarene 88 was prepared by Wittig reaction of the tetraformylcalixarene 87

with benzyltriphenylphosphonium bromide 84 in 64 % yield (Scheme 2.9). A molecular

ion peak at m/z = 1056 in the FAB mass spectrum identifies compound 88. Again one

conformation of the stilbene units is preferred and relatively simple NMR spectra are

obtained. The methyl group of the main isomer appears at 1.96 ppm in the 1H NMR and

17.3 ppm in the 13C NMR spectrum.

Irradiation of tetrastyrylcalixarene 88 resulted in a complex mixture of products. The

crude product was submitted to flash chromatography repeatedly, but no pure

compound was isolated. Diagnostic phenanthrene signals above 8 ppm were observed in

several of the obtained 1H NMR spectra.

3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.89.0ppm

Figure 2.10. Top: Calixdiphenanthrenes 86, bottom: One fraction obtained from the photolysis

of tetastyrylcalixarene 88. Spectra recorded at 200 MHz in CDCl3.

30 Theoretical Part

The spectrum depicted in (Figure 2.10) resembles the calix[4]diphenanthrenes 86.

Another fraction, however, showed a peak at m/z = 1052 in a FAB mass spectrum

indicating that a maximum of two phenanthrene units has been formed. The mass would

also be in accord with a cyclobutane-bridged diphenanthrene like 41. Indeed, several

spectra show peaks between 5.5 and 6.0 ppm as well as around 50 ppm in the 13C NMR

spectrum, similar to the cycloaddition products.

2.4 Conclusion

Introducing steric hindrance at the styryl moiety successfully suppressed the

transannular [2+2] cycloaddition, giving a mixture of the calix[4]diphenanthrene

stereoisomers 86a and 86b. Since the stereoisomers were formed approximately in a 1:1

ratio, apparently no regioselectivity is induced by the first cyclization.

In the case of proximal disubstitution the photocyclization proceeded smoothly,

yielding all possible diastereoisomeric calixdiphenanthrenes, but favouring the sterically

overcrowded and thermodynamically disfavoured isomer. According to NMR as well as

X-ray crystal structure data the calixphenanthrenes prefer a pinched cone conformation

with the sterically demanding phenanthrene units pushed outwards.

However, the yields are only low to moderate and photolysis of a modified

tetrastyrylcalix[4]arene 88 resulted in a complex mixture of steroisomers. The

separation of these mixtures is already difficult in the case of the lower homologues.

Moreover, steric crowding seems to prevent complete cyclization of the tetrasubstituted

starting material. Cycloaddition might be favoured over the ring closure even for the

modified tetrastyrylcalixarene, as remaining styryl units get close to each other due to

the pinched cone conformation the calixdiphenanthrene adopts. Calixtetraphenanthrenes

do not seem to be accessible by this route, especially without a method to control the

regioselectivity of the reaction.

31

3 Anellated calixarenes by dehydrohalogenation

3.1 Introduction

Since the multiple oxidative photocyclization of calixarenes resulted in only moderate

yields and the purification of products proved to be difficult and time-consuming, an

alternative route to anellated rings at the calixarene framework was sought. The central

problem in any other synthesis is the intramolecular C–C bond formation in the meta

position of a phenol unit.

Scheme 3.1. Different routes to C–C bond formation depicted as intramolecular reaction.

The classical approach to link two aryl units would be by traditional transition-metal

catalyzed cross-coupling reactions like Suzuki,91 Stille,92 Negishi93 or Kumada94

(route a), Scheme 3.1).95 All these methods require prefunctionalization of both

coupling partners or reaction sites as usually aryl halides and an organometallic species

are employed. The latter can be difficult to prepare and are often problematic in terms of

stability and compatibility with functional groups. Besides, the necessary

prefunctionalization steps generate additional waste to the stoichiometric amount of

metal waste created in the coupling step. Moreover, in the case of calixarenes

functionalization of the position meta to the alkoxy group is not possible, thus excluding

this approach for the intramolecular C–C bond formation.

32 Theoretical Part

Route b) as depicted in Scheme 3.1 would provide the best way, economically and

ecologically, to synthesize biaryls as both coupling partners are simple arenes.

However, oxidative coupling processes like these are thermodynamically unfavoured

and problematic concerning regioselectivity as the substrates usually have several C–H

bonds which might react. Nevertheless, some examples are known in literature, for

instance the synthesis of Mukonine 90 (Scheme 3.2) or the intermolecular coupling of

indoles with benzene, both reported by Fagnou et al.96,97

Scheme 3.2. Pd(II)-catalyzed intramolecular oxidative coupling to Mukonine 90.

In recent years, investigations have focused on direct arylation reactions (route c),

Scheme 3.1), in which only one coupling partner needs prefunctionalization.98 The

organometallic species is usually substituted for a simple arene which is coupled with

an aryl halide under transition metal catalysis. Since functionalization of the meta

position in a calixarene is thus unnecessary, this method was chosen for the calixarenes.

As catalysts for direct arylation reactions palladium, ruthenium or rhodium species

are commonly used and a broad range of ligands has been employed. The nature of the

ligand, however, greatly varies depends on the scope of the reactions. Usually the

coupling reactions are carried out in polar aprotic solvents such as DMA, DMF or NMP

under addition of an inorganic base. As the prefunctionalized species aryl bromides,

chlorides, iodides and tosylates can be used respectively, though metal salt additives are

often necessary in reactions with aryl iodides.99

Figure 3.1. Intermediates for the electrophilic aromatic substitution pathway (left) and for the

concerted metalation-deprotonation pathway (right).

Anellated calixarenes by dehydrohalogenation 33

In the first step of the mechanism an oxidative addition of the transition metal into the

aryl halide occurs. For the C–C bond forming step, however, various models have been

proposed. An electrophilic aromatic substitution pathway (SEAr) has been favored

especially for electron-rich heteroarenes.102 Experimental and computational studies by

Echavarren et al. and Fagnou et al. provided evidence that simple and electron-deficient

arenes are more likely to react by a concerted metalation-deprotonation pathway

(CMD), where the ligated base abstracts the proton (Figure 3.1.).100,101,104b The exact

mechanism may highly depend on the respective substrates and reaction conditions

used.

One of the early examples of direct arylations was reported by Ames and Opalko with

the intramolecular reaction to dibenzofurans like 92 as depicted in Scheme 3.3.

Scheme 3.3. Synthesis of dibenzofuran 92 employing 10 mol% Pd(OAc)2 and 1.2 eq base.

Electron-rich heteroarenes have been successfully employed in inter- and

intramolecular direct arylations (Scheme 3.4).102

Scheme 3.4. Reaction of an indole with iodobenzene.

Simple arenes are less nucleophilic and ortho-directing groups are often used to

facilitate the reaction as aryl-transition metal interactions are weak (a, Scheme 3.5).103

The use of a palladium-pivalic acid co-catalyst system, where the pivalate ion acts as

“proton-shuttle”, has also been proved to be useful for the direct arylation of simple

arenes or heteroarenes (b, Scheme 3.5).104

34 Theoretical Part

Scheme 3.5. a) Direct arylation with an amide directing group. b) Use of palladium-pivalic acid

co-catalyst system in the direct arylation of benzene.

Examples where one catalyst is employed to perform different types of catalytic

reactions in a one-pot procedure are also known. Fagnou et al., for example, reported

the tandem catalysis reaction depicted in Scheme 3.6, where a Heck reaction is followed

by direct arylation and subsequent hydrogenation.105

Scheme 3.6. Tandem catalysis comprising Heck reaction, direct arylation and hydrogenation.

Direct arylations have been also applied to the synthesis of bowl-shaped PAHs like

the corannulene depicted in Scheme 3.7. 106,107

Scheme 3.7. Double direct arylation to 1,2-Dihydrocyclopenta[b,c]dibenzo[g,m]-corannulene

106.106


Scheme 3.8. Inter- and intramolecular decarboxylative coupling.109a,c

Carboxylic acids provide an interesting alternative to aryl halides as the carboxy group

acts as a leaving group in decarboxylative biaryl synthesis (Scheme 3.8).108,109

Mattay et al.77,110 were the first to report successful intramolecular direct arylation at a

calixarene (Scheme 3.9), using reaction conditions optimized by Fagnou et al.99

Scheme 3.9. Intramolecular direct arylation at a calixarene.

An alternative to transition metal-catalyzed couplings are photoinduced ring closures.

Moorthy et al.111 reported the synthesis of diversely substituted fluorenones by

photolysis (Scheme 3.10).

Scheme 3.10.Synthesis of fluorenone 114 by photoinduced ring closure.

36 Theoretical Part

Several promising reaction conditions for the intramolecular direct arylation were to

be evaluated at model compounds before applying them to the synthesis of anellated

calixphenanthrenes and -fluorenones.

3.2 Phenanthrene model compounds

In order to find suitable reaction conditions for the intramolecular direct arylation at

calixarenes, the easily accessible model compound 118 was synthesized (Scheme 3.11).

2-Bromophenylacetic acid (115) was converted to the corresponding acid chloride

116 according to a literature method112 in quantitative yield and used in the subsequent

Friedel–Crafts acetylation of 2,6-dimethylanisole (117) without further purification.

Ethanone 118 was obtained in 94 % yield by using reaction conditions reported by

SanMartin et al.113 for the corresponding compound without methyl groups. Substitution

in para position to the methoxy group is verified by a 2 H singlet at δ = 7.73 ppm in the 1H NMR spectrum. The carbonyl group shows a peak at δ = 195.8 ppm in the 13C spectrum as well as a peak at 1684 cm-1 in the IR spectrum. Furthermore, the mass

peak at m/z = 333 in the FAB spectrum also confirms the formation of 118.

Scheme 3.11. Synthesis of ethanone model compound 118.

First, cyclization of 118 (Scheme 3.12) was attempted using Pd(OAc)2 (5 mol%),

tetrabutylammonium bromide (2 eq) and potassium carbonate (8 eq) in DMF, similar to

conditions described in literature.114 Neither heating to 70 °C for 5 days nor to 100 °C

for 2 days in a screw-capped flask produced the desired compound 119. Only traces of

the dimeric phenanthrene 120b were detected in the 1H NMR spectra.


Scheme 3.12. Attempted palladium-catalyzed cyclization of 118; a: 24 h, 145 °C b: 3 d, 170 °C.

Only starting material was recovered when the reaction conditions were changed to

PdCl2 (5 mol%), PCy3·HBF4 (2 eq per Pd) in DMA with DBU (2 eq) as base for 24 h at

145 °C,106 as described for the synthesis of PAHs (Scheme 3.7). Likewise conditions

reported by Ames et al. for cyclization of 2-bromobenzophenone―employing

Pd(OAc)2 (10 mol%), sodium carbonate in DMA and heating to 170 °C overnight―

failed to produce the product.115

Very promising seemed the reaction conditions optimized by Fagnou et al.,99 which

employed Pd(OAc)2 (5 mol%), PCy3·HBF4 (2 eq per Pd), potassium carbonate (2 eq) in

DMA, usually at 130 °C for 24 h (hereafter referred to as the ‘usual conditions’). These

conditions were applied to a wide range of substrates and are compatible with aryl

bromides as well as chlorides and iodides (Scheme 3.13). However, reaction of 1 mmol

of ethanone 118 employing these conditions resulted in dimerization after 24 h at 145

°C. Dihydrophenanthren 120a was isolated in 19 % yield, whereas phenanthrene 120b

was produced in 38 % yield. Both compounds were identified by their mass peaks at

m/z = 505 [M+H]+ for 120a and m/z = 503 [M+H]+ for 120b, leading to the conclusion

that dimers had been formed. In the 1H NMR spectrum of dihydrophenanthrene 120a

the additional protons appear as a 2 H singlet at δ = 5.47 ppm with the corresponding

carbon at δ = 48.9 ppm.

38 Theoretical Part

Scheme 3.13. Reaction conditions established by Fagnou et al. and examples of the compounds

synthesized.99

When the reaction was heated to 170 °C for 3 d, phenanthrene 120b was obtained in

8 % yield as well as 23 % of an unidentified compound. The latter shows peaks at

m/z = 511 [M+Na]+ and 488 [M+H]+ in the FAB mass spectrum. Interestingly, the NMR

spectra are almost identical to those of phenanthrene 120b (Figure 3.2). However, both

the 1H as well as the 13C NMR spectrum show two different methyl groups at δ = 2.12

and 2.18 ppm with the respective carbons at δ = 15.9 and 16.3 ppm. The singlet of 120b

at 7.44 ppm splits into two signals for the other compound 120a, resulting in an

additional peak at 7.46 ppm. Noteworthy is also a peak at 157.7 ppm in the 13C NMR

spectrum, indicating an aromatic carbon with a free hydroxyl group. Thin-layer

chromatography of the different substances in PE/EtOAc 2:1 shows a spot with

Rf = 0.58 for 120b and one with Rf = 0.41 ppm for the other phenanthrene, which shows

the latter is more polar than 120b. These findings suggest that 120c has been formed by

partial dealkylation of 120b (Scheme 3.12), which would also be consistent with the

observed mass and integration of the 1H NMR spectrum (Figure 3.2).

For the formation of phenanthrene derivatives 120a-c two molecules of 118 obviously

undergo Ullman-type coupling followed by coupling of enolates and reductive

elimination.

In an attempt to suppress dimerization, the reaction was carried out in dilute solution,

c = 0.07 M instead of 0.2 M, at 130 °C for 24 h. According to the 1H NMR of the crude

product again the two dimers 120a and 120b had been formed approximately in a 1:1

ratio and were therefore not further purified.


Figure 3.2. Partial 1H NMR spectra of phenanthrendimer 120b (top) and an unidentified

compound, presumably 120c, recorded at 200 MHz in CDCl3.

Even if the Ullman-type dimerization could be successfully suppressed, it is still

questionable if the envisaged cyclization would take place. Miura et al.116 report that

ketone 121, formed by previous α-arylation, does not undergo ortho-arylative coupling

to the cyclic ketone 122 (Scheme 3.14). Instead arylation takes place at an intermediary

enolate oxygen leading to benzufuran 123. Accordingly, 119 would probably undergo

α-arylation as well as oxygen arylation yielding a benzofuran.

Scheme 3.14. Oxygen arylation leading to 2,3-diphenyl-2,3-dihydrobenzofuran 123 as reported

by Miura et al.116

40 Theoretical Part

Scheme 3.15. Reduction of ethanone 118 and subsequent protection of the alcohol 124.

To decrease the acidity of the methylene protons, ketone 118 was reduced to the

corresponding alcohol 124 with sodium borohydride in THF, yielding 87 % alcohol

after 24 h reflux (Scheme 3.15). A 1 H doublet of doublet assigned to the proton at the

carbon bearing the hydroxyl group at δ = 4.92 ppm and the corresponding carbon at δ =

73.3 ppm in the 13C NMR spectrum confirm the formation of the alcohol. The alcohol

was protected with trimethylsilyl chloride to yield 74 % of 125.117 The methyl groups at

the silane appear at δ = −0.19 ppm in the 1H NMR spectrum and δ = −0.24 ppm in the

carbon NMR. Cyclization using again the usual conditions for 3 days at 170 °C did not

give the desired product 126. Instead, the desilylated dehalogenation products 127 and

128 were obtained in 56 % and 28 % yield, respectively (Scheme 3.16).

Scheme 3.16. Attempted cyclization of Silane 125: 5 mol% Pd(OAc)2, PCy3·HBF4 (2 eq per

Pd), 2 eq potassium carbonate, DMA, 170 °C, 3 d.

Removal of the carbonyl group by Wolff–Kishner reduction118 yielded 5-(2-Bromo-

phenethyl)-2-methoxy-1,3-dimethylbenzol (129) in 71 % (Scheme 3.17). The NMR

spectra verify the reduction as the methylene groups appear as two 2 H multiplets,

which are ‘roof effect’, at δ = 2.80 and 3.00 ppm with the carbons at δ = 35.8 and

38.7 ppm. Applying standard cyclization conditions successfully gave 69 % of


dihydrophenanthrene 130. The 1H NMR shows only a 1 H singlet at δ = 6.95 ppm for

the proton meta to the methoxy group as well as two different signals for the methyl

groups at δ = 2.32 ans 2.55 ppm. The molecular ion at m/z = 238 in the EI mass

spectrum also confirms the formation of 130.

Scheme 3.17. Wolff–Kishner reduction of ethanone 118 and subsequent intramolecular direct

arylation to dihydrophenanthrene 130.

3.3 Syntheses of calix[4]phenanthrene derivatives

Friedel–Crafts acetylation at calixarenes has been reported to yield tetrasubstituted

calixarenes. Usually dichloromethane or nitrobenzene are employed as solvents and

aluminium chloride as the Lewis acid to yield the para-substituted products in moderate

to good yields.119

Selective monofunctionalization by Friedel–Crafts reactions at calixarenes is

problematic.120,121 Matt et al. prepared the monoacetyl- and diacetylcalixarene by

Friedel–Crafts acetylation by presequent introduction of two propoxy groups at the

lower rim.121 Thus only the free phenol units, which are more reactive, were acetylated

in nitrobenzene at room temperature using one and two equivalents of aluminium

chloride and acetylchloride, respectively.

Dipropoxycalixarene 131 was reacted accordingly with acetyl chloride 116 for 2 h at

room temperature in dichloromethane (Scheme 3.18). After flash chromatography using

PE/EtOAc and subsequent recrystallization from DCM/MeOH about 13 % of the

desired product 132 were isolated, still slightly impure. The 1H NMR spectrum shows a

characteristic singlet for the methylene protons adjacent to the carbonyl group at

42 Theoretical Part

Scheme 3.18. Friedel–Crafts acetylation of dipropoxycalix[4]arene 131.

6.44

3.92

3.74

4.42

3.27

2.26

3.37

6.09

2.08

4.00

1.52

1.32

1.99

2.16

3.46

3.99

4.28

4.38

6.76

6.92

7.04

7.23

7.61

7.80

9.16

Figure 3.3. 1H NMR spectrum of Bisethanonecalix[4]arene 132, recorded at 200 MHz in CDCl3.

δ = 4.38 ppm (Figure 3.3). Integration of the NMR and a [M+H]+ peak at m/z = 903 in

the FAB spectrum confirm disubstitution.

Modelled on the protocol by Matt et al., monosubstitution of tetrapropoxycalixarene

76 was attempted (Scheme 3.19). Subsequent cyclization of 133 would only lead to a

racemic mixture of enantiomers. This would circumvent the difficult separation of

stereoisomers which would be obtained from polysubstituted derivatives. One

equivalent each of aluminium chloride and the benzoyl chloride 116 in dichloromethane

were employed. A solution of the acetyl chloride was added dropwise to a suspension of

aluminium chloride and calixarene in dichloromethane over a period of two hours at

room temperature. However, only 25 % of the desired product 133 were obtained under

these reaction conditions while 22 % tripropoxycalixarene 134 were formed (Scheme

3.19).


Scheme 3.19. Synthesis of calixarene 133.

Bromophenylacetylcalixarene 133 was identified by one- and two-dimensional NMR

spectroscopy. The 1H NMR spectrum shows the methylene group next to carbonyl as a

2 H singlet at 4.14 ppm. In addition, the proton next to the bromo substituent appears as

a doublet of doublets at 7.57 ppm. Monosubstitution is verified by a 2 H singlet at 7.21

ppm assigned to the aryl protons of the substituted phenol unit. The signal pattern

observed for the propoxy groups as well as the bridging methylene groups in both the

proton and carbon NMR spectra also confirms monosubstitution. The carbonyl group

appears at 195.6 ppm and the adjacent methylene carbon at 45.3 ppm in the 13C NMR

spectrum. Moreover, the FAB mass spectrum shows the [M+H]+ peak at m/z = 789,

which is consistent with compound 133.

Adding a suspension of aluminium chloride to a solution of the other starting

materials, again over a period of two hours, resulted in the formation of 15 % of 133

and increased 29 % tripropoxycalixarene. Additionally, about 32 % of the starting

material was recovered. When the same reaction was carried out in nitrobenzene 16 %

133 and 24 % 134 were obtained, respectively. The yields being about the same as in

the reaction performed in dichloromethane, nitrobenzene showed no advantage besides

completely dissolving the aluminium chloride.120 Dichloromethane might be preferred

because it can be easier removed.

Various attempts to synthesize 133 by lithiation of monobromocalixarene80b 135 with

n-butyllithium and different reactions times did not yield any product (Scheme 3.20).

When warmed to room temperature overnight after addition of acetyl chloride 116 only

starting material was recovered quantitatively, suggesting the lithiation failed. Further

attempts yielded only tetrapropoxycalixarene 76 after reaction at room temperature for

two or three hours, respectively.

44 Theoretical Part

Scheme 3.20. Attempted synthesis of 133 by lithiation: 1. THF, nBuLi, –78°C, 45 min; 2. acetyl

chloride 116, –78 °C to rt overnight or room temperature for 2 h and 3 h,

respectively.

Similar to the synthesis of model compound 118, tetrapropoxycalixarene 76 was

reacted with 1.6 eq AlCl3 and 2.7 eq acetyl chloride 116 per position under reflux. Only

the tetrasubstituted calixarene 136 was isolated in a very low 8 % yield (Scheme 3.21).

The NMR spectra confirm the symmetry of the molecule with a singlet at 4.10 ppm

assigned to the methylene protons adjacent to the carbonyl group and the corresponding

carbon at 45.4 ppm in the 13C NMR. The carbonyl groups cause a signal at

δ = 195.5 ppm, as well as a strong carbonyl band at 1682 cm-1 in the infrared spectrum.

Scheme 3.21. Synthesis of tetrasubstituted calixarene 136.

In analogy to the Wolff–Kishner reduction of model compound 118, the same reaction

conditions were applied to calixarene 133 (Scheme 3.22). After running the reaction for

1 h 20 min and subsequent purification by multiple flash chromatography about 12 % of

a solid, exhibiting signals of the desired product 137a in the NMR spectra, were

isolated.

An alternative route to calixarene 137a is the reduction of the corresponding

acetylene, which can be prepared by Sonogashira coupling (Scheme 3.23).


Scheme 3.22. Attempted Wolff–Kishner reduction of calixarene 133.

Therefore, monoiodocalixarene 139a was synthesized by transhalogenation of the

corresponding bromide 135 in 36 % yield, modelled on a protocol for

resorcin[4]arenes.122 Monosubstitution is confirmed by the expected molecular ion at

m/z = 718 in the FAB mass spectrum as well as NMR analyses. The iodo-substituted

carbon appears at δ = 86.0 ppm in the 13C NMR spectrum.

OO

n 4-n

Br 1. nBuLi, THF, -78 °C,15 min

2. I2/THF, overnight, rt

OO

n 4-n

I

OO

n 4-n

Br

OOn 4-n

Br

135 (n=1) 139a (36 %)139b (69 %)

141a (75 %)141b (70 %)

137a (84 %)137b (85 %)

Br

Pd(PPh3)2Cl2, CuI,NEt3, 3 d , 80 °C

140

1. p-toluenesulfonylhydrazide, DME, 8 h,85 °C, NaOAc/H2O, with a: n = 1

b: n = 2

138 (n = 2)

2. 6 h, 85 °C

Scheme 3.23. Alternative route to 2-bromophenethyl calixarenes 137.

The acetylene 141a was obtained by subsequent Sonogashira coupling84,123 with 1-

bromo-2-ethynylbenzene (140) in 75 % yield. The Pd-catalyst was generated in situ

from PdCl2 and triphenylphosphine, using 5 mol% Pd-catalyst and 10 mol% CuI per

iodo group according to reaction conditions described previously by our group.123a

46 Theoretical Part

Scheme 3.24. Preparation of 1-bromo-2-ethynylbenzene (140).

Diagnostic are the acetylene carbons at δ = 86.5 and 95.3 ppm in the 13C NMR

spectrum as well as the signal of the C≡C valence vibration at 2010 cm-1 in the IR

spectrum. The FAB mass spectrum shows the molecular ion at m/z = 772.

1-Bromo-2-ethynylbenzene (140) was synthesized from o-dibromobenzene (142) by

Sonogashira coupling with either trimethylsilylacetylene or 2-methyl-3-butyn-2-ol and

subsequent deprotection (Scheme 3.24). Following a literature procedure124 coupling

with the butynol gave product 143 in 86 % yield as brown oil after column

chromatography. In contrast to the literature the catalyst was generated in situ and the

mixture was stirred overnight instead of only 5 h. Deprotection was problematic,

yielding acetylene 140 in only 33 % when refluxed with sodium hydride and distilled at

a water separator to remove acetone.125 In contrast, the silylacetylene 144 was obtained

in 78 % yield, employing the same reaction conditions used to prepare 143, and

deprotected to give very good 85 % of 1-bromo-2-ethynylbenzene (140) following a

literature procedure.126

Calixarene 141a was finally reduced to 137a by treatment with p-toluenesulfonyl

hydrazide.99,127 Under the reaction conditions diimide is generated in situ and

hydrogenates the multiple bond by cis-addition of hydrogen.128 Calixarene 137a was

obtained in a very good 84 % yield. Characteristically the 1H NMR spectrum shows the

methylene protons at δ = 2.60 and 2.79 ppm with the corresponding carbon atoms at

δ = 35.5 and 38.6 ppm in the 13C NMR spectrum. Both the proton and the carbon NMR

show a great number of additional small peaks, indicating either impurities or a

conformational flexibility on the NMR time scale. In fact, elemental analysis is

unexeptionally close to the calculated values with 77.33 % carbon (∆C = 0.02) and

7.10 % hydrogen (∆H = 0.05). Moreover, both the spectra of the substance obtained by

Wolff–Kishner reduction or reduction of the alkine as well as those of the disubstituted


compound 137b show these smaller signals. This strengthens the previous assumption

of conformational flexibility.

The disubstituted calixarene 137b was synthesized accordingly. Hennrich et al.84 and

similarly Friedrichsen et al.129 reported a procedure, which employs

benzyltrimethylammonium dichloroiodate130 and calcium carbonate in a mixture of

dichloromethane/methanol to iodinate the dipropoxycalixarene. Subsequent alkylation

of the free hydroxyl groups would lead to diiodotetrapropoxycalixarene 139b. However,

the first step only gave inseparable mixtures of mono- and diiodinated products as well

as unreacted starting material, even with prolonged reaction times or heating. A

procedure by Dondoni et al.,131 employing NaHCO3 instead of CaCO3 in the iodination

step, was not tested. When the crude product was submitted to the alkylation step, only

about 25 % of compound 139b were obtained. The 1H NMR spectrum still shows

contamination, presumably with the monosubstituted compound. An attempt to

synthesize 139b like the corresponding dibromocalixarene85 by lithiation of the

tetraiodocalixarene and subsequent reaction with methanol, gave only traces of product

according to NMR spectra. Finally, transhalogenation of the bromocalixarene gave the

desired product in 69 % yield (Scheme 3.23).

Sonogashira coupling of the diiodocalixarene 139b gave 141b in 70 % yield. The

product was identified unambiguously by its diagnostic acetylene carbons at δ = 87.0

and 95.0 ppm in the 13C NMR spectrum and the C≡C valence vibration at 2010 cm-1 in

the IR spectrum. Subsequent reduction lead to 137b in 85 % yield. NMR spectra show

the methylene protons at δ = 2.71 and 2.93 ppm with the corresponding carbons at 35.5

and 38.7 ppm.

Both, the mono- and the disubstituted phenethylcalixarene 137a and 137b, were

subjected to the Pd-catalyzed intramolecular direct arylation (Scheme 3.25). Variations

of the usual already used for the preparation of model compound 130 (Scheme 3.17)

were employed.

For the conversion of bromophenethylcalixarene 137a 5 mol% catalyst were used.

Purification by flash-chromatography failed to yield completely pure material, but about

20 % seemed sufficiently pure to obtain a FAB mass spectrum and NMR data. The

mass spectrum shows only the peak at m/z = 694, consistent with the molecular ion. The

NMR spectra confirm that the material is not completely pure as there are clearly more

carbon signals than expected for the racemic mixture of 145.

48 Theoretical Part

Scheme 3.25. Attempted intramolecular direct arylation of calixarenes 137 to calix[4]-

dihydrophenanthrenes.

Figure 3.4. Partial 1H NMR spectra of calix[4]dihydrophenanthrene 145 (top) and calix[4]bis-

dihydrophenanthrenes 146a and 146b (bottom), recorded at 400 MHz in CD2Cl2.


Moreover, two spots are observed in thin-layer chromatography with PE/EtOAC 30:1.

The 1H NMR shows peaks at δ = 2.63 and 2.82 ppm, presumably the hydrogens at the

central ring of the dihydrophenanthrene moiety (Figure 3.4). Coupling to the signals at

around 31 ppm in the HMQC spectrum confirms this assumption, supported by the fact

that the corresponding carbons of the model compound also appear at 30 ppm.

The disubstituted compound 137b was reacted 3 d at 170 °C using 10 mol% catalyst

per group (20 % overall). After flash column chromatography and subsequent

recrystallization from DCM/EtOH, 32 mg (~ 18 %) of material were isolated. The FAB

spectrum shows the base peak at m/z = 796 which is in accord with molecular ion of

compound 146. Moreover, the 13C NMR spectrum shows 4 different peaks for the

propyl groups with signal patterns that strongly resemble the mixture of

calixdiphenanthrenes 86a and 86b (Figure 3.5). Thus the peaks at δ = 10.3 and

23.3 ppm are assigned to the propoxy groups attached to the dihydrophenanthrene units.

The signals at around δ = 11 and 24 ppm in an approximately 1:2:1 ratio belong to the

propoxy groups at the unsubstituted aryl units. Furthermore, the aryl carbons substituted

by the propoxy groups are also in accordance with a mixture of steroisomers 146a and

146b, in ratio presumably about 1:1. Accordingly, there are three signals for the aryl

units at around 155 ppm, in an approximate 1:2:1 ratio, and two signals at 150 ppm for

the dihydrophenanthrene subunits. The hydrogens at the positions nine and ten of the

dihydrophenanthrene ring give multiplets at δ = 2.69 and 2.87 ppm, very similar to the

mono compound 145.

Figure 3.5. Details from the 13C NMR spectrum of bisdihydrophenanthrene 146. Spectrum

recorded at 100 MHz in CD2Cl2.

Interestingly, both the mono- and the disubstituted compound show a 2 ppm upfield

shift of one bridging methylene group to 28.3 and 28.6 ppm, respectively. The

50 Theoretical Part

corresponding protons appear at around δ = 4.10 and 4.45 ppm for both substances,

revealing a strong downfield shift of around 1 ppm for the equatorial hydrogens. These

are presumably the bridging methylene groups in the bay-region of the

dihydrophenanthrene rings. The model compound 130 also exhibited an upfield shift for

the corresponding carbon and a downfield shift for the respective hydrogens compared

to those on the opposite site. Moreover, the upfield shift of signals assigned to the aryl

protons of the unsubstituted units to 5-6 ppm indicates that both 145 and 146 adopt a

pinched cone conformation as already observed for the calixdiphenanthrenes 86. It is

also noteworthy that the 13C NMR spectra of both compounds show small peaks at 35.9

and 39.0 ppm (145) as well as 37.7 and 38.7 ppm (146). These indicate that the reaction

did not go to completion and the isolated material is contaminated with starting material

or, in case if 146, partially cyclized product.

3.4 Synthesis of a fluorenone model compound

Since the palladium-catalyzed cyclization of 2-(2-bromophenyl)-1-(4-methoxy-3,5-

dimethylphenyl)ethanone (118) and its derivatives was unsuccessful (Chapter 3.2), the

corresponding methanones 149 were chosen as a new precursor.

One method to prepare the acid chlorides 148 is by stirring the respective benzoic acid

147 with oxalyl chloride in dichloromethane at room temperature.112b Thus, the

chlorobenzoyl chloride 148a was obtained in 99 % yield and the bromobenzoyl chloride

148b in nearly quantitative yield according to NMR (Scheme 3.26). Alternatively,

reaction with thionyl chloride and DMF in dichloromethane at reflux for three hours led

to 148a in 86–94 %, 148b in 92–98 % and 148c in 81 % yield.

Scheme 3.26. Synthesis of acid chlorides 148 and subsequent Friedel–Crafts acetylation: a)

oxalyl chloride, drop DMF, CH2Cl2, 3.5 h, rt; b) SOCl2 (2.2 eq), DMF, CH2Cl2, 3 h,

reflux.


All acid chlorides were used without further purification in the subsequent Friedel–

Crafts acetylation of 2,6-dimethylanisole (117).113 Chlorophenylmethanone 149a was

obtained in 88 % yield, whereas the corresponding bromide gave slightly better 91 % of

149b. The iodide 149c was isolated in a good 83 % yield. The three compounds were

identified by mass spectrometry and their respective NMR spectra. The

chlorophenylmethanone 149a was identified by its molecular ion at m/z = 274 in the EI

mass spectrum. In addition, the IR spectrum shows the carbonyl band at 1665 cm-1 with

the corresponding NMR signal at 194.7 ppm in the 13C NMR spectrum. For

bromophenylmethanone 149b a [M+H]+ peak at m/z = 319 in the FAB mass spectrum is

observed and the 13C NMR spectrum shows the carbonyl carbon at 195.3 ppm. Another

characteristic signal is the bromo-substituted carbon at 119.6 ppm. The iodo compound

149c shows the corresponding iodo-substituted carbon at 94.4 ppm and the molecular

ion causes a signal at m/z = 366 in the EI mass spectrum.

Table 3.1 summarizes the different conditions that were tested with methanone 149

for the intramolecular direct arylation to fluorenone 151 (Scheme 3.27). Reaction of the

bromide 149b with 10 mol% palladium acetate and potassium carbonate as base

(entry 1) yielded about 34 % of the fluorenone, not completely pure after flash

chromatography. No product was obtained using only 5 mol% Pd(OAc)2 and tri-o-

tolylphosphine as ligand (entry 2). By employing Pd(OAc)2 and tetrabutylammonium

bromide only starting material was recovered (entry 3). Good results were achieved

with 5 mol% Pd(OAc)2 as catalyst, two equivalents tricyclohexylphosphine

tetrafluoroborate per palladium as ligand and potassium carbonate as base in DMA at

170 °C (entries 4–7). The reaction was carried out for 3 days or 24 hours, respectively.

The yields did not increase significantly when the reaction time was prolonged,

indicating that the reaction is completed after 24 hours. Aryl chloride 149a produced

better yields than the corresponding bromide compound 149b, yielding good 74 %

(entry 5). The best yield was obtained when the Bedford catalyst132 150 depicted in

Figure 3.6 was used instead of palladium(II) acetate (entry 8). The reaction was carried

out in DMA/toluene (2:1) with 3 mol% of the catalyst, pivalic acid as co-catalyst and

potassium carbonate as base to yield 90 % of the pure fluorenone 151. Further attempts

following the literature procedures described by Ames and Opalko115 for cyclization of

bromo- or iodobenzophenones (entries 9-11) were only in one case successful. The

fluorenone was obtained in 38 % yield according to NMR, when the bromide 149b was

52 Theoretical Part

Table 3.1. Conditions tested for the intramolecular direct arylation of 149.a,b

Entry starting

material catalyst ligand base yield

1 bromide 149b Pd(OAc)2

(10 mol%) - K2CO3

(1.2 eq) 34 %e

2 bromide 149b Pd(OAc)2 (5 mol%)

o-tolyl phosphine (2 eq per Pd)

K2CO3 (2 eq)

0 %


nBu4Br (2 eq)

K2CO3 (8eq)

0 %


PCy3·HBF4 (2 eq per Pd)

K2CO3 (2 eq)

66 %

5 chloride 149a Pd(OAc)2 (5 mol%)


K2CO3 (2 eq)

74 %



K2CO3 (2 eq)

64 %c

7 chloride 149a Pd(OAc)2 (5 mol%)


K2CO3 (2 eq)

73 %c

8 bromide 149b 150

(3 mol%) PivOH as co-catalyst

K2CO3 (6 eq)

90 %d


- Na2CO3

(1.2 eq) 38 %c,e


PPh3 (2 eq per Pd)

NaOAc (2.5 eq)

0 %c

11 iodide 149c Pd(OAc)2 (10 mol%)

- NMI 0 %c,f

12 bromide 149b photolysis 18 %c,e,g

a Generally all the reactions were carried out only once; b Reactions were carried out in DMA at

170 °C for 3 d if not stated otherwise; c 24 h reaction time; d Bedford catalyst, 1 eq PivOH per

149b, DMA/toluene (2:1), 10 h, 120 °C; e purity estimated from NMR; f NMI is the solvent,

reaction at 190 °C; g in CH3CN

PO O

O

tButBu

tBu

tBu

tBu

tBu

Pd Cl

2

150

Scheme 3.27. Intramolecular direct arylation to fluorenone. Figure 3.6. Bedford catalyst.


reacted with palladium(II) acetate and sodium carbonate for 24 h. Only 18 %

fluorenone, estimated from the NMR spectra, were obtained by photolysis according to

Moorthy (entry 12).111

Sannicolo prepared the yellow fluorenone 151 by intramolecular Friedel–Crafts

acetylation from the corresponding dimethylanisole bearing a phenyl group meta, and

an acid chloride functionalization para to the methoxy substituent (Scheme 3.28).133

Scheme 3.28. Preparation of fluorenone 151 according to Sannicolo.133

1H NMR data of the fluorenone obtained by Pd-catalyzed cyclization are in accord

with those reported in the literature. Additionally, the 13C NMR spectrum shows the

peak assigned to the carbonyl group at 193.7 ppm, which also causes a strong

absorbance at 1707 cm-1 in the infrared spectrum. The successful cyclization is

confirmed by two different signals for the methyl groups, δ = 2.50 and 2.29 ppm as well

as 12.8 and 16.6 ppm. The molecular ion appears at m/z = 238 in the EI mass spectrum.

The UV spectrum shows a strong absorbance at 255 nm and smaller ones at 289, 301,

323 and 336 nm.

With regard to further reaction conditions that might lead to fluorenone 151,

methanones 154 and 156 were synthesized, bearing carboxy groups instead of halogens

(Scheme 3.29).

Scheme 3.29. Syntheses of benzoic acids 154 and 156 by Friedel–Crafts acetylation with

phthalic anhydride (153).

54 Theoretical Part

The synthesis of 154 was initially based on a protocol by Yamato et al.134 in which the

substructure was synthesized at a cyclophane, but starting with a tert-butyl group in

para position of the methoxy group. Only starting material was recovered when the

exact protocol―adding the aluminium chloride solution at 0 °C and stirring at room

temperature for one hour―was applied to 117. The reaction conditions were changed to

refluxing the mixture for one hour after addition of the aluminium chloride solution at

room temperature. Beside unreacted starting material, the benzoic acid 154 was isolated

in 9 % yield. The 13C NMR spectrum shows the carbonyl carbons at δ = 196.6 and

169.7 ppm, the strong bands appear at 1603 and 1669 cm-1 in the IR spectrum.

Using 2,6-Dimethylphenol (155) and applying the same reaction conditions used for

the Friedel–Crafts acetylation with the 2-halobenzoyl chlorides, yielded 49 % of an

unidentified compound. At first sight the 1H NMR seems to be in accordance with the

expected benzoic acid 156 (Figure 3.7). The aromatic signals at 7.66, 7.89 and 8.06 ppm

integrate to a 2:1:1 ratio as expected for the aryl ring bearing the carboxy group.

Moreover, there is only one kind of methyl group and a singlet at δ = 7.10 ppm, which

is assigned to the protons meta to the hydroxyl group. Integration, however, reveals that

this singlet equals only three protons instead of the expected two. Furthermore, the 13C NMR spectrum does only show 12 instead of the expected 13 carbon atoms.

Notably, there is no signal for a keto carbonyl group and the HMBC spectrum does not

show coupling from an expected carbonyl group either. However, a 13C NMR spectrum

obtained in DMSO-d6 exhibited 13 carbon atoms, but also no carbonyl group of a

ketone. The three signals with the largest downfield shift appear at δ = 172.5, 164.9 and

148.3 ppm. The latter is assigned to the carbon bearing the hydroxyl group of a 2,6-

dimethylphenol substructure as the HMBC shows coupling to the methyl groups as well

as the meta aryl protons (Figure 3.8). The other two signals, which could well be

carbons of carboxyl groups, show coupling to a substructure of the phthalic anhydride.

It is also noteworthy that the singlet at 7.10 ppm shows coupling to two different

carbons at δ = 126.3 and 128.9 ppm in the HMQC spectrum (Figure 3.8). The FAB

mass spectrum shows peaks at m/z (%) = 563 (12), 293 (56) and 271 (100). The latter

two are in accordance with the [M+H]+ and [M+Na]+ peaks of the expected carboxylic

acid. The first signal would indicate a dimer of 156 complexing an additional sodium

ion, possible for a carboxylic acid. No plausible empirical formula could be deduced

from the mass spectrum in combination with the elemental analysis, which is consistent

with structure 156, assuming this was the molecular ion. Therefore, it was concluded


that the molecular mass is indeed 270. Since other findings are also in accord with the

carboxylic acid, with the one crucial exception of the missing carbonyl carbon, it is

assumed that the acid 156 is in an equilibrium with its tautomer 157 (Scheme 3.30).

6.38

3.10

2.03

1.01

1.00

2.27

7.10

7.65

7.68

7.88

7.91

8.05

8.07

2.03

1.01

1.00

7.65

7.68

7.88

7.91

8.05

8.07

16.6

126.3

128.9

129.7

130.0

130.7

131.4

131.9

132.0

148.3

164.9

172.5

126.3

128.9

129.7

130.0

130.7

131.4

131.9

132.0

Figure 3.7. Partial NMR spectra of an unidentified compound obtained by Friedel–Crafts

reaction of 2,6-dimethylphenol (155) and Phthalic anhydride (153). Spectra

recorded at 400 and 100 MHz, respectively, in CDCl3. Residual solvent signals are

marked with an asterisk.

56 Theoretical Part

Figure 3.8. Details from the HMBC (left) and the HMQC (right) spectrum of the unidentified

compound (for full cross-peak table see Appendix).

Such ring-chain tautomerism has been reported to occur for 2-benzoylbenzoic acids like

156 and related structures. The position of the equilibrium strongly depends on the kind

and position of substituents at either of the phenyl rings. The complexation of one

molecule of water by 157 is assumed since an 1H NMR spectrum in CDCl3 interestingly

shows a broad peak at about 5 ppm that integrates to 3 H. Further experiments have to

be conducted in order to confirm this assumption.

Another attempt was made to synthesize the anthracene-9,10-dione 159 directly by a

double Friedel–Crafts acetylation from 2,6-dimethylsanisole (117) and phthaloyl

chloride (158) (Scheme 3.31).

Scheme 3.30. Assumed ring-chain tautomerism of carboxylic acid 156 and the pseudo-ester

157.

The FAB mass spectrum shows a base peak at m/z = 403 and it was initially assumed

that the phthaloyl chloride (158) reacted twice with the anisole to give 160. The 13C NMR spectrum, however, does not show a keto carbonyl carbon. Moreover, 14

different signals instead of the 10 expected for 160 appear in the carbon NMR, one of


these unexpectedly at δ = 91.8 ppm. The IR spectrum exhibits a carbonyl band at

1769 cm-1 and a signal at 170.1 ppm in the 13C NMR spectrum is also in accord with a

carbonyl carbon in an ester. Based on these findings structure 161 was assigned to the

compound obtained in 67 % yield. The structure was confirmed by HMQC and HMBC

spectra and is also consistent with the [M+H]+ peak at m/z = 403.

Scheme 3.31. Attempted double Friedel–Crafts acetylation to anthracene-9,10-dione 159.

3.5 Syntheses of calix[4]fluorenones

Intramolecular direct arylation of benzoylcalixarenes 162, substituted by either bromine

or chlorine, under the reaction conditions established for the model compound, should

lead to the corresponding calixfluorenone.

First Friedel–Crafts acetylation of tetrapropoxycalixarene 76 with the benzoyl

chlorides 148 was attempted to synthesize the precursor (Scheme 3.32). Addition of a

suspension of aluminium chloride in dichloromethane to a solution of calixarene and

bromobenzoyl bromide 148b at room temperature over a period of 2 h yielded mostly

unreacted starting material and little tripropoxycalixarene 134 (10 %). Only traces (2 %)

of calixarene 162 were isolated and identified by its [M+H]+ at m/z = 775 and 1H NMR

spectra.

58 Theoretical Part

Scheme 3.32. Friedel–Crafts acetylation at calixarene 76.

Chlorobenzoyl chloride 148a was employed under the same reaction conditions, but

the aluminium chloride was added at an inner temperature of 0 °C. According to NMR

16 % of monocarbonyl 163 were obtained alongside tripropoxycalixarene and recovered

starting material. All isolated compounds were insufficiently pure after flash

chromatography. Repeating the reaction at room temperature produced about 7 % of

163 estimated by NMR. Again starting material and tripropoxycalixarene were obtained

as well.

Prompted by the very low yield, the reluctance to react at all and the occurrence of

ether hydrolysis as a side-reaction, alternative routes to produce the precursor were

investigated.

Scheme 3.33. Attempted synthesis of benzoylcalixarenes 165 and 166 by lithiation of

dibromocalixarene 138 and reaction with bezonitriles 164.

After lithiation of dibromocalixarene 138 with n-butyllithium for an hour at –78 °C

and reaction with 2-bromobenzonitrile (164a) overnight, surprisingly starting material

138 was recovered (Scheme 3.33). This indicated that the lithiation had failed.

Exchanging n-butyllithium for t-butyllithium and warming the mixture to –20 °C during

the lithiation produced the same result. Both times the solution of calixarene 138 in


THF turned yellow upon addition of butyllithium, indicating that the lithiation actually

took place. Furthermore, all the reaction mixtures were dark green the next day, also

when 2-chlorobenzonitrile (164b) was employed. In the latter case a complex mixture

was obtained. The crude product showed at least six spots in thin-layer chromatography

with PE/EtOAc 2:1. Tetrapropoxycalixarene 76 and chlorobenzonitrile were the only

compounds isolated in sufficient purity. Further fractions showed calixarene signals, but

purification was unsuccessful even after multiple flash chromatography. However,

NMR and mass spectra indicated partially hydrolyzed compounds. It is interesting that a

reaction took place with the chlorobenzonitrile, while the dibromocalixarene 138 was

recovered unchanged in reactions with bromobenzonitrile. Moreover, a reference

reaction run parallel to a lithiation where the bromobenzonitrile was used, gave

diformylcalixarene 78 in the usual yield. This suggests that instead of acetylation a

lithium-bromine exchange might take place when the bromo compound 164a is

employed.

Scheme 3.34. Lithiation of dibromocalixarene 138 and reaction with aldehydes 167 or benzoyl

chloride 148a.

Replacing benzonitrile with benzaldehydes 167 (Scheme 3.34) yielded a complex

mixture when bromine was the substituent in ortho position of the aldehyde. Several

fractions obtained after multiple flash chromatography showed signals characteristic for

calixarenes. Interestingly, 6 % of the monosubstituted carbonyl calixarene 162 were

60 Theoretical Part

identified in one fraction and about 9 % of the corresponding disubstituted 165 in

another. Three other fractions seemed to contain some of the desired alcohol 168a or at

least the corresponding monosubstituted compound, as they show signals between 5.5–

6.0 ppm consistent with the proton at the carbon bearing the hydroxyl group. Since this

carbon is chiral, a mixture of stereoisomers would be obtained in the case of the

disubstituted calixarene 168. None of the supposed alcohols, however, could be purified

enough for identification. From the analogous reaction with the chlorobenzaldehyde

167b about 4 % of pure 166 were isolated after crystallization from DCM/MeOH.

Furthermore, about 7 % of the corresponding monosubstituted compound were detected

by 1H NMR spectrometry in a second fraction. Another fraction showed a signal at

δ = 5.83 ppm in the 1H NMR spectrum, indicating that alcohol 168b has also been

formed as a mixture of stereoismers, but further attempts at purification failed.

More of compound 166, about 13 % according to NMR, was obtained when

chlorobenzoyl chloride 148a was employed in the reaction. Another fraction contained

about 20 % of the corresponding monosubstituted calixarene 163 according to the 1H NMR spectrum.

A last attempt, employing a Weinreb amide,135 finally turned out more successful.

Amide 169b was obtained by reaction of chlorobenzoyl chloride 148a with N,O-

dimethylhydroxylamine hydrochloride in 93 % yield after distillation (Scheme 3.35).136

Scheme 3.35. Synthesis of Weinreb amides 169.

Lithiation of dibromocalixarene 138 and subsequent reaction of six equivalents amide

169b gave monochlorobenzoylcalixarene 163 in 33 % and the disubstituted compound

166 in 28 % yield (Scheme 3.36). Just warming the reaction mixture to room

temperature overnight instead of heating to 60 °C slightly decreased the yield. This

route turned out to be quite economical despite the moderate yield. In fact, the crude

product consists only of the two products, which can be easily separated by flash

chromatography, and unreacted amide can be also recovered. The 1H NMR spectrum of

163 shows four partly superimposed doublets for the bridging methylene units at


δ = 3.17 and 4.46 ppm. These as well as a 2 H singlet at 7.01 ppm, assigned to the meta

aryl protons of the substituted phenol units, confirm monosubstitution. The 13C NMR

also clearly shows three different types of phenol units as well as the carbonyl carbon at

194.2 ppm. The FAB mass spectrum exhibits peaks for [M+H]+ and [M+Na]+ at

m/z = 731 and 753, respectively. In comparison, 166 has a peak at m/z = 869 [M+H]+ in

the FAB mass spectrum and NMR spectra indicate symmetry as there are only two

different phenol units. The carbonyl carbon exhibits a signal at 194.3 ppm in the 13C NMR spectrum as well as a strong absorbance at 1666 cm-1 in the infrared

spectrum.

Scheme 3.36. Lithiation of 138 and reaction with Weinreb amide 169b.

Preparation of the Weinreb amide with a bromine in ortho position in analogy to 169b

yielded 169a in 95 % yield (Scheme 3.35). However, only unreacted starting material

was recovered using four equivalents of 169a under the same reaction conditions that

had yielded the chloro compounds 163 and 166. This further supports the hypothesis of

a lithium-bromine exchange when bromo-substituted arenes are employed as

nucleophiles in the lithiation reaction.

Since the bromo compounds were not available by lithiation reactions, once again

Friedel–Crafts acetylation was attempted. This time dipropoxycalixarene 131 was

employed as starting material to induce a difference in reactivity between the phenol

subunits of the calixarene (Scheme 3.37).121

Dipropoxycalixarene 131 was initially reacted with 3.95 equivalents 2-bromobenzoyl

chloride (148b) and 4.8 eq aluminium chloride at room temperature for 25 min. The

disubstituted bromobenzoylcalixarene 171 was obtained in 15 % yield along with 27 %

of the trisubstituted calixarene 172. Consequently, the amount of bromobenzoyl

chloride was reduced to 2.2 equivalents and the reaction was carried out at different

temperatures and with different reaction times to improve the selectivity.

62 Theoretical Part

Scheme 3.37. Friedel–Crafts acetylation of dipropoxycalixarene 131 with bromobenzoyl

chloride 148b.

No clear optimum was observed as the reaction seems to be also sensitive to the

amount of starting material employed (entries 1 and 4, Table 3.2). After 10 min at room

temperature 57 % of the disubstituted 171 and only 3 % of trisubstituted 172 were

obtained, while a smaller experiment yielded 13 % of the monosubstituted 170 and

80 % of 171, but no 172. As might be expected the same reaction time at 0 °C gave

considerably more mono compound 170 (43 %), but also 52 % of 171. When the

reaction was prolonged to 35 min at 0 °C, 25 % monocarbonyl calixarene 170 and 58 %

of the disubstituted 171 were isolated. In addition, traces of 172 were detected in the

NMR spectra.

Table 3.2. Tested reaction conditions for the Friedel–Crafts acetylation of 131 with 2-

bromobenzoyl chloride (148b) (2.1 eq) and aluminium chloride (4.5 eq).

Entry 131

(mmol)

time

(min)

T

(°C) 170 171 172

1 0.69 10 rt 13 % 80 % -

2 1.97 35 0 25 % 58 % traces

3 2.36 10 0 43 % 52 % -

4 4.11 10 rt - 57 % 3 %

An attempt to synthesize 170 selectively by employing only 1.1 equivalents of the

bromobenzoyl chloride 148b for 10 min at room temperature resulted in 22 % of 170

and 41 % 171 beside unreacted starting material. This experiment indicates that the

mono compound cannot be obtained just by reducing the amount of benzoyl chloride

since the monosubstituted compound reacts readily at the second free phenol unit.

Bis(bromobenzoyl)calixarene 171 shows a [M+H]+ peak at m/z = 875 as well as a base

peak at m/z = 183. The latter is the mass of the bromobenzoyl fragment and is also


detected in the FAB mass spectra of 170 and 172. The NMR spectra of 171 confirm its

symmetry, showing a characteristic signal at 9.25 ppm for the free hydroxyl groups and

the carbonyl carbon at 194.6 ppm. Tris(bromobenzoyl)calixarene 172 shows three

different phenol subunits and the signal of the hydroxyl groups experiences an upfield

shift to δ = 8.77 ppm in the 1H NMR spectrum. The mono compound 170 shows two

different peaks for its hydroxyl groups at δ = 8.26 ppm and 9.28 ppm. All three 13C NMR spectra show the brominated carbon at about 119 ppm.

Dipropoxycalixarene 131 was also reacted with 2.1 equivalents 2-chlorobenzoyl

chloride (148a) at 0 °C for 35 min. Thus chlorobenzoyldipropoxycalixarene 173 and

bis(chlorobenzoyl)dipropoxycalixarene 174 were obtained in 35 % and 53 % yield,

respectively (Scheme 3.38). NMR spectra clearly show three different phenol subunits

for 173. Characteristic are again the two signals for the hydroxyl groups at δ = 8.26 and

9.27 ppm as well as the carbonyl carbon at 194.0 ppm. The FAB mass spectrum shows

the [M+H]+ peak at m/z = 647 and the base peak at m/z = 139, which is the chlorbenzoyl

fragment. The disubstituted 174 also shows the fragment at m/z = 139 as well as a

[M+H]+ peak at m/z = 785. NMR spectra confirm the symmetrical substitution of the

molecule with a peak at 9.23 ppm for the hydroxyl groups in the 1H NMR spectrum.

Scheme 3.38. Friedel–Crafts acetylation of dipropoxycalixarene 131.

Standard reactions conditions,72a using sodium hydride and propyl iodide in DMF at

60 °C–70 °C for 2 h, were initially used to achieve tetralkylation of the disubstituted

calixarene 171 (Scheme 3.39). From the reaction mixture cone product 165 (21 %) and

paco product 175 (37 %) were isolated. Besides the only partially alkylated 176 was

formed in about 12 % yield according to 1H NMR spectra (entry 1, Table 3.3). When

reacted overnight at 80 °C with more sodium hydride and 19 equivalents of propyl

iodide per hydroxyl group, the alkylation went to completion to yield 34 % of 165 and

33 % of 175 (entry 2).

64 Theoretical Part

Scheme 3.39. Alkylation of dipropoxycalixarenes 174 and 171.

Table 3.3. Reaction conditions tested for the alkylation of 171.

Entry base RX reaction

time

T

( °C)

cone

165

paco

175 176

1a 5.0 eq

NaH 7.6 eq PrI

2 h 70-80 21 % 37 % 12 %c

2a 6.6 eq

NaH 19 eq PrI

14 h 80 34 % 33 % -

3a

13 eq Na2CO3

14 eq PrI

3 d reflux 77 % - -

4b

13 eq Na2CO3

14 eq PrBr

3 d reflux 39 % - 58 % a DMF as solvent; b CH3CN as solvent; c calculated from NMR spectra.

However, to suppress the undesired change of the calixarene confirmation, reaction

conditions were modelled on a protocol by Bonini et al.137 for the alkylation of

diformyldipropoxycalixarene. Using sodium carbonate in acetonitrile for three days

under reflux and propyl iodide as alkylating agent gave a good 77 % yield of the cone

conformer 165 (entry 3).

Since 165 is the sole product of this reaction, workup is easily achieved by either

treating the crude product with methanol in an ultrasonic bath or recrystallization from

DCM/MeOH.

The original protocol employed propyl bromide under otherwise unchanged

conditions. Following this procedure, however, the alkylation did not go to completion,

yielding 39 % of the tetraalkylated 171 as well as 58 % of the trialkylated 176 (entry 4).


Integration of the signals caused by the hydrogens of the propoxy group for 176 clearly

shows trialkylation, as well as a peak at δ = 6.07 ppm from the free hydroxyl group. The

FAB mass spectra of 165 and 175 confirm that the products are tetraalkylated.

Furthermore, the NMR spectra do not show free hydroxyl groups and integration of the

signals belonging to the propoxy groups also confirms tetraalkylation. Crystals of 165

were obtained from DCM/EtOH and the crystal structure reveals that the substituted

units are coplanar to each other, while the aryl rings are pushed outwards (Figure 3.9).

Figure 3.9. Crystal structure of Bis(bromobenzoyl)tetrapropoxycalixarene 165 in a pinched cone

conformation (disorder of the propyl groups is not sufficiently refined).

The partial cone conformation of 175 is verified by two signals for the bridging

methylene groups at δ = 30.7 and 36.0 ppm in the 13C NMR spectrum. The

corresponding protons exhibit the characteristic pattern of two doublets and a singlet in

a 1:2:1 ratio at δ = 3.10, 3.67 and 4.10 ppm. There are three different sets of signals for

the propoxy groups and thus three different aryl subunits. Two aryl units are substituted

and show different carbonyl carbons at δ = 195.1 and 195.5 ppm. The meta aryl protons

give two 2 H singlets at 7.57 and 7.75 ppm, while the unsubstituted subunits are

identical. The meta aryl protons of the latter appear at 6.28 and 6.94 ppm with the para

proton at 6.47 ppm.

The corresponding chloro compounds were obtained when disubstituted

chlorobenzoylcalixarene 174 was reacted with NaH and propyl iodide at 80 °C

overnight according to entry 2. Cone 166 was isolated in 40 % yield beside 29 % of the

paco calixarene 177b. Traces of 178b were detected in the NMR spectra, but the

66 Theoretical Part

compound was not isolated in its pure form. NMR data of these three compounds show

the same characteristics as their bromo counterparts.

Alkylation of the monosubstituted dipropoxycalixarenes 170 and 173 was also carried

out with sodium hydride and propyl iodide in DMF at 80 °C overnight (Scheme 3.40).

In the case of the bromo compound 33 % of the monosubstituted 162 along with 6 %

partial cone 180 and 27 % trialkylated 179 were isolated.

Bromobenzoyltetrapropoxycalixarene 162 exhibits a [M+H]+ peak at m/z = 775 in the

FAB mass spectrum and NMR spectra clearly show three different phenol subunits. The

complementary partial cone calixarene 180 shows the same mass peak, but the 13C NMR spectrum shows peaks at δ = 30.7 and 36.2 ppm, indicating that a subunit is

trans to the others. That this is the unit bearing the bromobenzoyl substituent was

determined from two-dimensional NMR spectra. The third compound, 179, has a signal

assigned to the free hydroxyl group at 5.99 ppm and integration as well as a [M+H]+

peak at m/z = 733 in the FAB mass spectrum verify trialkylation.

Scheme 3.40. Alkylation of Monocarbonyldipropoxycalixarenes 170 and 173.

Slightly lower yields were obtained from the reaction of the corresponding chlorides.

Cone chlorobenzoylcalixarene 163 was isolated in 24 % yield as well as 2 % of its

partial cone counterpart 182. According to 1H NMR spectra about 16 % of the

trialkylated 181 were also formed. The compound was not characterized further, but

identified by comparison with the corresponding bromo compound 179. Integration of

the proton NMR as well as a peak at 5.99 ppm, caused by the free hydroxyl groups, are

characteristic. Partial cone compound 182 exhibits the characteristic pattern for the

bridging methylene groups with doublets at δ = 3.05 and 4.07 as well as a singlet at

3.68 ppm in the 1H NMR spectrum. The 13C NMR shows the corresponding carbon

atoms at 30.7 and 36.2 ppm, respectively.


Scheme 3.41. Intramolecular direct arylations to calix[4]fluorenones.

Intramolecular direct arylation was attempted with reactions conditions used for the

corresponding model compound 149 (Scheme 3.41). First, cyclization of

chlorobenzoylcalixarene 163 was attempted employing 5 mol% catalyst for 3 d at

170 °C. Mainly unreacted starting material was recovered, which was again submitted

to the reaction, using 10 mol% of the catalyst. NMR spectra indicated that little of

calixmonofluorenone 183 had been formed. When 163 was reacted with 20 mol%

catalyst at 130 °C for 3 days no reaction took place and the crude product was again

reacted under the same conditions, but at 170 °C for a further 3 days. Again traces of

183 were detected in NMR, but could not be obtained in sufficient purity for

characterization. The same applies to an attempt carried out with the corresponding

bromo compound 162 under the exact reaction conditions reported by Mattay et al. The

crude product obtained by photolysis of 162 clearly exhibited product signals in the 1H NMR. Two fractions of the first flash chromatography (silica gel, PE/EtOAc 8:1 to

2:1) were submitted to a second column. A large excess silica gel along with an unpolar

eluent mixture (PE/EtOAc 100:1 to 50:1) was employed. Under these conditions it was

possible to isolate 25 mg (20 %) of the pure calixfluorenone 183. In addition, a further

9 % of the product were detected in NMR spectra, resulting in an overall yield of 29 %.

The material isolated exhibits a [M+H]+ peak at m/z = 695. NMR spectra reveal the

existence of four different phenol units as expected for the cyclized compound (Figure

3.10).

68 Theoretical Part

6.66

6.48

8.67

3.23

4.27

4.15

1.04

4.14

6.00

1.15

1.92

1.03

1.02

0.97

1.00

1.00

0.92

0.95

1.12

1.14

1.85

1.96

1.98

2.12

3.16

3.18

3.25

3.65

3.79

3.98

4.09

4.26

4.33

4.45

4.47

4.53

6.11

6.23

6.92

7.13

7.28

7.45

7.51

7.65

7.88

10.19

10.24

11.26

23.58

23.89

24.16

25.97

31.43

31.58

77.12

77.70

77.77

122.50

122.68

122.71

123.21

124.26

125.74

127.27

127.74

128.29

128.44

128.77

129.46

129.57

132.26

132.75

134.09

134.18

134.94

134.98

137.74

137.76

137.91

155.77

156.07

158.52

165.80

193.73

Figure 3.10. NMR spectra of calixfluorenone 183, recorded at 400 and 100 MHz in CD2Cl2,

respectively.

The carbonyl carbon appears at 193.7 ppm in the 13C NMR spectrum. This carbon

(C6) shows coupling to a doublet at 7.65 (H8) and a 1 H singlet (H4) at 7.51 ppm in the

HMBC spectrum. The latter is assigned to the proton meta to the propoxy substituent at

the fluorenone unit. The bridging methylene carbon (C15) experiences anisotropic

effects from the fluorenone moiety and exhibits a strong upfield shift of 5 ppm to

26.0 ppm. Weak characteristic absorbances at 328 nm and 274 nm as well as a strong

absorbance at 263 nm are observed in the UV spectrum of the yellow fluorenone.

35 14

4

15

OOO O

6

11

10

98

O


When the disubstituted chlorobenzoylcalixarene 166 was reacted with 10 mol%

catalyst for 24 h at 130 °C, 29 % of 184 were obtained as a mixture of both

stereoisomers. However, 7 % of the overall yield were pure isomer 184a, isolated by

column chromatography. The solid shows the characteristic yellow of the fluorenones.

From the other reaction conditions tested with the bromo compound 165 (Table 3.4),

only mixtures of the stereoisomers were obtained. Generally flash chromatography was

insufficient to yield pure material and recrystallization from DCM/EtOH was necessary.

Table 3.4. Tested reaction conditions for the cyclization to calixdifluorenones 184.

Entry starting

material catalyst

a T in °C time yield

1 166 10 mol% 130 °C 24 h 29 %

2 165 10 mol% 130 °C 3 d 23 %b

3 165 10 mol% 150 °C 3 d 31 %b

4 165 10 mol% 170 °C 3 d 12 %b

5 165 5 mol% 130 °C 24 h 46 %b

17 %c

6 165 photolysis 24 h 78 %b

55 % c

7d 165 3 mol% 120 °C 10 h 37 %b

8d 165 3 mol% 120 °C 10 h

76 %b

57 %c

All reactions were carried out only once; a Pd(OAc)2 except for entries 7 and 8 where a Bedford

catalyst 150 was used; b estimated from NMR spectra; c isolated after recrystallization; d PivOH,

K2CO3 in DMA/toluene (entry 7) or DMA (entry 8).

However, when the reaction was carried out in a DMA/toluene mixture (entry 7, Table

3.4), a mixture of the desired fluorenones and starting material was obtained. Separation

by flash chromatography was unsuccessful. According to NMR spectra, the mixture

contained 37 % of the calixdifluorenones and 40 % starting material. The yield

improved to 76 %, estimated from NMR, when DMA was the sole solvent (entry 8).

Satisfying 57 % 184 were isolated after a single flash chromatography and subsequent

recrystallization from DCM/EtOH.

70 Theoretical Part

Photolysis of bis(bromobenzoyl)calixarene 165 in acetonitrile for 24 h (entry 6), was

the only reaction with comparable yields, but the material thus obtained was less pure

even after recrystallization.

The FAB mass spectrum of the isomer mixture of 184 shows the [M+H]+ as base peak

at m/z = 797. NMR data are very similar to those of the calixmonofluorenone 183.

Structure 184a was assigned to the single isolated isomer based on the symmetry

observed in the spectra. Only two different subunits are observed in the NMR spectra;

the signals obtained for the carbons substituted by the propoxy groups are diagnostic.

Isomer 184a shows one peak at 165.1 ppm for the fluorenone unit and a second signal at

155.3 ppm for the unsubstituted ring. As would be expected the steroisomeric mixture

exhibits three different unsubstituted aryl units at 155.0, 155.3 and 155.6 ppm.

In contrast to the calixphenanthrenes and calixdihydrophenanthrenes, the

calixfluorenones 184 do not seem to be fixed in a pinched cone conformation. The

protons of the unsubstituted aryl unit appear as a multiplet at about 6.2 ppm comparable

to the shift observed for the tetrapropoxycalixarene 76.

3.6 Previous studies on calix[4]triphenylenes

As previously reported by our group, dehydration of Bisbiphenylcalix[4]arene 185

yielded 68 % of spiro-calixarene 186 (Scheme 3.42).72a,74 Due to the lack of hydrogen-

bonding that could stabilize the cone conformation, 186 shows fast ring inversion at

room temperature. Time-dependent NMR studies established that 186 prefers a partial

cone structure. Acid-catalyzed rearrangement of spiro-compounds like this should make

calix[4]triphenylenes like 187 available. Plieninger et al.138 reported an analogous

reaction to fluorenonylcyclohexadienones.

Since the basicity of the pyridyl groups might be unfavourable for the acidic

conversion, replacement of these substituents by benzyl or benzoyl groups was

attempted in preliminary studies.78 However, in both cases the new substituents were

lost, or partially lost, during the Suzuki coupling to the corresponding

biphenylcalixarenes (Scheme 3.43).

Therefore, conditions of the Suzuki coupling have to be readjusted to prevent loss of

the lower rim substituents. Besides, the corresponding dipropoxycalixarene is to be

synthesized and submitted to Suzuki coupling. Furthermore, problems occurred in


reproducing spiro-calixarene 186, necessitating investigations into alternative methods

to produce the spiro compound.

Scheme 3.42. Synthesized spiro-calixarene 186 and planned acid-catalyzed rearrangement to

calix[4]triphenylene 187.

188 or 189

OHOH OO

R R

Br Br

OHOH HOOH

191 (42 %)

OHO HOOH

193 (22 %)

O

OHOH HOOH

+

191 (29 %)

OHOH HOOO

192 (6 %)

+

B(OH)2+

190

R = Bn

R = Bz

Scheme 3.43. Suzuki coupling of dibromodibenzylcalixarene 188 or dibromodibenzoyl-

calixarene 189 resulting in loss of R. 10 mol% Pd(PPh3)4, 2 N K2CO3, THF, 20 h,

120 °C.

72 Theoretical Part

Hypervalent iodine(III) reagents139 like (diacetoxyiodo)benzene (PIDA)139 or

[bis(trifluoroacetoxy)iodo]benzene (PIFA)140,141 seem to provide a promising alternative

(Figure 3.11). They are easy to handle, readily available and have low toxicity, while

their reactivity is similar to heavy metal reagents or aniodic oxidations.142

Figure 3.11. The hypervalent iodine reagents PIDA and PIFA.

Oxidation of p-substituted phenols with hypervalent iodine(III) reagents in the

presence of nucleophiles, yields 4,4-disubstituted cyclohexa-2,5-dienones (Scheme

3.44).143 In the intramolecular reaction, spiro-annulated cyclohexadienones comparable

to calixarene 186 are obtained (Scheme 3.45).144

Scheme 3.44. Oxidation of p-substituted phenol 196 and trapping with nucleophile.143a

Kita et al. reported that the reactions proceed with better yields in poorly nucleophilic

protic solvents like the fluorinated alcohols 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-

hexafluoro-2-propanol (HFIP).144c With phenol ethers nucleophilic substitution occurs

in these solvents, leading to biaryl compounds and yields can be improved by addition

of BF3·Et2O (Scheme 3.46). Phenols react with the iodine center in the hypervalent

iodine compound via intermediate 206, while in reactions with phenol ethers a cation

radical intermediate like 207 is generated (Scheme 3.47).145,146


OH O

PIDA, CH3CN,reflux, 4 h

198 199 (30 %)

OH O

PIDA, MeOH, rt

200 201 (50 %)

a)

b)

OH O

PIFA,TFE,-40 °C

202 203 (61 %)

N NCOCF3 COCF3

c)

OMe

Scheme 3.45. Spiro-annulated cyclohexadienones.

Scheme 3.46. p-substituted phenol ether reacting under nucleophilic substitution.

Scheme 3.47. Mechanistic pathways for hypervalent iodine oxidations.

74 Theoretical Part

3.7 Synthesis of a triphenylene model compound

In order to find suitable reaction conditions for the synthesis of the spiro compound,

2,6-dimethylphenol (155) was chosen as precursor for the model compound 209

(Scheme 3.48).

Scheme 3.48. Synthesis of Triphenylene 211.

Winzler et al. reported that bromination of 155 with bromine in glacial acetic acid at

10 °C yielded the brominated compound 208 in 88 % after recrystallization.147 The

initial attempt to reproduce this protocol gave only a 41 % yield after recrystallization.

Using bromine in chloroform the yield was increased to 69 %.148 The EI mass spectrum

showed the molecular ion at m/z = 199 and 1H NMR data were in accord with those

reported by Fischer et al.149 Subsequent Suzuki coupling with 2-biphenylboronic acid

(190) yielded 66 % of phenol 209, using reaction conditions previously established for

the calixarenes.150 NMR data as well as the peak at m/z = 274 from the molecular ion

verify the formation of 209.

Conversion to the spiro compound 210 was attempted using PIFA in various solvents

(Table 3.5). When the reaction was carried out in acetonitrile for 15 min, modelled on a

protocol by Swenton et al.,142a about 28 % product were obtained according to NMR

(entry 1). Only traces of product were detected in the 1H NMR spectra of the reaction in


chloroform (entry 2). When 2,2,2-trifluoroethanol was used as solvent as described by

Kita et al.,144c,151 spiro compound 210 was formed in about 53 % according to NMR

(entry 3). With regard to the poor solubility of most calixarenes in alcohols, different

solvent mixtures were investigated (entries 4 to 6) since also the biphenylphenol 209

exhibited only moderate solubility. Good yields of 210 around 70 % were obtained from

1:3 and 1:1 mixtures of CH2Cl2/CF3CH2OH, respectively. The reaction conditions

originally employed in the synthesis of spirocalixarene 186 failed to yield any product

at all (entry 7).74

Table 3.5. Reaction conditions for the synthesis of spiro compound 210 with PIFA at room

temperature.

Entry reaction time solvent yield

1 15 min MeCN 28 %a

2 20 min CHCl3 tracesb

3 15 min CF3CH2OH 53 %a

4 15 min 1:3 MeCN/CF3CH2OH 28 %a

5 15 min 1:3 CH2Cl2/CF3CH2OH 70 %

6 15 min 1:1 CH2Cl2/CF3CH2OH 73 %a

7b c CH2Cl2, MeNO2 -

a purity estimated from NMR spectra; b detected in 1H NMR spectrum; c 1. CH2Cl2, 15 min, Ar,

2. FeCl3, MeNO2, 40 min, rt.

Spiro compound 210 shows the [M+H]+ base peak at m/z = 273. The diagnostic signal

for the quaternary carbon atom appears at δ = 56.9 ppm in the 13C NMR spectrum and

the carbonyl carbon is observed at 187.9 ppm. The carbons meta to the carbonyl group

give a peak at 144.6 ppm, while the corresponding protons exhibit a singlet at 6.30 ppm

in the 1H NMR spectrum.

Rearrangement of the spiro compound 210 to triphenylene 211 was achieved applying

the protocol by Plieninger et al.,138 whereby concentrated sulfuric acid catalyzes the

reaction at 100 °C in acetic anhydride. Triphenylene 211 was obtained in a very good

92 % yield with a molecular ion at m/z = 314 in the FAB mass spectrum. The 1H NMR

spectrum confirms the asymmetry of the rearranged molecule, exhibiting two 3 H

singlets at δ = 2.42 and 2.76 ppm, as well as a 1 H singlet at 8.37 ppm for the proton

76 Theoretical Part

meta to the ester group. The 13C NMR spectrum shows the carbonyl peak at 169.1 ppm

and a strong carbonyl band also appears at 1749 cm-1 in the IR spectrum.

3.8 Syntheses of calix[4]triphenylenes

To prevent removal of the benzyl groups in the Suzuki coupling, the reaction conditions

were changed from potassium carbonate in THF to sodium carbonate in

toluene/methanol. In addition, the reaction time was reduced to 4 h at only 100 °C

(Scheme 3.49).131,152 Thus, the biphenylcalixarene 212 was synthesized once in 34 %

yield after multiple flash chromatography. The FAB mass spectrum of 212 shows the

molecular ion at m/z = 908. In the 1H NMR spectrum the free hydroxyl groups give a

2 H singlet at 7.56 ppm and the meta aryl protons another 4 H singlet at 6.87 ppm.

Employing the dibromodipropoxycalixarene 213 under the same reaction conditions

resulted in a considerably better 77 % yield of biphenylcalixarene 214. The free

hydroxyl groups appear as a singlet at 8.04 ppm and the protons meta to the hydroxyl

groups give a 4 H singlet at 6.87 ppm.

B(OH)2

213190 214 (77 %)

OO HOOH

Br Br

OO HOOH

Pd(PPh3)4, 2 M Na2CO3,toluene, MeOH, 4 h, 100 °C

OO HOOH

Pd(PPh3)4, 2 M Na2CO3,toluene, MeOH, 4 h, 100 °C

OO HOOH

Br Br

188 212 (34 %)

B(OH)2

190

Scheme 3.49. Synthesis of biphenyldibenzylcalixarene 212 and biphenyldipropoxy-calixarene

214 by Suzuki coupling.


Several attempts to oxidize compound 214 with PIFA, using acetonitrile or

dichloromethane as solvents, showed signs that a reaction had taken place, but only

starting material was recovered and identified. The same applies to reactions carried out

in the solvent mixtures also used in the synthesis of model compound 211.

Identification is complicated by the supposed conformational flexibility of spiro

calixarene 215 also observed for the corresponding dipyridylcalixarene 186.

Scheme 3.50. Attempted oxidation and rearrangement of biphenylcalixarene 214 followed ester

hydrolysis to 217. Only one steroisomer of the calix-triphenylenes is depicted.

Rearrangement to the calixtriphenylene may reduce the flexibility since the free

hydroxyl groups are available for hydrogen bonding. Accordingly, no further attempts

at isolating the spiro compound 215 were made. Biphenylcalixarene 214 was reacted

with PIFA in a 1:1 mixture of dichloromethane and trifluoroethanol at room

temperature for 15 min. After removal of the solvent the crude product was directly

submitted to the rearrangement in acetic anhydride with sulfuric acid (Scheme 3.50).

One fraction obtained after purification by flash chromatography with PE/toluene 1:1

was considered relatively pure. The FAB mass spectrum gives evidence that it is indeed

calixtriphenylene 216, exhibiting a peak at m/z = 915 consistent with [M+Na]+. An

additional peak at m/z = 850 is in accord with the loss of one ester group. The 1H NMR

spectrum clearly differs from the starting material and shows signals around 8.5 ppm

78 Theoretical Part

characteristic for the bay-region protons of the triphenylene moiety (Figure 3.12). The

methyl groups of the acetyl groups give two singlets at δ = 2.36 and 2.38 ppm,

respectively. Other calixarene signals like the bridging methylene groups, however, are

superimposed by a large number of additional signals between 3.0–4.5 ppm. The mass

of signals observed is not surprising considering that a mixture of steroisomers is

formed in the reaction and the product itself is asymmetric. The upfield shift of signals

to the region between 5 and 6.5 ppm, indicate that the compound adopts a pinched cone

conformation since these signals are assigned to the aryl protons of the unsubstituted

rings.

Figure 3.12. 1H NMRs of the assumed calixtriphenylene 216 (top) and the deprotected 217

(bottom), recorded at 200 MHz in CDCl3.

Compound 216 was not further purified and analysed, but submitted to ester cleavage.

After subsequent purification by flash chromatography and recrystallization from

DCM/MeOH, 18 mg (40 %) of a colorless solid were obtained. The molecular ion

observed in the FAB mass spectrum at m/z = 808 is in accord with triphenylene 217.

NMR spectra confirmed that the material is quite pure and approximately a 1:1 mixture

of the steroisomers (Figure 3.12). Again characteristic triphenylene signals are observed

as multiplets at about 8.32, 8.57 ppm and a third at 7.50–7.66 ppm. Coupling in the

HMBC shows that the 1 H singlets of the protons meta to the hydroxyl groups are

superimposed by the 8.32 multiplet and appear at 8.32 and 8.38 ppm. The two singlets

at higher field, δ = 6.68 and 6.78 ppm, do not show cross-peaks in the HMQC and were


assigned to the hydroxyl groups. This was confirmed by the HMBC spectrum as

coupling to the aryl carbons bearing the hydroxyl groups at δ = 154.90 and 154.94 ppm

was observed. The corresponding carbons of the unsubstituted aryl units appear at

δ = 152.8, 153.2 and 153.6 ppm. Three different types of these units are expected for a

stereoisomeric mixture of 217. Consequently, the number of signals as well as their

approximate 1:2:1 ratio confirms that both stereoisomers have been formed. Identical

signal patterns can be observed for the propoxy substituents at these units. It is

noteworthy that two methylene signals experience an upfield shift of about 1–2 ppm to

29.0 and 29.2 ppm due to anisotropic effects from the triphenylene moiety. Comparable

shifting has already been observed in the case of the calixfluorenones (Chapter 3.5).

Furthermore, these two signals exhibit coupling only to a multiplet at 4.75–4.90 ppm,

which consists of several superimposed doublets. These are assigned to the protons of

the bridging methylene groups, indicating that the equatorial protons influenced by the

triphenylene moiety experience a large downfield shift of more than one ppm. For

comparison, the equatorial protons of the other methylene bridges appear at 3.64 and

3.68 ppm, their axial counterparts at 4.46 and 4.49 ppm.

Signals of the unsubstituted aryl units exhibit an upfield shift and it was possible to

distinguish three sets of signals in the H,H-Cosy spectrum (Figure 3.13). In accordance

with the shifts observed for the methyl substituted diphenanthrene 86, the protons of the

aryl ring towards which both triphenylene units are directed (ring B) should experience

the largest shift due to anisotropic effects. Therefore, the signals at 5.69 and about

5.87 ppm were assigned to the meta and para protons of this ring in isomer 217b. In

fact, the muliplets at 5.86–5.89 as well as 6.62–6.68 ppm each consist of a doublet and a

triplet. The latter are the para aryl protons of isomer 217b, the first the meta aryl

protons of 217a. A triplet at 6.24 ppm is assigned to the para protons in isomer 217a.

Practically no shift is observed for the meta aryl protons of ring C in 217b, from

which both triphenylene units are directed away. These exhibit a doublet at 6.91 ppm.

A 1:1 ratio of the stereoisomers 217a and 217b was determined from the 1H NMR

spectrum by integration of the aryl protons.

Since Pd-catalyzed dehydrohalogenation was successfully employed in the synthesis

of the fluorenone model compound an alternative approach to calixtriphenylenes was

developed (Scheme 3.51). Consequently, the bromosubstituted biphenylcalixarene 220

80 Theoretical Part

5.75.96.16.36.56.76.97.0(ppm)

5.6

5.7

5.8

5.9

6.0

6.1

6.2

6.3

6.4

6.5

6.6

6.7

6.8

6.9

7.0

(ppm)

Ha

HbH

c

Hd

He

Hf

Hg

Hf

Hg

He

Ha

Hc

Hb

Hd

OH

OPr

OPr

HOA'

B'

Hc

Hb

Ha

Ha

OH

OPr

OPr

HOA

B

A

C

Hf

Hg

Hf

Hd

Hb

Hc

He

Hd

A'

B'

Figure 3.13. Detail of the H,H-Cosy spectrum of the stereoisomeric mixture 217, recorded at

400 MHz in CDCl3.

had to be prepared by using reverse starting materials in the Suzuki coupling, reacting

the calixareneboronic acid 218 with 2,2'-dibromobiphenyl (219).

The latter was easily prepared according to a literature procedure by Gilman et al.

from two equivalents 1,2-dibromobenzene and one equivalent n-butyllithium at low

temperature.153 2,2'-Dibromobiphenyl (219) was obtained in 88 % yield as colorless

crystals with a melting point of 78-79 °C (lit. 80-81°C) and the molecular ion at

m/z = 312 in the EI mass spectrum.

Synthesis of the calixareneboronic acid in 42 % yield was reported by Larsen et al. by

lithiation of the dibromocalixarene and reaction with trimethyl borate.85 Purification

was achieved by conversion of the crude product into the 1,3-propanediol ester as it was

problematic to purify the crude boronic acid directly. The pure ester was then

hydrolyzed to give pure 218 (Scheme 3.52).

First attempts to reproduce this procedure gave about 50 % of the boronic acid ester, but

with 42 % after hydrolization considerably less than the 71 % reported for this step in

the literature. Furthermore, a pure 1H NMR, which unambiguously verified the

deprotection and purity of the obtained compound, could neither be obtained in

DMSO-d6 nor in chloroform-d1. Since this method was time-consuming and did not

yield satisfying amounts of pure material, another procedure reported by Atwood et al.

was adopted.154 The crude product was sonificated with hexane and filtered to yield


Scheme 3.51. Alternative approach to calixtriphenylenes.

OO OO

(HO)2B B(OH)2

OO OO

Br Br

OO OO

B B

OO OO

(HO)2B B(OH)2O

O OO

1. nBuLi, THF,-78 °C, 15 min

2. 4 eq B(OMe)3,2 h, -78°C to rt

propanediol,benzene

THF/H2O (8:3),0.1 N HCl, reflux, 1h

1. nBuLi, -78 °C,THF, 15 min

2. 19 eq B(OMe)3,overnight,-78°C to rt

3. 4 N HCl, 90 min

218

218 222 (~ 50%)

138

~ 42%

53 %

Scheme 3.52. Synthesis of calixareneboronic acid 218 (left) in comparison to a method

described in the literature (right).

82 Theoretical Part

53 % of supposed 218. The isolated compound was used without further purification in

the Suzuki coupling.

Initially the same reaction conditions used for the corresponding unbrominated

compound were applied―Tetrakis(triphenylphosphine)palladium(0) with 2 N

potassium carbonate in THF for 20 h at 120 °C.72a,150 No product at all was isolated and

the reaction time was prolonged to 3 d. However, the desired biphenylcalixarene 220

was still obtained in only about 11 % yield. Once again the reaction conditions were

changed, using sodium carbonate in toluene/methanol at 100 °C for 5 h.152 After

subsequent flash chromatography and recrystallization from DCM/MeOH 25 % of

220 were isolated. The formation of 220 confirms that the calixareneboronic acid 218

has been obtained in the previous step. However, the low yield might be due to

insufficient purity of the material. Otherwise it should be possible to increase the yield

by further optimization of the reaction conditions.

The FAB mass spectrum depicts a molecular ion at m/z = 1054 in accord with

calixarene 220. In the 1H NMR spectrum slight impurities can be detected and it was

not possible to obtain analytically pure material for elemental analysis. However, a 2 H

doublet assigned to the protons next to the bromo substituent appears at 7.65 ppm. The

existence of two different aryl subunits is also confirmed. The signal pattern of the

peaks for the bridging methylene groups suggests that the molecule adopts an

asymmetric conformation. In accordance with this assumption is the splitting of signals

observed for the protons at the aryl units. The meta aryl hydrogens of the biphenyl

substituted ring appear at δ = 6.88 and 6.97 ppm. Contrary to the expected singlets for

each one, a more complex pattern is observed. Moreover, the HMBC shows coupling

between the two signals. This indicates that the calixarene prefers a structure with the

biphenyl substituent directed to one side of the aryl subunit comparable to the structure

of the triphenylene (Figure 3.14). It would have also been conceivable that one of the

biphenyl moieties is directed into the cavity and the other pointing away from it. There

has been evidence that the monobiphenyltetrapropoxycalixarene without bromo

substituents prefers a comparable structure with its biphenylmoiety inside the calixaren

cavity.72a

However, only two types of subunits can be distinguished. This suggests that the

structure shows conformational flexibility, which might also explain the splitting of the

respective signals. The aryl protons of the unsubstituted phenol units also exhibit

splitting, resulting in more complex signals than the expected doublet and triplet.


Figure 3.14. Possible conformations the bisbiphenylcalixarene 220 might adopt.

The observed upfield shift to δ = 5.50–5.55 for the meta aryl protons and to δ = 5.97–

6.26 for the ones in para position is a sign for a pinched cone conformation of

calixarene 220.

Biphenylcalixarene 220 was subsequently submitted to reaction conditions described

by Müllen et al. (Scheme 3.51).107c The molecular ion at m/z = 892 in the FAB mass

spectrum is in accordance with the triphenylene 221. The 13C NMR spectrum exhibits

signals for five types of subunits, which is the number of subunits expected for the

mixture of stereoisomers The 1H NMR shows the signals characteristic for the

triphenylene moieties as multiplets δ = 7.60, 8.33 and 8.63 ppm. Additionally, two

singlets for the protons in meta position to the propoxy groups appear at δ = 8.36 and

8.42 ppm, respectively. Moreover, the NMR spectra show that indeed a mixture of both

isomers has been formed. The 1H NMR is in fact very similar to that obtained for the

calix[4]diphenanthrene with additional methyl groups 86 (Chapter 2.3). The protons of

the unsubstituted aryl units exhibit distinct signals between δ = 5.0 and 6.5 ppm, which

can be assigned to the three different types of aryl rings (Figure 3.15). The aryl unit of

isomer 221a has two different meta aryl protons, which appear at δ = 5.28 and 6.06 ppm

with the para protons as a triplet at 5.91 ppm. Isomer 221b on the other hand has two

different aryl subunits, each with identical meta protons. Both triphenylene moieties

point towards one of these units, which causes a large upfield shift to 5.04 ppm for the

meta and 5.57 ppm for the para protons. The corresponding signals of the opposite unit,

from which the triphenylene moieties are directed away, give a doublet at 6.38 and a

triplet at 6.27 ppm. Integration of the aryl signals reveals that stereoisomers 221a and

221b have been formed in a ratio of about 1:1.4. The observed upfield shifts are larger

than those for the corresponding dialkylated compound 217. This suggests that

calixarenes 221 prefer a pinched cone conformation with the bulky triphenylene

moieties pushes outwards. In that case, shielding of the aryl protons caused by the ring

84 Theoretical Part

current of the opposite aryl unit results adds to the observed upfield shift. The

calixphenanthrenes have also been shown to adopt a pinched cone conformation and

exhibit similar shifts (Chapter 2.3).

1.44

1.25

0.77

1.01

1.00

0.92

1.46

5.04

5.28

5.57

5.91

6.06

6.27

6.38

Figure 3.15. Aromatic region of the 1H NMR spectrum of the mixture of steroisomers 221a and

221b, recorded at 400 MHz in CDCl3.

3.9 Conclusion

A number of 2-bromobenzoyl- and 2-chlorobenzoylcalixarenes have been prepared by

Friedel–Crafts acetylation after initial attempts failed to yield the desired products. In

order to succeed, it was crucial to employ the dipropoxycalixarene and thus introduce a

difference in reactivity between the different aryl units. Low temperatures and short

reaction times as well as equimolar amounts of the reagents gave good results, albeit

mixtures of mainly mono- and disubstituted compounds. Further optimization of the

reaction conditions might improve the yields and the selectivity of this reaction.

Moreover, the bromophenylacetylcalixarene 132, already obtained in low yield by

Friedel–Crafts acetylation after two hours, and the corresponding disubstituted

compound should also be accessible by employing the optimized conditions with


shorter reaction times. Direct Pd-catalyzed cyclization of 223 to calix[4]-

phenanthrenones 227 seems not be possible due to the α-acidic hydrogens.

The alternative route depicted in Scheme 3.53 could circumvent this problem. First

reduction of 223 to the corresponding alcohol and subsequent protection to 225 with

chloromethylmethyl ether would be necessary. Parisien et al. reported the successful

Pd-catalyzed cyclization of a similar MOM ether.155 However, considering the number

of steps, the overall yield would probably be very low and the product is formed as a

mixture of different steroisomers.

The separation of the stereoisomers obtained in the successful cyclizations to

calix[4]dihydrophenanthrenes 146, calix[4]fluorenones 184 and calix[4]triphenylenes

221 proves to be a crucial problem. Since the stereoisomeric mixtures are inseparable

by normal flash chromatography, it is necessary to employ HPLC. The low solubility of

the calixarenes in eluents usually used for the flash chromatographic separations might

pose a problem. Chiral HPLC columns might be useful as the anellated calixarenes are

inherently chiral.

Both possible isomers seem to be formed in a ratio of about 1:1. This indicates that the

first cyclization does not influence the regioselectivity of the second ring closure.

Similar observations were also made by Barton et al. for the intramolecular direct

arylation to a calixarene containing benzochromene units 57.77

Although several calix[4]arenes containing anellated subunits have been isolated, the

reaction conditions have to be further improved as yields so far have been low. Very

promising seems to be the use of a Bedford catalyst 150 in combination with pivalic

acid co-catalyst. The model compound 151 was obtained in a very good 90 % yield

under these conditions and a first attempt with bis(bromobenzoyl)calixarene 165

yielded the calix[4]difluorenone 184 in a good 60 % yield.

The calix[4]triphenylenes 217 and 221 have been synthesized by two different routes.

In the case of the oxidation of biphenylcalixarenes with PIFA and subsequent acid-

catalyzed rearrangement to 216, it could not be determined what the yields of the

intermediate spirocalixarene 215 are. Its purification and identification was

unsuccessful, probably due to the assumed conformational flexibility of this compound

Alternatively, the intramolecular biaryl coupling of phenol ethers leads directly to

calixtriphenylenes. Kita et al. reported that using PIFA in DCM at low temperatures in

combination with BF3·Et2O yielded the anellated compound 205 (Scheme 3.54).156

86 Theoretical Part

OO HOOH OO HOOH

O O

131 116 132

BrBr

OO OO

O O

223

BrBr

OO OO

OH HO

224

BrBr

OO OO

OMOM MOMO

225

BrBr

OO OO

OMOM MOMO

OO OO

O O

226 227

Br

O

Cl+

Scheme 3.53. Alternative route to calix[4]phenanthrenones 227.

Scheme 3.54. Intramolecular biaryl coupling of phenol ethers with PIFA.


Furthermore, they report that employing heteropoly acids in combination with PIFA

also leads either to biaryl coupling (230) or selectively to spirodienone formation

(228).157 Direct intramolecular biaryl coupling would make the rearrangement and

subsequent ester cleavage unnecessary and save two steps in the synthesis of

calix[4]triphenylenes.

The second route, employing Pd-catalyzed cyclization of the bromobiphenyl-

calixarene 220, also suffers from low yields. One problem is the formation of the

boronic acid at the calixarene, which gave low yields and might also lack sufficient

purity. The reaction conditions of the subsequent cyclization require further

optimization. Similar reaction conditions to those already employed were reported by

Scott et al. and Rabideau et al. for the synthesis of dibenzocorannulenes.106,107a

Nevertheless, the Bedford catalyst/pivalic acid system should be also tested for the

synthesis of calix[4]triphenylenes.

89

4 Syntheses of unsymmetrical tetrazines

4.1 Introduction

1,2,4,5-Tetrazines are six-membered aromatic rings containing four nitrogen atoms.158

Their deep purple color is attributed to an n–π* transition in the visible with a maximum

usually between 510 and 530 nm. Its position is only weakly dependent on the

substituents in 3- and 6-position, contrary to the strong absorption in the UV region

corresponding to a π–π* transition.

Tetrazines exhibit interesting electrochemical as well as optical properties and their

potential applications include energetic materials, active molecules for nonlinear optics

and inclusion in conducting polymers.158b Attempts to include them in supramolecular

structures by synthesis of tetrazine-containing cyclophanes or coupling of tetrazines to

the hydroxyl function of cyclodextrins have also been reported recently.158b,159 The

basicity and coordination ability of the tetrazine nitrogens is low, but esters of 3,6-

dicarboxylic acids and 3,6-bis(pyridyl)-substituted derivatives (bptz or dptz) have

become popular in coordination chemistry (Figure 4.1).160 The 3,3’- and 4,4’-analogues

of bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) have been reported to form complexes with

trimesic acid, which exhibit interesting two-dimensional structures.161

Symmetrically substituted tetrazines can be obtained by the reaction of aromatic nitriles

with hydrazine via imidoethers as reported by Pinner.162 A modified procedure employs

aromatic nitriles, hydrazine and sulfur.163 Both methods yield 1,2- or 1,4-

dihydrotetrazines (Scheme 4.1), which are subsequently oxidized to the 1,2,4,5-

Figure 4.1. Examples of 3,6-disubstituted tetrazines used as ligands.

90 Theoretical Part

Scheme 4.1. Synthesis of dihydrotetrazines from aromatic nitriles according to Pinner162(left)

and a modified procedure (right).

tetrazines, usually by employing nitrous gases or sodium nitrite in combination with

acetic acid.

Synthesis of unsymmetrically substituted tetrazines is more problematic. One method

is the functionalization of certain precursors, e.g., 3,6-dichlorotetrazine, by nucleophilic

aromatic substitution. Thereby, one chlorine is usually readily replaced at room

temperature whereas disubstitution requires harsher conditions.158b Another useful way

to unsymmetrically substituted tetrazines is a stepwise synthesis starting with an acid

chloride 231 and an aryl hydrazide 232 (Scheme 4.2). These react to a diacylhydrazide

233, which can be converted into the corresponding hydrozonoyl chloride 234. From

here, 1,2,4,5-dihydrotetrazines164,165,166 235 as well as 1,2,4-triazoles167 236 are

accessible by reaction with hydrazine or ammonia, respectively.

Scheme 4.2. Stepwise method to synthesize unsymmetrically substituted 1,2,4,5-

dihydrotetrazines or 1,2,4-triazoles.

Functionalization of a calixarene with tetrazine moieties might in itself give

supramolecular structures with interesting optical and electrochemical properties.

However, fixing the nitrogens in an orientation in which they are directed towards the

Syntheses of unsymmetrical tetrazines 91

inside of the calixarene cavity would probably be more effective for the formation of

complexes inside of it.

The electron-deficient tetrazines are well-known diene compounds in inverse electron

demand Diels–Alder reactions.165,168,169,164 Electron-rich dienophiles already react with

tetrazines at room temperature while other dienophiles require higher temperatures. The

first example of the formation of pyridazines by Diels–Alder reaction of tetrazines is the

reaction of 3,6-diphenyl-1,2,4,5-tetrazine with acetylenes to give, for example, 238

(Scheme 4.3), reported by Carboni et al.170

Scheme 4.3. Examples of tetrazines in the inverse electron demand Diels–Alder reaction: 238170,

239169b, 241

169f, 242169a.

Cycloaddition of diphenylacetylene, or other sterically demanding olefins and

acetylenes, to the tetrazine ring would yield tetrapyridazinecalixarenes like 243, in

which the nitrogens should be oriented towards the cavity with the phenyl rings pointing

outwards due to steric reasons (Scheme 4.4). This preoriented, the substituent is

predestined to act as a bis-chelating ligand with the pyridyl nitrogen as additional

coordination site.

92 Theoretical Part

Scheme 4.4. Envisaged Diels–Alder reaction of bistetrazinecalixarene 48 with

diphenylacetylene.

4.2 Syntheses of tetrazine model compounds

Construction of the asymmetric tetrazine moiety was first tested at the 2,6-dimethyl

anisole to find suitable reaction conditions. A method described by Tsefrikas et al.164

seemed promising and the initial synthesis was planned following the reported protocols

(Scheme 4.5).

N

O

NHNH2O

HN

NH

O N

O

Cl

NN

Cl N

ONN

HN NH

N

O

NN

N N

N

O

PCl5, CHCl3,ref lux, 20 h

NH2NH2·H2O,K2CO3, CH3CN,reflux, 25 h

NOx, CH2Cl2, rt

O

OCl

pyridine, 48 h, rt+

244 245 246

247 248(or 1,4-dihydrotetrazine)

249

Scheme 4.5. Initially planned route to asymmetric tetrazine 249.164


The route starts with picolinohydrazide (244) and acyl chloride 245. Acetylation of

the hydrazine gives diacylhydrazide 246, which is then transformed to hydrazonoyl

chloride 247. Subsequent reaction with hydrazine hydrate yields the 1,2- or 1,4-

dihydrotetrazine 248, which is then oxidized with nitrous gases to the desired tetrazine

249.

First, precursors 245 and 244 had to be prepared. For the synthesis of acyl chloride

245, as outlined in Scheme 4.6, methods also described for calix[4]arenes were chosen.

Starting from 2-methoxy-1,3-dimethylbenzene (117) the aldehyde function was

introduced by a Duff–reaction. Aldehyde 250171a,172

was obtained in 85 % yield

employing modified literature procedures.171 Oxidation to the corresponding carboxylic

acid 251173 in excellent 97 % yield was achieved by treatment with sodium chlorite and

sulfamic acid174 upon which the product precipitated from the reaction mixture. The

acid 251 was converted into the acid chloride 245175 with thionyl chloride in

dichloromethane under reflux conditions in a very good 90 % yield.

Scheme 4.6. Synthesis of acid chloride 245.

The picolinohydrazide 244 was obtained as colorless solid with mp 99–101 °C (lit.: 176

100–102 °C) in an excellent 95 % yield by reaction of the ethyl picolinate (252) with

hydrazine hydrate (Scheme 4.7). The yield was even better than the 83 % reported in the

literature.176

Dicarbonylhydrazide 246 was prepared in a good 82 % yield according to a protocol

described by Wang et al.177 for 1,2-dibenzoylhydrazide (Scheme 4.8). The use of

Scheme 4.7. Preparation of picolinohydrazide 244.

94 Theoretical Part

Scheme 4.8. Synthesis of Dicarbonylhydrazide 246.

THF/water and sodium carbonate for 3 h is preferable over the use of pyridine and

longer reactions times as depicted in the original route. Upon addition of hydrazide 244

and sodium carbonate in THF/water to a solution of acid chloride 245 in THF, 246

precipitated from the solution. Extraction with dichloromethane and subsequent

recrystallization of the crude product from ethanol/methanol 4:1 was found to give

better results than collecting the product by filtration. The IR shows bands at 3230 cm-1

and 1643 cm-1 for the NH stretching vibrations and the carbonyl group, respectively.

The NH protons give two 1 H doublets at δ = 9.18 and 10.52 ppm.

Employing the method described by Tsefrikas et al., using PCl5, hydrazonoyl chloride

247 was synthesized.164,165 Initial experiments yielded about 40 % of a yellowish oil,

indicating impurity of the product as 247 was expected to be a solid. All attempts to

crystallize the compound failed. Finally, hydrazonoyl chloride 247 was isolated as a

yellow oil, which solidified upon standing, in 61 % yield.

Tsefrikas et al. also reported a low yield of the hydrazonoyl chloride (36 %) in this

step and observed the formation of the corresponding 1,3,4-oxadiazole in 30 % yield.

However, except for one experiment, when 253 and 247 were isolated in about 35 %

each, only traces of oxadiazole 253 could be detected in the NMR spectra when 246

was employed. Since except for that experiment dry chloroform had been used, the

presence of water might favour the formation of the oxadiazole.178

On the first look, oxadiazole 253 and hydrazonoyl chloride 247 can be hardly

distinguished by their respective 1H NMR spectra (Figure 4.2). However, elemental

Scheme 4.9. Synthesis of hydrazonoyl chloride 247 and oxadiazole 253.


Figure 4.2. Partial 1H NMR spectra of hydrazonoyl chloride 247 (top) and oxadiazole 253

(bottom). Spectra recorded at 400 MHz in CDCl3.

analyses as well as mass spectra with a [M+H]+ peak at m/z = 336 in the FAB mass

spectrum of 247 and a molecular ion at m/z = 281 in the EI mass spectrum of 253

unambiguously identified the different compounds. Moreover, Rf values in PE/EtOAc

2:1 are 0.46 for 247 and 0.18 for 253, the latter appearing blue under UV light. For

hydrazonoyl chloride 247 the carbons bearing the chlorines appear at δ = 143.9 and

144.2 ppm in the 13C NMR spectrum. The corresponding carbons being part of the

oxadiazole ring in 253 show resonances at 163.8 and 165.8 ppm.

Prompted by the low yields of the initial experiments an alternative method was

sought. Taylor et al. reported the conversion of aroylhydrazones 254 into chloroazines

Scheme 4.10. Formation of benzylidenebenzohydrazonoyl chloride 255 as reported by

Taylor.179

96 Theoretical Part

255 utilizing thionyl chloride in toluene (Scheme 4.10).179 However, treatment of 246

with thionyl chloride in dry toluene yielded 88 % of oxadiazole 253 as the sole product.

Indeed, the reaction of hydrazonoyl chlorides with thionyl chloride is one method to

provide 1,3,4-oxadiazoles.178a

Oxadiazole 253 was also formed in about 20 % when reaction conditions, used by

Tsefrikas et al.164 for the conversion of the hydrazonoyl chloride to the dihydrotetrazine,

were applied to hydrozonyl chloride 247 (Scheme 4.11).

Changing the conditions and refluxing 247 with hydrazine hydrate in ethanol for 1 h,

as reported by Hu et al.180 and Sauer et al.,166 followed by oxidation of the crude product

using sodium nitrite in acetic acid161,180a,181 failed to produce the tetrazine. This result

indicates that the dihydrotetrazine was not formed. A mass spectrum obtained from the

crude product further supports this conclusion, showing a peak at m/z = 281, which

hints again at the formation of the oxadiazole 253. Using hydrazine dihydrochloride in

pyridine,182 dihydrotetrazine 248 was obtained in around 40 % after column

chromatography (Scheme 4.11).

Scheme 4.11. Synthesis of dihydrotetrazine 248 and subsequent oxidation to tetrazine 249.

However, fractions obtained by chromatography and identified as product already

exhibited a red colour. This indicates oxidation of 248 to tetrazine 249 in air, yielding a

mixture of both compounds (Figure 4.3). Because of this 248 was submitted to

oxidation without further attempts at purification and characterization.

Tetrazine 249 was finally obtained by oxidation of the dihydrotetrazine 248

employing aqueous sodium nitrite and acetic acid in up to 47 % yield as purple solid.


Addition of diethylether was necessary since the product is formed as a purple solid

upon addition of sodium nitrite and the reaction mixture could not be stirred properly.

The FAB mass spectrum shows the base peak at m/z = 294 for [M+H]+. The tetrazine

carbons give peaks at δ = 163.3 and 164.4 ppm in the 13C NMR spectrum, respectively.

The UV/Vis spectrum shows the absorbance at 528 nm, characteristic for tetrazines.

Attempts to substitute the pyridine used in the synthesis of dihydrotetrazine 248 as

well as conversion of the crude product without complete purification failed. With

acetonitrile instead of pyridine unreacted starting material was recovered. Only trace

amounts of product could be detected by NMR, when small quantities of pyridine in

acetonitrile as the main solvent were employed. Likewise, using the crude product from

the reaction in pyridine directly in the next step after removal of the solvent gave only

traces of the product.

2.53.03.54.04.55.05.56.06.57.07.58.08.59.0ppm

Figure 4.3. 1H NMR spectrum of dihydrotetrazine 248 (bottom) showing traces of tetrazine 249

(top), recorded at 200 MHz in CDCl3.

Since only oxadiazole 253 was formed in the initial attempts to synthesize

dihydrotetrazine 248, the pyridyl substituent was replaced by a phenyl group to examine

if the same problems would occur (Scheme 4.12).

Benzohydrazide (257) was prepared in analogy to picolinohydrazide (244) in almost

quantitative yield as colorless solid with mp 112 °C (lit.176 111–113 °C). Reaction with

98 Theoretical Part

acid chloride 245 yielded 89 % of the dicarbonylhydrazide 258. The product

precipitated from the reaction mixture and was collected by filtration as it exhibited

very low solubility in contrast to the corresponding pyridyl-substituted compound 246a.

The [M+H]+ and [M+Na]+ peaks in the FAB mass spectrum at m/z = 299 and 321,

respectively, confirm formation of the product. The IR band at 3226 cm-1 is attributed to

NH stretching vibrations and the hydrogens attached to the nitrogens give a broad

singlet at δ = 10.38 ppm. Furthermore, the 13C NMR spectrum shows two different

carbonyl groups at 165.0 and 165.3 ppm.

O

HN

NH

O

O

Cl

NN

Cl

O

NN

HN NHO

NN

N NO

PCl5, CHCl3,ref lux, 20 h

258 (89 %)

260 (17 %)

261262 (51 %)

O

OMe

O

NHNH2

NH2NH2·H2O,ref lux, 18 h

257 (99 %)256

245, Na2CO3, THF,H2O, 3 h, 0 °C

O

259 (65 %)

O

NN

+

NH2NH2·H2O,EtOH, ref lux,30 min

SOCl2, toluene,ref lux, overnight

NaNO2 (10 %),CH3COOH, Et2O,0 °C, 15 min

Scheme 4.12. Synthesis of tetrazine 262.

When the carbonyl compound 258 was reacted with phosphorus pentachloride in

chloroform, a mixture of the desired hydrazonoyl chloride 259 and the oxadiazole 260

was obtained in 65 % and 17 % yield, respectively. However, a larger experiment gave

reverse yields with only about 18 % of the chloride, but 65 % oxadiazole. The reaction

could either be sensitive to scale-up or this again indicates sensitivity to water.


Chloroform was dried over aluminium oxide, which might have been insufficient for the

larger reaction.

The compounds were identified by their respective [M+H]+ peaks at m/z = 335 for the

hydrazonoyl chloride 259 and 281 for the oxadiazole 260 in the FAB mass spectra. The 13C NMR spectrum of 259 showed peaks at δ = 144.1 and 144.3 ppm for the carbons

bearing chlorine, while the oxadiazole carbons give signals at δ = 164.5 and 164.7 ppm.

Additionally, in TLC the oxadiazole gave a spot which appeared blue under UV light,

which was also observed for the corresponding pyridyl compound 253.

By employing thionyl chloride in toluene again only oxadiazole 260 was formed in

about 70 % yield as shown by the 1H NMR spectrum. According to literature reports,

the oxadiazole can be converted to the dihydrotetrazine under the same conditions that

would be used for the hydrazonoyl chloride.183 However, only starting material was

recovered unreacted when 260 was refluxed with hydrazine hydrate in ethanol for

30 min,180 or heated to 40–50 °C for three hours in acetonitrile183 (Scheme 4.12).

Figure 4.4. 1H NMR spectra of Phenyldihydrotetrazine 261 (bottom) and the

pyridyldihydrotetrazine 248a (top), recorded at 200 MHz in CDCl3.

100 Theoretical Part

Upon treating 259 with hydrazine hydrate in ethanol the solution turned red,

indicating formation of dihydrotetrazine 261 and subsequent oxidation to tetrazine 262.

The precipitate was collected by filtration and washed to yield 52 % of almost colorless

material. The 1H NMR was not contaminated with the corresponding tetrazine and

shows strong similarities to the impure material obtained of the corresponding

pyridyldihydrotetrazine 248a (Figure 4.4). Furthermore, the UV/Vis spectrum shows

only one absorbance at 251 nm. The molecular ion appears in the FAB mass spectrum

at m/z = 294 as the base peak. The hydrogens attached to the nitrogen atoms give a

broad 2 H singlet at 7.12 ppm and the NH stretching vibrations cause a peak at

3268 cm-1 in the infrared spectrum.

When 261 was reacted with sodium nitrite in acetic acid and diethyl ether at 0 °C a

purple precipitate was formed immediately and 41 % of tetrazine 262 were isolated. The

[M+H]+ peak at m/z = 293 in the FAB mass spectrum as well as the characteristic

absorbance at 514 nm in the UV/Vis spectrum confirm the identity of 262. The 13C NMR spectrum shows the carbons of the tetrazine ring at δ = 163.8 and 163.9 ppm,

respectively.

4.3 Synthesis of tetrazine moieties at calix[4]arenes

The first steps of the synthesis have been described for calixarenes in literature. The

diformylcalix[4]arene 78 has been converted to the corresponding carboxylic acid85,184

263 (Scheme 4.13) in 90 % yield by Ungaro et al.184, using chloroform/acetone (1:1).

Various other formylcalixarenes have been transformed by similar procedures.60c,185,186

Since the calixarene would not be soluble in water or water/acetone, as used for the

model compound, the reactions are carried out in chloroform/acetone, usually in 1:1 or

1:3 ratios. The procedures generally employ more sodium chlorite and sulfamic acid as

well as longer reaction times and give yields about 80 % or higher.

However, when the protocol by Ungaro et al. was applied to the diformylcalix[4]arene

only about 30 % of dicarboxycalixarene 263 were obtained. The yield did not improve

on running the reaction for two days and consequently the reaction conditions were

modified. The same amounts or reagents used for the model compound, 1.2 equivalents

sodium chlorite and 1.7 equivalents sulfamic acid, were employed and the concentration

was increased to c = 0.06 mol/l from c = 0.03 mol/l in accord to Ungaro. Indeed, 263

was obtained in a considerably better 74 % yield (Scheme 4.13). It could not be


determined why the literature procedure failed to give the expected yield. The outcome

of the reaction might be further improved by employing CHCl3/acetone in a 1:3 ratio or

increasing the amounts of reagents used.

Conversions of carboxycalixarenes to the corresponding acid chlorides have also been

described in the literature. Ungaro et al. reported the reaction of the tetracarboxy-

25,26,27,28-tetrapropoxycalix[4]arene with oxalyl chloride in dichloromethane184 or in

thionyl chloride/dichloromethane4c (1:1). The synthesis of the disubstituted 264 was

achieved by Jørgensen et al.187 in thionyl chloride in 62 % yield. Since thionyl chloride

is the less expensive reagent, a mixture of thionyl chloride/dichloromethane (1:3) was

employed to give about 73 % of the acid chloride 264, which was approximately 90 %

pure according to NMR and therefore used without further purification in the

subsequent transformation.

Scheme 4.13. Synthesis of dicarboxycalixarene 263 and subsequent conversion to acid chloride

264.

The phenylsubstituted tetrazine model compound exhibited low solubility and the

pyridyl unit offers an additional coordination site. Therefore, calixarene 264 was reacted

with the picolinohydrazide 244 under the same reaction conditions used for the model

compounds (Scheme 4.14). The 1H NMR spectrum obtained from the crude product

differs significantly from the starting materials. Especially the aromatic region (Figure

4.5) shows strong similarities to model compound 246, exhibiting a signal at about δ =

10.3 ppm assigned to NH, suggesting 265 has been formed.


OO OO

O OCl Cl

264

OO OO

O ONH HN

NH HN OO

N N

OO OO

Cl ClN N

N NClCl

N N

OO OO

HN NHN N

N NNHHN

N N

OO OO

N NN N

N NNN

N N

Na2CO3, THF,H2O, 3 h, 0 °C-rt

PCl5, CHCl3,ref lux, overnight

265

266

267 268

HOAc,NaNO2,Et2O, 0 °C

pyridine,NH2NH2·2 HCl,1.5 h, ref lux

Scheme 4.14. Envisaged synthesis of tetrazinecalixarene 268.

The 13C NMR spectrum gives clear evidence of two different phenol units and shows

20 of the expected 22 carbon peaks (Figure 4.6). The missing signals are those of the

methylene group next to the phenolic oxygen, which are superimposed by the

chloroform signal. Furthermore, carbonyl resonances at 165.1 and 162.0 ppm, similar to

those of the model compound, can be observed. The signals at 148 ppm are

characteristic of the pyridyl ring and a peak in the FAB mass spectrum at m/z = 941

[M+Na]+ gives further evidence for the successful coupling.

However, no eluent suitable for flash chromatography was found and crystallization

from DCM/MeOH failed. Therefore, the material was submitted to the next reaction

step, again using the reaction conditions tested with the model compounds. The NMR


spectra give evidence for the formation of the hydrazonoyl chloride 266. The aromatic

region of the 1H NMR spectrum shows signals similar to those of the model

hydrazonoyl chloride 247 but also the oxadiazole 253 (Figure 4.8). The proton shifts

show closer resemblance to the hydrazonoyl chloride and the 13C NMR spectrum gives

further evidence of the formation of corresponding calixarene 265 (Figure 4.6). In fact,

the peaks at 144.4 and 144.9 ppm are consistent with the carbons

6.66.87.07.27.47.67.88.08.28.48.68.89.09.29.49.69.810.010.210.410.610.8ppm

Figure 4.5. Partial 1H NMR of model compound 246 (top) and the crude product obtained from

the reaction to 265 (bottom), recorded at 200 MHz in CHCl3.

Figure 4.6. 13C NMR spectrum of carbohydrazide calixarene 265, recorded at 50 MHz in

CDCl3.


Figure 4.7. 13C NMR spectrum of calixarene 266, recorded at 50 MHz in CDCl3.

Figure 4.8. Partial 1H NMR of the oxadiazole and hydrazonoyl chloride model compounds 253

(top) and 247 (middle) versus the crude product obtained from the reaction to 266

(bottom), recorded at 200 MHz in CHCl3.

substituted by chlorine as also observed for the model compound. There are no signals

higher at around 160 ppm, which would indicate the formation of the corresponding

oxadiazole. Two sets of signals appear for the propoxy groups in the 13C NMR

spectrum, confirming two different phenol units. Again, two signals are superimposed

by the chloroform signal. A peak at δ = 149.7 ppm is characteristic for the pyridyl ring.


Purification of the brown residue by flash chromatography, however, proved to be

difficult as already observed for the starting material. Therefore, no material was

obtained in sufficient purity for unambiguous identification.

Material thus obtained was reacted with hydrazine dihydrochloride in pyridine in

analogy to the model compound. Flash column chromatography with PE/EtOAc 3:1 to

1:2 yielded little amounts of colorless solid in two fractions. However, NMR spectra of

the fractions gave no clear evidence of the formation of the desired dihydrotetrazine

267. A FAB mass spectrum obtained from one fraction shows a peak at m/z = 832,

which would be consistent with the loss of one pyridyl group, but no molecular ion is

detected. Comparison of the 1H NMR spectra of a second fraction and the pyridyl

tetrazine shows great similarities, but interestingly the material is colorless (Figure 4.9).

Upon oxidation with sodium nitrite in acetic acid an orange solid precipitated from the

reaction mixture, but the 1H NMR spectrum obtained from the crude product showed no

change. The same applies to the attempted oxidization of the other fraction.

Figure 4.9. Partial 1H NMR spectra of pyridyl model tetrazine (top) and a substance obtained by

flash chromatography of the dihydrotetrazinecalixarene crude product (bottom),

recorded in CDCl3 at 200 MHz.

4.4 Conclusion

The two model compounds 249 and 262 have been successfully prepared, albeit in

moderate yields. First attempts to apply the tested reaction conditions to the calixarene

indicate that the 1,2-diaroylhydrazine 265 as well as the hydrazonoyl chloride 266 are

indeed formed. However, purification and unambiguous identification have been


unsuccessful so far. When the crude calixarene mixture was further converted, no

evidence for the formation of the corresponding tetrazine could be observed.

The main problem in the synthetic route is the preparation of the hydrozonoyl

chloride, which is formed in varying yields along with 1,3,4-oxadiazole. Optimization

of this step, concerning the reproducibility and the yield of the reaction, is crucial for

the synthesis of unsymmetrical tetrazines, especially at a calixarene. Gautun et al.167 use

1,2-dichlorobenzene as solvent instead of chloroform, but the yields for the four

hydrazonoyl chlorides reported are mostly moderate between 28 and 75 %.

The only alternative reported in literature for the synthesis of hydrazonoyl chlorides,

is the chlorination of benzaldehyde azine 269 with chlorine in acetic acid or CCl4

(Scheme 4.15).188 However, Rosenberg et al.188b also detected 38 % of the

corresponding oxadiazole by GC, indicating that this method is unlikely to solve the

problem. Moreover, this method is unfavorable on a small scale and hardly any

unsymmetrical azines like 269 are known.

Scheme 4.15. Alternative for the synthesis of chloro(phenyl)methylene)benzo-hydrazonoyl

chloride 270: a) Cl2, HOAc, rt and b) Cl2, CCl4, K2CO3.

Scheme 4.16. Alternative approach to tetrazinecalixarenes by nucleophilic aromatic substitution

of dichlorotetrazine 272.


Audebert et al. reported the functionalization of hydroxy groups with tetrazines in the

synthesis of supramolecular compounds.158b,159 Consequently, another approach to

tetrazinecalixarenes might be considered (Scheme 4.16). Starting from the p-

hydroxycalixarene 271, coupling with 3,6-dichloro-1,2,4,5-tetrazine would yield

calixarene 273, in which the tetrazine moieties are linked to the calixarene by an oxygen

atom. Tetrazines substituted by a heteroatom have fluorescent properties,159 which

might be an interesting aspect of calixarene 273. Moreover, the chlorine offers another

reaction site for further functionalization of the tetrazine by nucleophilic aromatic

substitution. Although the oxygen bridge adds flexibility to the tetrazine moeity, Diels–

Alder reaction of the tetrasubstituted analogue should lead to endo-orientation of the

nitrogens. In fact, being less rigid might be an advantage for the complexation of

differently sized guests.

Recently, bistriazoylcalixarene 274, bisisochinolinylcalixarene 275 and

bislutidinylcalixarene 276 depicted in Figure 4.10 were successfully synthesized in our

group.189 Considering the difficulties in synthesizing unsymmetrical tetrazines, these N-

heteroaryl substituted calixarenes might be a more promising route to calixarenes with

endo-oriented nitrogen coordination sites.

Figure 4.10. N-heteroaryl functionalized calixarenes.

However, the reaction conditions leading to these compounds have also to be

optimized. Moreover, tetrazine moieties could be functionalized in the 6-position. This

would offer the advantage of adding coordination sites, as already planned with the

pyridyl substituent, and further enhancement of the calixarene cavity.

109

5 Conclusion and Outlook

New members of the calix[4]phenanthrene family have been prepared by intramolecular

oxidative photocyclization of styrylcalixarenes (Figure 5.1). Introduction of an

additional methyl group was necessary to prevent the transannular [2+2] cycloaddition

of opposite styryl moieties in the synthesis of 86a by steric hindrance.

184a

OO OO

81a

OO OO

86a

OO OO

146a

OO OO

221a

OO OO

OO

Figure 5.1. Newly synthesized calix[4]phenanthrenes and examples of the new classes of

calix[4]fluorenones, calix[4]dihydrophenanthrenes and calix[4]triphenylenes.

Only one of the possible stereoisomers is depicted, respectively.

Furthermore, several other inherently chiral calixarenes containing anellated subunits

have been synthesized by palladium-catalyzed intramolecular direct arylation. Thereby,

the first examples of the new classes of calix[4]fluorenones (184a),

calix[4]dihydrophenanthrenes (146a) and calix[4]triphenylenes (221a) have been

isolated. This may also provide an alternative route to calixphenanthrenes, which should

be accessible either by oxidation of the calixdihydrophenanthrene 146a or

intramolecular cyclization of the corresponding Z-styrylcalixarene. The latter can be

obtained by reduction of the bromophenylacetylenecalixaren 141b with Lindlar catalyst.

The acetylene calixarene has already been prepared in the synthesis of the

calixdihydrophenanthrenes.


Scheme 5.1. Alternative routes to calix[4]phenanthrenes.

Further oxidation of calixphenanthrenes and subsequent reductive amination should

further enhance the calixarene cavity. Moreover, in the N-heterocyclic 279 the electron-

rich cavity has been converted into an electron-deficient one (Scheme 5.2).

Calix[4]fluorenones 184 already provide the carbonyl groups for further

functionalization by reductive amination.

Scheme 5.2. Oxidation of calixdiphenanthrene 64 and subsequent reductive amination.

Although double cyclization might be more problematic, calixdibenzotetracene 281

seems to be a realistic development from calix[4]triphenylenes (Scheme 5.3). The

molecule provides the advantage of being symmetric, whereby separation of

stereoisomers would not be a problem. Nevertheless, molecule 281 should set the limit

Conclusion and Outlook 111

to this reaction as multifold cyclizations leading to polyaromatic hydrocarbon

substructures at calixarenes seem unlikely.

Scheme 5.3. Envisioned double intramolecular cyclization to calixdibenzotetracene 281.

However, so far the yields of the Pd-catalyzed direct arylations are only low to

moderate and the reaction conditions employed require further optimization. Moreover,

the reaction yields a mixture of stereoisomers. The first cyclization obviously does not

influence the regioselectivity of the second, neither for the photo- nor the Pd-catalyzed

cyclizations. If the regioselective outcome cannot be influenced, the separation has to be

greatly improved. It seems unlikely that higher homologues of the anellated calixarenes

will be obtained due to steric crowding as well as the complex mixtures of steroisomers

that would be formed.

Figure 5.2. Unsymmetrical tetrazine model compounds synthesized and tetrazinecalixarene

precursors, which seem to have been formed but were not isolated pure.


A first step towards tetrazine-substituted calixarenes has been made with the

successful synthesis of two asymmetric model tetrazines 249 and 262 (Figure 5.2). The

moderate yields, however, are insufficient for the multifold functionalization at

calixarenes. First attempts to employ the reaction conditions tested in the synthesis of

tetrazinecalixarenes indicated that carbohydrazide 265 and the hydrazonoyl chloride

266 have indeed been formed. The purification of the complex mixtures obtained has so

far been unsuccessful.

Subsequent Diels–Alder reaction of the tetrazinecalixarenes with sterically demanding

acetylenes should provide the corresponding pyridazinecalixarenes like 282. These

would provide interesting ligands with endo-oriented coordination sites for the

complexation of transition metal salts or complexes. However, considering the

difficulties in the synthesis of asymmetric tetrazines, the easier accessible tetrazoles

might provide a better alternative for calixarenes with endo-coordination sites.

Figure 5.3. Pyridazinecalixarene 282 and triazolecalixarene 274.

113

II. Experimental Part

1 Methods and Materials

1.1 Reaction control and separation methods

Thin-layer chromatography:

Reactions were monitored by thin-layer chromatography (TLC) using commercial TLC

plates “Polygram SIL G/UV254” with fluorescence indicator from Macherey-Nagel &

Co. Substances were detected by absorption of UV light (254 nm and 366 nm). Spots

were coloured with basic KMnO4 solution or ethanolic vanillin solution and subsequent

heating in a hot-air stream in the case of weakly absorbing substances.

Flash chromatography:

Separation and purification of products was achieved by flash chromatography using

glass columns with silica gel 60 (0.040–0.063 mm by Fluorochem Ltd. or Geduran® by

Merck), as stationary phase and applying overpressure. For the separation an eluent with

a Rf value of about 0.2–0.5 for the desired compound was chosen. Eluent mixtures were

prepared by volumetric measurement. Column length and diameter were adjusted

depending on the respective separation.

HPLC:

HPLC was performed using a unit consisting of a Knauer HPLC pump 64, a Knauer

differential refractometer and a mechanical recorder. Separations were carried out with

a LiChrospher Si 60 (5 µ) column from Merck of 20 cm length and 2 cm diameter.

Injections of about 200 µl were carried out over a six-port injection valve.

Distillation and sublimation:

Distillations and sublimations, respectively, were either carried out under reduced

pressure using short-path stills or by bulb-to-bulb distillation with a ball tube oven by

Büchi.

114 Experimental Part

1.2 Analytical chemistry: apparatus, instruments, acquisition

methods and comments on analytical data

Melting-point determination:

Melting points (°C) were determined with a Kofler instrument, model Reichert

Thermovar, or a melting-point apparatus by Dr. Tottoli from Büchi and are uncorrected.

Elemental analysis:

Elemental analyses were determined with a Vario EL by the analytical department of

the faculty for chemistry and biochemistry. Substance samples may deviate

∆C,H,N = ± 0.4 % from the calculated formula.

Infrared spectroscopy:

Infrared spectroscopy was performed with a Bruker Equinox 55 FT-IR. Solid

substances are scanned as KBr pellets. The position of absorption bands (ν~ ) is given in

cm-1. The following abbreviations are used for the characterization of absorption bands:

vs = very strong, s = strong, m = medium, w = weak, br = broad.

UV-VIS spectroscopy:

UV/Vis spectra were recorded on a Varian Cary 1. Absorption bands (λmax) are given in

nm, the corresponding absorption coefficient (ε) in cm² mmol-1. The following

abbreviations are used for the characterization of absorption bands: sh = shoulder,

br = broad

1H NMR spectroscopy:

1H NMR spectra were recorded with a Bruker DPX 200 (200.1 MHz), a Bruker DPX

250 (250.1 MHz), a Bruker DPX 400 (400.1 MHz) or a Bruker DRX 600 (600.1 MHz).

The chemical shifts (δ) are given in ppm, the coupling constant (J) in Hertz (Hz). The

spectra were calibrated on the internal solvent peak δ(CHCl3) = 7.26 ppm, δ(CH2Cl2) =

5.32 ppm or δ(DMSO-d6) = 2.50 ppm.190 Spectra were recorded at 303 K if not stated

otherwise. Spectra were processed and analyzed with MestReNova (6.0.4 and preceding

versions). The following abbreviations are used describing the style of signals: s =

singlet, d = doublet, t = triplet, q = quartet, m = multiplet, double letters like i.e. dd

stand for doublet of doublets etc., broad signals are marked with br as prefix. Multiplets

Methods and Materials 115

with a strong basic signal structure are marked with the appropriate letter in quotation

marks. Signal assignments to the structural fragment given are marked in italics

Residual solvent signals in the NMR spectra depicted are marked with an asterisk.

13

C NMR spectroscopy:

13C NMR spectra were recorded with a Bruker DPX 200 (50.1 MHz), a Bruker DPX

250 (250.1 MHz), a Bruker DPX 400 (100.1 MHz) or a Bruker DRX 600 (150.1 MHz).

All 13C NMR spectra are proton decoupled. Signal multiplicities are determined by

HMQC and HMBC experiments and are assigned the same abbreviations as for 1H NMR spectra. The chemical shifts (δ) are given in ppm. The spectra were calibrated

on the internal solvent peak δ(CHCl3) = 77.16 ppm, δ(CH2Cl2) = 54.00 ppm or

δ(DMSO-d6) = 39.52 ppm.190 Spectra were recorded at 303 K if not stated otherwise.

Spectra were processed and analyzed with MestReNova (6.0.4 and preceding version).

Signal assignments to the structural fragment given are marked in italics Residual

solvent signals in the NMR spectra depicted are marked with an asterisk.

31

P NMR spectroscopy:

31P NMR spectra were recorded with a Bruker DPX 250 (250.1 MHz) and are

decoupled and uncalibrated. The chemical shifts (δ) are given in ppm. Spectra were

processed and analyzed with MestReNova (6.0.4 and preceding versions).

Mass spectrometry:

Mass spectroscopy was performed with a Varian MAT CH5, a VG Autospec or a Jeol

AccuTOF GCv. The m/z ratios are given as dimensionless numbers. The abundance of

the peaks is given relative to the base peak (100 % abundance). For EI experiments

(electron-impact ionization) with 70 eV only peaks with an intensity of at least 5 % or

particularly characteristic fragments are listed. The spectra were recorded in mNBA (m-

nitrobenzyl alcohol) or lactic acid as matrix. High-resolution mass spectrometry

(HRMS) was performed as EI measurement at the Jeol Accu TOF GCv. Substance

samples may deviate less than 10 ppm from the calculated formula.


X-ray structure analysis:

The intensity data were collected on an Oxford Diffraction Xcalibur2 diffractometer

with a Sapphire2 CCD. The crystal structures were solved by direct methods using

SHELXS-97191 and refined with SHELXL-97191. For refinement details see appendix or

cif-files. CCDC-787366 (for 60), CCDC-787367 (for 81a), and CCDC-787368 (for

86a). These data are also available from The Cambridge Crystallographic Data Centre

via www.ccdc.cam.ac.uk/data_request/cif.

1.3 Solvents and reagents

Solvents were dried according to common methods.192 Anhydrous solvents were stored

under argon in flasks with T-type connectors over molecular sieve and kept oxygen- and

moisture-free. Small amounts were dried by filtration over aluminium oxide 90 active

basic (0.003-0.200 nm), activity stage I from Merck. Solvents for extraction and column

chromatography are technical grade and distilled over Vigreux columns at standard

pressure prior to use. All commercially available chemicals were used without further

purification.

2,2,2-Trifluoroethanol: Riedel de Häen.

2-Butanone: Purchased from Riedel de Häen.

Acetone: Purchased from J. T. Baker.

Acetonitrile (for UV/Vis): spectrophotometric grade 99+%, Acros Organics.

Acetonitrile: Purchased from J. T. Baker.

Acetonitrile (dry): Refluxed over phosporus pentoxide for 3–4 h, distilled and stored

over molecular sieves 3 Å.

Benzene: Purchased from Normapur or J. T. Baker.

Chloroform: Purchased from Normapur or J. T. Baker.

Deuterochloroform-d1: 99.8 % D, Deutero GmbH.

Dichloromethane: technical grade, distilled.

Dichloromethane-d2: 99.6 % D, Deutero GmbH.

Dichloromethane (dry): Refluxed over calcium hydride, distilled and stored over

molecular sieves 4 Å under argon.

Diethylether: anhydrous, purchased from J. T. Baker.

Dimethyl sulphoxide-d6: 99.9 % D, Deutero GmbH.


Dimethylformamide: DMF, purchased from J. T. Baker, dried twice over molecular

sieve 3 Å for 24 h each.

Ethanol: technical grade, distilled.

Ethanol: anhydrous, purchased from Aldrich or Baker.

Ethyl acetate: technical grade, distilled.

i-Propanol: technical grade, distilled.

Methanol: technical grade, distilled.

Methyl-tert-butyl ether: technical grade, distilled.

N,N-Dimethylacetamide: 99+%, extra pure, purchased from Acros.

n-Hexane (for UV/Vis): 95+%, spectrophotometric grade purchesed from Sigma-

Aldrich.

n-Hexane: technical grade, distilled.

Nitromethane: Purchased from Merck, dried over CaCl2, distilled and stored over

molecular sieve 3 Å under argon.

Pentane: technical grade, distilled.

Petroleum ether 40/60: technical grade, distilled.

Pivalic acid: Purchased from Fluka.

Tetrahydrofurane (dry): Refluxed over sodium or a sodium dispersion in

paraffin/benzophenone until blue, distilled and used directly.

Toluene: technical grade, distilled.

Toluene (dry): Refluxed over sodium or a sodium dispersion in paraffin/benzophenone

until blue, distilled and stored over molecular sieves 3 Å under argon.

Triethylamine (dry): Purchased from J.T.Baker and dried over CaH2, distilled and

stored over molecular sieves 4 Å under argon.

Trifluoroacetic acid: 99 %, extra pure, purchased from Acros.

Reagents were used and stored as follows:

1-Bromopropane: Purchased from Riedel de Haën or 99 % from Acros and stored in a

refrigerator.

1-Iodpropane: Purchased from Fluka, ≥ 98 % (GC).

2-Biphenylboronsäure (190): Purchased from Aldrich.

2-Bromobenzaldehyde: 97 % from Acros.


2-Bromobenzoic acid: 97 % from Aldrich.

2-Bromobenzonitrile: 99 % Acros.

2-Bromobenzoyl chloride: 98 % Acros.

2-Bromophenylacetic acid: Purchased from Fluka oder 98 % from Acros.

2-Chlorobenzaldehyde: purum, ≥ 98% (GC) from Fluka.

2-Chlorobenzoic acid: Merck or 98 % from Aldrich.

2-Chlorobenzonitrile: 98 % from Aldrich.

2-Iodobenzoic acid: Laboratory chemical.

2-Methyl-3-butyn-2-ol: 98 % from Aldrich.

Aluminium chloride: 98 %, anhydrous, sublimated, purchased from Merck or 99 %,

extra pure, anhydrous from Acros.

Benzoyl chloride: Purchased from Merck.

Benzyl bromide: Purchased from Riedel de Haën.

Benzyltrimethylammonium chloride: 98+% from Acros.

Benzyltriphenylphosphonium chloride: Purchased from Janssen Chimica.

Bromine: Riedel de Häen or Merck.

Chlorotrimethylsilane: Laboratory chemical.

Copper(I) iodide: Purchased from Acros, 98 %.

Ceasium carbonate: 99 % from Aldrich.

Ethyl 2-picolinate: 99 % from Aldrich and ABCR.

Ethylene glycol: Laboratory chemical.

Hexamethylenetetramine (HMTA): Purchased from Riedel de Haën.

Hydrazine hydrate: 100 % (64 % hydrazine) from Acros.

Hydroxylamine hydrochloride: Merck.

Potassium carbonate: J.T.Baker or 98-100% from Riedel de Häen. Was dried in

vacuum prior to use at 250 °C.

Potassium hydroxide: J.T.Baker.

Methyl benzoate: Riedel de Häen.

N,O-Dimethylhydroxylamine hydrochloride: 98 % EGA-Chemie.

Sodium carbonate: anhydrous from Riedel de Häen or J.T.Baker.

Sodium borohydride: 98 % from Aldrich.

Sodium hydride: 60 % dispersion in mineral oil. Purchased from Fluka and Acros,

stored in a desiccator over silica gel and washed with pentane or hexane under argon

prior to use to remove the mineral oil.


N-Bromosuccinimide (NBS): 99 %, purchased from Acros and ABCR and stored in a

refrigerator.

Oxalyl chloride: Riedel de Häen or 98 % from Acros.

Phosphorus pentachloride: Purchased from Merck.

Palladium(II) acetate: Purchased from Merck 47 % Pd.

Pd(PPh3)2Cl2: 98 % from Acros.

Tetrakis(triphenylphosphine)palladium(0): 99% purchased from Aldrich.

Bis(triphenylphosphine)palladium(II) chloride: Janssen Chimica (59 % Pd) or 98 %

from Aldrich and Acros.

Phthalic anhydride: Purchased from Acros.

PIFA ([Bis(trifluoroacetoxy)iodo]benzene): 98 % from Acros.

p-Toluenesulfonyl hydrazide: From Merck.

Sodium chlorite (NaClO2): Purchased from Acros and Aldrich, 80 %, technical grade.

Sodium peroxodisulfate (Na2S2O8): 98 % from Acros.

Sulfamic acid: Purchased from Acros.

Tetramethylammonium iodide: 99 % from Acros.

Tricyclohexylphosphonium tetrafluoroborate: 99 %, purchased from Acros.

Trimethyl borate: 99 % from AcroSeal®.

Trimethylsilylacetylene: 98 % from Aldrich.

Triphenylphosphine: Riedel de Häen.

Thionyl chloride: 95.5 % from Acros or > 99 % from Merck.

Iodine: Baker Grade 99.5-110.5 % from J.T.Baker or 99.9 % from Aldrich.

1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): 98 % from Aldrich.

1,2-Dibromobenzene: 99 % from Acros.

2,6-Dimethylanisole: 98 % from Avocado or purchased from ABCR.

n-Butyllithium: 15 % in hexane from Merck or 1.6 M in hexane from AcroSeal® and

stored in a refrigerator.

t-Butyllithium: 15 % in pentane from Merck or 1.6 M in pentane from AcroSeal® and

stored in a refrigerator.

4-Bromo-2,6-dimethylphenol (208): 99 % from Acros.

121

2 Syntheses

2.1 Syntheses of reagents and model compounds

2.1.1 Triphenyl(1-phenylethyl)phosphonium bromide (84)

(1-Bromoethyl)benzene (83) (2.71 g, 14.6 mmol) and triphenylphosphine (283) (4.00 g,

15.3 mmol) were dissolved in toluene (15 mL) and stirred at 110–120 °C for 3 d in a

srew-cap flask. The colorless precipitate was filtered off, washed with toluene and dried

in vacuo (0.76–2.5 mbar, 100 °C, 3 h) to give 5.77 g (88 %) of 84 as a solid with mp

229–231 °C (lit.193 mp 231–234 °C).

1H NMR (200 MHz, CDCl3): δ = 1.82 (dd, J = 19.1 Hz, J = 7.2 Hz, 3 H, CH3), 6.82

(dq, J = 14.2 Hz, J = 7.3 Hz, J = 7.1 Hz, 1 H, CH), 7.10–7.26 (m, 5 H, ArH), 7.58–7.88

(m, 15 H, ArH) ppm.

31

P{1H} NMR (101 MHz, CDCl3): δ = 27.30 ppm.

MS (FAB): m/z (%) = 367 (100) M+.

NMR spectroscopic data are in accord with the literature.89,90


1H NMR (200 MHz, CDCl3): Triphenyl(1-phenylethyl)phosphonium bromide (84)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0

f1 (ppm)

3.03

1.00

4.83

14.66

1.82

6.82

7.10

7.25

7.58

7.88

Syntheses 123

2.1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118)

2,6-Dimethyl anisole (117) (1.22 mL, 8.45 mmol), aluminium chloride (686 mg, 5.09

mmol) and 2-bromophenylacetyl chloride (116) (1.00 g, 4.28 mmol) were suspended in

dry dichloromethane (10 mL) and refluxed for 1 h 15 min. After addition of HCl (2 N,

15 mL), the layers were separated and the aqueous layer was extracted twice with

dichloromethane (20 mL). The combined organic extracts were washed with NaOH

(10 %, 20 mL), water (20 mL), dried over MgSO4 and the solvent was removed at a

rotary evaporator. Excess dimethylanisole was removed in vacuo (0.78 mbar, 50 °C).

The resulting yellow solid was washed with methanol and dried in vacuo (0.89 mbar,

50 °C, 30 min) to yield 1.35 g (94 %) of 118 as a colorless solid with mp 101 °C.

C17H17BrO2 (333.22)

calcd.: C 61.28, H 5.14

found: C 61.52, H 5.24

IR (KBr): ν~ = 3058 (w), 2948 (w), 2915 (w), 2857 (w), 2828 (w), 1684 (s, C=O), 1595

(m), 1567 (w), 1471 (m), 1439 (w), 1408 (m), 1377 (w), 1332 (s), 1293 (m), 1272 (w),

1225 (w), 1178 (w), 1147 (s), 1059 (w), 1045 (w), 1025 (m), 1009 (m), 946 (w), 892

(w), 868 (w), 837 (w), 779 (w), 760 (w), 744 (s) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 260 (4.0) nm.

1H NMR (400 MHz, CDCl3): δ = 2.34 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 4.40 (s, 2 H,

C(O)CH2), 7.14 ( “t”, “J” = 7.6 Hz , 1 H, ArH), 7.23–7.30 (m, 2 H, ArH), 7.59 (d, J =

8.0 Hz, 1 H BrArH), 7.73 (s, 2 H, m-ArH) ppm.


13

C{1H} NMR (100 MHz, CDCl3): δ = 16.43 (q, CH3), 45.78 (t, C(O)CH2), 59.81 (q,

OCH3), 125.26 (s, Ar’CBr), 127.63 (d, Ar’CH), 128.77 (d, Ar’CH), 129.57 (d, m-

ArCH), 131.44 (s, ArCCH3), 131.80 (d, Ar’CH), 132.49 (s, ArCC=O), 132.92 (d,

Ar’CH), 135.42 (s, Ar’CCH2)), 161.61 (s, ArCO), 195.80 (s, C=O) ppm.

MS (FAB): m/z (%) = 333 (55) [M+H]+, 169 (16), 163 (100) [M–C7H6Br]+.

Syntheses 125

1H NMR (400 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanone (118)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

2.96

2.90

2.00

0.91

2.10

0.85

1.88

2.34

3.77

4.40

7.14

7.23

7.30

7.59

7.73

13C NMR (100 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanone (118)

0102030405060708090100110120130140150160170180190200f1 (ppm)

16.4

45.8

59.8

125.3

127.6

128.8

129.6

131.4

131.8

132.5

132.9

135.4

161.6

195.8

127128129130131132133f1 (ppm)

127.6

128.8

129.6

130.4

131.4

131.8

132.5

132.9


2.1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124)

Under argon ketone (118) (650 mg, 1.95 mmol) was dissolved in 15 mL dry

tetrahydrofuran and NaBH4 (170 mg, 98 %, 4.40 mmol) was added. The mixture was

refluxed for 24 hours. After cooling down to room temperature water (20 mL) followed

by HCl (2 N, 20 mL) were added. The mixture was extracted with diethyl ether

(2 x 25 mL). The organic layers were dried over MgSO4 and the solvent was removed

by rotary evaporation. After purification by flash chromatography (silica gel, PE/EtOAc

10:1, Rf (PE/EtOAc 10:1) = 0.14) and subsequent drying in vacuo (1.6 mbar, 75 °C,

45 min) 570 mg (87 %) of 2-(2-bromophenyl)-1-(3,5-dimethyl-4-methoxyphenyl)-

ethanol (124) were obtained as a white solid with a melting point of 104 °C.

C16H19BrO2 (335.24)

calcd.: C 60.91, H 5.71

found: C 60.94, H 5.67

IR (KBr): ν~ = 3446 (vs, OH), 3056 (w), 2998 (w), 2972 (w), 2947 (w), 2919 (m), 2880

(w), 2835 (w), 1597 (w), 1556 (w), 1475 (m),1436 (m), 1393 (w), 1341 (w), 1314 (w),

1276 (w), 1214 (m), 1172 (w), 1135 (m), 1114 (w), 1068 (m), 1023 (m), 1000 (m), 939

(w), 878 (w), 856 (w), 833 (w), 769 (w), 744 (m) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.05 (dd, J = 13.7 Hz, J = 9.2 Hz,

1 H, CH2), 3.19 (dd, J = 13.7 Hz, J = 4.0 Hz, 1 H, CH2), 3.72 (s, 3 H, OCH3), 4.92 (dd,

Syntheses 127

J = 9,2 Hz, J = 4.0 Hz, 1 H, CH), 7.06 (s, 2 H, m-ArH), 7.09–7.14 (m, 1 H, ArH’), 7.24

(d, J = 4.1 Hz, 2 H, ArH’), 7.58 (d, J = 7.9 Hz, 1 H, Ar-3’-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 46.3 (t, CH2), 59.8 (q, OCH3),

73.3 (d, CH(OH)), 125.0 (s, Ar’CBr), 126.3 (d, m-ArCH), 127.5 (d, Ar’CH), 128.4 (d,

Ar’CH), 131.0 (s, ArC), 132.2 (d, Ar’CH), 133.1 (d, Ar’CH), 138.1 (s, ArC), 139.3 (s,

Ar’C), 156.6 (s, ArCO) ppm.

MS (FAB): m/z (%): 335 (6) [M+H]+, 319 (49) [M–CH3]+, 165 (100) [M–C6H7Br]+, 154

(16), 137 (12).


1H NMR (400 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanol (124)

13C NMR (100 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanol (124)

Syntheses 129

2.1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethyl-

silane (125)

A solution of 2-(2-bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124)

(343 mg, 1.02 mmol), chlorotrimethylsilane (274 mg, 2.53 mmol) and imidazole

(351 mg, 5.15 mmol) in anhydrous DMF (25 mL) was stirred under argon at 40 °C for

18 h. The mixture was hydrolyzed with water (25 mL), extracted with CH2Cl2 (3 x

20 mL) and dried over sodium sulfate. The solvent was removed under reduced pressure

and the crude product purified by flash chromatography (silica gel, PE/EtOAc 10:1;

Rf = 0.56) and dried in vacuo (2.6–5.1 mbar, 50–75 °C). The product 125 (309 mg,

74 %) was obtained as slightly yellow oil.

HRMS (EI, 70 eV): C20H27BrO2Si (407.42)

calcd.: 406.0964 g/mol

found: 406.0898 g/mol

1H NMR (400 MHz, CDCl3): δ = -0.19 (s, 9H, SiCH3), 2.28 (s, 6H, CH3), 2.89 (dd, J =

9.4 Hz, J = 13.3 Hz, 1H, CH2), 3.12 (dd, J =3.6 Hz, J = 13.3 Hz, 1H, CH2), 3.72 (s, 3H,

OCH3), 4.86 (dd, J = 3.6 Hz, J = 9.3 Hz, 1H, CH), 7.01 (s, 2H, m-ArCH), 7.05–7.09 (m,

ArCH), 7.15–7.21 (m, ArCH), 7.55 (dd, J = 0.9 Hz, J = 7.9 Hz, 1H, ArCBrH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = –0.24 (q, SiCH3),16.3 (q, CH3), 47.8 (t, CH2),

59.8 (q, OCH3), 73.4 (d, CH), 124.9 (s, Ar’CBr), 126.0 (d, m-ArCH), 127.0 (d, Ar’CH),

128.1 (d, Ar’CH), 130.4 (s, CCH3), 132.6 (d, Ar’CH), 133.2 (d, Ar’CH), 138.8 (s,

Ar’C), 140.3 (s, p-ArC), 156.1 (s, ArCO) ppm.


MS (EI, 70 eV): m/z (%): 407 M+, 393, 378, 317 (3) [M–OTMS]+, 237 (100)

[M–C7H6Br]+, 73 (32).

Syntheses 131

1H NMR (400 MHz, CDCl3): (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethoxy)trimethylsilane (125)

13C NMR (100 MHz, CDCl3): (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethoxy)trimethylsilane (125)


2.1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-

phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-3,5-

dimethylphenyl)methanone) (120b)

Ketone 118 (334 mg, 1.00 mmol), potassium carbonate (276 mg, 2.00 mmol) and

tricyclohexylphosphonium tetrafluoroborate (42 mg, 113 µmol) were suspended in

DMA (5 mL) in a screw-cap flask. The suspension was degassed with argon for 10 min

before Pd(OAc)2 (11 mg, 49 µmol) was added. The mixture was heated to 145 °C for

24 h, cooled to room temperature and extracted with CH2Cl2 (3 x 20 mL). The organic

layer was washed with HCl (2 N, 20 mL), water (20 mL), brine (20 mL) and dried over

MgSO4. The solvents were removed under reduced pressure and the residue purified by

flash chromatography (silica gel, PE/EtOAc 15:1 to 10:1) to yield after subsequent

drying in vacuo (1.7 mbar, 75 °C, 45 min):

1st fraction (Rf (PE/EtOAc 5:1) = 0.26): 47 mg (19 %) of dihydrophenanthrene 120a

after recrystallization from DCM/MeOH as colorless crystalline solid with

mp 222–224 °C.

C34H32O4 (504.62)

calcd.: C 80.93, H 6.39

found: C 80.61, H 6.15

IR (KBr): ν~ = 3063 (w), 2990 (w), 2949 (w), 2927 (w), 2864 (w), 2828 (w), 1674 (vs),

1592 (s), 1483 (s), 1445 (m), 1411 (w), 1339 (s), 1293 (s), 1231 (m), 1206 (m), 1886

(w), 1144 (vs), 1056 (w), 1008 (s), 952 (w), 828 (w), 905 (w), 874 (w), 856 (w), 793

(w), 773 (w), 753 (s), 731 (w) cm-1.


Syntheses 133


CH), 6.95 (d, J = 7.5 Hz, 2 H, PhenH), 7.17 (td, J = 7.6 Hz, J = 1.1 Hz, 2 H, PhenH),

7.37 (td, J = 7.7 Hz, J = 1.0 Hz, 2 H, PhenH), 7.77 (s, 4 H, ArH), 7.83 (dd, J = 7.8 Hz, J

= 1.0 Hz, 2 H, PhenH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 48.9 (d, CH), 59.8 (q, OCH3),

124.5 (d, PhenCH), 127.0 (d, PhenCH), 127.9 (d, PhenCH), 128.2 (d, PhenCH), 130.0

(d, ArCH), 131.7 (s, CCH3), 133.8 (s, ArC), 134.4 (s, PhenC), 136.4 (s, PhenC), 162.0

(s, ArCO), 201.7 (s, C=O) ppm.

MS (FAB): m/z (%):505 (20) [M+H]+, 163 (79).


1H NMR (400 MHz, CDCl3): (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethylphenyl)methanone) (120a)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

12.42

6.07

2.00

1.94

1.96

1.96

3.90

2.22

2.30

3.77

5.47

6.95

7.17

7.37

7.77

7.83

7.07.27.47.67.8f1 (ppm)

1.94

1.96

1.96

3.90

2.22

6.95

7.17

7.37

7.77

7.83

13C NMR (100 MHz, CDCl3): (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethylphenyl)methanone) (120a)

0102030405060708090100110120130140150160170180190200f1 (ppm)

16.4

48.8

59.8

124.5

127.0

127.9

128.2

130.0

131.7

133.8

134.4

136.4

162.0

201.7

Syntheses 135

2nd fraction (Rf (PE/EtOAc 5:1) = 0.19): 96 mg (38 %) of phenanthrene 120b as a

colorless solid of which some was recrystallized from DCM/MeOH to yield colorless

crystals with mp 242–243 °C.

C34H30O4 (502.60)

calcd.: C 81.25 , H 6.02

found: C 81.14, H 6.34

IR (KBr): ν~ = 3060 (w), 3037 (w), 2946 (w), 2925 (w), 2861 (w), 2829 (w), 1664 (vs),

1592 (s), 1480 (m), 1446 (s), 1413 (m), 1374 (m), 1323 (vs), 1297 (s), 1222 (s), 1185

(s), 1172 (s), 1147 (vs), 1111 (w), 1092 (w), 1070 (w), 1042 (w), 1006 (s), 951 (w), 906

(w), 886 (w), 864 (w), 814 (w), 787 (w), 761 (s), 724 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 244 (4.9), 252 (4.9) nm.


ArH), 7.53 (“t”, “J” = 7.6 Hz, 2 H, Phen-H), 7.69 (d, J = 8.3 Hz, 2 H, Phen-H), 7.73

(„t“, „J“ = 7.6 Hz, 2 H, Phen-H), 8.81 (d, J = 8.4 Hz, 2 H, Phen-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59.7 (q, OCH3), 123.1 (d,

PhenCH), 127.5 (d, PhenCH), 127.9 (d, PhenCH), 128.9 (s, PhenC), 130.6 (s, PhenC),

131.3 (s, CCH3), 131.4 (d, ArH), 133.6 (s, ArC), 135.5 (s, PhenC), 162.0 (s, ArCO),

197.6 (s, C=O) ppm.

MS (FAB): m/z (%): 525 (15) [M+Na]+, 503 (76) [M+H]+, 367 (39), 163 (100) [M–phenanthrene]+.


1H NMR (400 MHz, CDCl3): Phenanthrene-9,10-diylbis((4-methoxy-3,5-dimethyl-phenyl)methanone) (120b)

11.90

6.00

3.60

2.05

2.01

2.13

1.96

2.18

3.72

7.44

7.53

7.69

7.73

8.81

2.05

2.01

2.13

7.53

7.69

7.73

13C NMR (100 MHz, CDCl3): Phenanthrene-9,10-diylbis((4-methoxy-3,5-dimethyl-phenyl)methanone) (120b)

0102030405060708090100110120130140150160170180190200f1 (ppm)

16.3

59.7

123.1

127.5

127.9

128.8

130.6

131.3

131.4

133.6

135.5

162.0

197.6

Syntheses 137

2.1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and

1-(4-hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)

(2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethylsilane (125)

(257 mg, 631 µmol), potassium carbonate (177 mg, 1.28 mmol) and tricyclohexyl-

phosphonium tetrafluoroborate (25 mg, 67 µmol) were suspended in DMA (3 mL) in a

screw-cap flask. The suspension was degassed with argon for 5 min before Pd(OAc)2

(7 mg, 31 µmol) was added. The mixture was heated to 170 °C for 3 d, cooled to room

temperature, hydrolyzed with water (10 mL) and extracted with DCM (3 x 10 mL). The

organic layer was washed with HCl (2 N, 10 mL), water (10 mL), brine (10 mL) and

dried over MgSO4. The solvents were removed under reduced pressure and the residue

purified by flash chromatography (silica gel, PE/EtOAc 20:1 to 5:1) to yield:

1st fraction (Rf (PE/EA 15:1) = 0.28): 90 mg (56 %) of 127 after drying in vacuo (0.65

mbar, 75 °C, 20 min) as colorless solid with mp 85-87 °C (lit.: 85°C)


CH2), 7.22–7.27 (m, 3 H, Ar’H), 7.30–7.34 (m, 2 H, Ar’H), 7.69 (s, 2 H, m-ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 45.4 (t, CH2), 59.8 (q, OCH3),

126.9 (d, p-Ar’CH), 128.8 (d, o-Ar’CH), 129.6 (d, m-Ar’CH), 129.9 (d, m-ArCH),

131.4 (s, CCH3), 132.5 (s, p-ArC), 135.1 (s, Ar’C), 161.5 (s, ArCO), 197.2 (s, C=O)

ppm.

MS (FAB): m/z (%) = 255 (98) [M+H]+, 163 (100), 91 (32).


1H NMR (400 MHz, CDCl3): 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127)

13C NMR (100 MHz, CDCl3): 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127)

Syntheses 139

2nd fraction (Rf (PE/EA 15:1) = 0.07): 42 mg (28 %) of 128 after drying in vacuo

(0.61 mbar, 75 °C, 20 min) as colorless solid with mp 116 °C.

1H NMR (400 MHz, CDCl3): δ = 2.28 (s, 6 H, CH3), 4.21 (s, 2 H, CH2), 5.16 (s, 1 H,

OH), 7.21-7.33 (m, 5 H, Ar’H), 7.69 (s, 2 H, m-ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.0 (q, CH3), 45.3 (t, CH2), 123.1 (s, CCH3),

126.8 (d, p-Ar’CH), 128.7 (d, Ar’CH), 129.4 (s, ArC), 129.5 (d, Ar’CH), 130.1 (d,

m-ArCH), 135.3 (s, Ar’C), 156.9 (s, ArCO), 196.8 (s, C=O) ppm.

MS (FAB): m/z (%) = 263 (38) [M+Na]+, 241 (100) [M+H]+, 149 (94).


1H NMR (400 MHz, CDCl3): 1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)

13C NMR (100 MHz, CDCl3): 1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)

Syntheses 141

2.1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)

A mixture of ketone 118 (501 mg, 1.50 mmol), hydrazine hydrate (0.77 mL) and

ethylene glycol (8 mL) was refluxed until a homogenous solution resulted. KOH

(1.12 g, 19.9 mmol) was added in small portions to the refluxing mixture over a period

of 2 h and heated for another hour. After cooling to room temperature, the mixture was

poured onto ice cold conc. HCl (10 mL) and extracted with MTBE (3 x 15 mL). The

organic layer was washed with water (3 x 15 mL), dried over MgSO4 and the solvent

was removed at a rotary evaporator. The crude product was purified by flash

chromatography (silica gel, PE/EtOAc 10:1 to 5:1, Rf (5:1) = 0.66) and dried in vacuo

(4.5 mbar, 100 °C) to yield 129 (339 mg, 71 %) as a colorless oil.

HRMS (EI, 70 eV): C17H19BrO (319.24)



1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 6 H, CH3), 2.78–2.82 (m, CH2), 2.98-3.02 (m,

CH2), 3.73 (s, 3 H, OCH3), 6.89 (s, m-ArH), 7.05–7.10 (m, Ar’H), 7.19–7.25 (m, Ar’H),

7.56 (dd, 2J = 7.9 Hz, 3J = 0.9 Hz, Ar’H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.2 (q, CH3), 35.8 (t, CH2) , 38.7 (t, CH2), 59.9

(q, OCH3), 124.6 (s, Ar’CBr), 127.5 (d, Ar’CH), 127.8 (d, ArC’H), 128.9 (d, ArCH),

130.6 (d, Ar’CH), 130.7 (ArCCH3), 133.0 (d, ArC’H), 136.9 (s, ArC), 141.3 (s, Ar’C),

155.4 (s, ArCO) ppm.


MS (FAB): m/z (%): 319 (37) [M+H]+, 183 (13) [M–C9H11O]+, 149 (100) [M–

C7H6Br]+.

Syntheses 143

1H NMR (400 MHz, CDCl3): 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)

13C NMR (100 MHz, CDCl3): 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)


2.1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)

5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) (299 mg, 937 µmol),

potassium carbonate (262 mg, 1.90 mmol) and tricyclohexylphosphonium

tetrafluoroborate (37 mg, 99 µmol) were suspended in DMA (5 mL) in a screw-cap

flask. The suspension was degassed with argon for 10 min before Pd(OAc)2 (10 mg,

45 µmol) was added. The mixture was heated to 170 °C for 3 d, cooled to room

temperature, hydrolyzed with water (15 mL) and extracted with DCM (3 x 15 mL). The

organic layer was washed with HCl (2 N, 15 mL), water (15 mL), brine (15 mL) and

dried over MgSO4. The solvents were removed under reduced pressure and the residue

purified by flash chromatography (silica gel, PE/EtOAc 10:1 to 5:1, Rf (5:1) = 0.28).

Recrystallization from DCM/MeOH and drying in vacuo (4 mbar, 50 °C) gave 130

(153 mg, 69 %) as colorless solid with mp 86–88 °C.

IR (KBr): ν~ = 3098 (w), 3057 (w), 3013 (w), 2981 (w), 2938 (m), 2890 (w), 2829 (w),

1558 (w), 1476 (m), 1442 (m), 1400 (w), 1373 (w), 1344 (w), 1324 (w), 1291 (w), 1243

(w), 1224 (m), 1194 (w), 1139 (s), 1107 (w), 1046 (w), 1013 (s), 990 (w), 969 (w), 947

(w), 881 (w), 799 (w), 781 (w), 747 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 299 (3.8, sh), 266 (4.3) nm.

1H NMR (400 MHz, CDCl3): δ = 2.32 (s, 3 H, CH3), 2.55 (s, 3 H, CH3), 2.71 (dd, 1

J =

16.6 Hz, 2J = 7.5 Hz, 4 H, CH2), 3.79 (s, 3 H, OCH3), 6.95 (s, 1H, Ar-1-H), 7.20 (“t”,

“J” = 7.3 Hz, 1 H, ArH), 7.26–7.30 (m, 2 H, ArH), 7.63 (d, J = 7.9 Hz, 1 H, Ar-5-H)

ppm.

Syntheses 145

13C{

1H} NMR (100 MHz, CDCl3): δ = 15.8 (q, CH3), 16.2 (q, CH3), 30.3 (t, CH2), 30.4

(t, CH2), 59.9 (q, OCH3), 125.8 (d, ArCH), 126.6 (d, ArCH), 127.6 (d, ArCH), 127.9 (d,

ArCH), 128.0 (s, ArC), 128.5 (d, ArCH), 129.4 (s, ArC), 133.8 (s, ArC), 135.0 (s, ArC),

135.3 (s, ArC), 139.9 (s, ArC), 156.9 (s, ArCO) ppm.

MS (EI, 70 eV): m/z (%) = 238 (100) M+, 223 (28) [M–CH3]+, 208 (16), 200 (10), 178

(11), 165 (15).


1H NMR (400 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)

13C NMR (100 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)

Syntheses 147

2.1.9 (2-Bromophenylethynyl)trimethylsilane (144)

In a screw-capped flask 1,2-dibromobenzene (142) (1.19 g, 4.95 mmol), palladium(II)

acetate (45 mg, 200 µmol), triphenylphosphine (209 mg, 797 µmol), copper(I) iodide

(80 mg, 412 µmol) and trimethylsilylacetylene (284) (0.86 mL, 5.96 mmol) were

suspended in dry triethylamine (11 mL) and heated to 70 °C for 17 hours. The solvent

was removed and the residue was dissolved in MTBE (20 mL) and water (20 mL), the

layers were separated and the organic layer washed with water (20 mL), dried over

MgSO4 and the solvent was removed in vacuo. The remaining residue was purified by

flash chromatography (silica gel, PE and PE/EtOAC 50:1, Rf in PE = 0.35) to yield Z

(982 mg, 78 %) as a yellow oil.

1H NMR (400 MHz, CDCl3): δ = 0.28 (s, 9 H, Si(CH3)3), 7.15 (“t”, “J” = 7.5 Hz, 1 H,

ArH), 7.24 (td, J = 7.6 Hz, J = 1.0 Hz, 1 H, ArH)), 7.49 (dd, J = 7.4 Hz, J = 1.7 Hz, 1 H,

ArH), 7.57 (d, J = 7.6 Hz, 1 H, ArH) ppm.

NMR data are in accord with the literature.126


1H NMR (200 MHz, CDCl3): (2-Bromophenylethynyl)trimethylsilane (144)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

8.69

2.00

1.00

0.94

0.28

7.15

7.24

7.49

7.57

7.07.17.27.37.47.57.6f1 (ppm)

2.00

1.00

0.94

7.15

7.24

7.49

7.57

Syntheses 149

2.1.10 1-Bromo-2-ethynylbenzene (140)

4-(2-Bromophenyl)-2-methylbut-3-yn-2-ol (143) (1.28 g, 5.37 mmol) and sodium

hydride (1.58 g, 39.5 mmol, 60 % dispersion in oil) were suspended in dry toluene

(12.5 mL) and heated to reflux for 1 h, after which half the solvent was removed at a

water separator. Water was added to the mixture (35 mL), the layers were separated and

the aqueous layer was extracted with dichloromethane (3 x 20 mL), the combined

organic layers were dried over MgSO4 and the solvent was removed in vacuo. The

resulting liquid (1.74 g) was submitted to flash chromatography (silica gel, PE,

Rf = 0.38) to yield 317 mg (33 %) 140 as colorless oil.

1H NMR (400 MHz, CDCl3): δ = 3.37 (s, 1 H, ≡CH), 7.20 and 7.27 (both td,

superimposed, J = 7.6, 1.9 Hz and J = 7.5, 1.6 Hz, 2 H, ArH), 7.54 (dd, J = 7.3, 2.0 Hz,

1 H, ArH), 7.59 (dd, J = 7.7, 1.4 Hz, 1 H, ArH) ppm.



1H NMR (200 MHz, CDCl3): 1-Bromo-2-ethynylbenzene (140)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

1.00

2.47

1.12

1.00

3.37

7.20

7.27

7.54

7.59

7.17.27.37.47.57.67.7f1 (ppm)

2.47

1.12

1.00

7.20

7.27

7.54

7.59

Syntheses 151

2.1.11 2-Chlorobenzoyl chloride (148a), 2-Bromobenzoyl chloride (148b),

2-Iodobenzoyl chloride (148c)

General procedure A:

2-Halobenzoic acid 147 (1 mmol) was dissolved in dry dichloromethane (2 mL), oxalyl

chloride (1.14 mmol) and one drop DMF were added and the mixture was stirred at

room temperature for 3.5 h. The solvent was removed at a rotary evaporator and the

crude product was used without further purification.

X = Cl: 99 % of 2-Chlorobenzoyl chloride 148a as slightly yellow oil.

X = Br: According to NMR nearly quantitative yield of 2-Bromobenzoyl chloride 148b

as slightly yellow oil.

General procedure B:

2-Halobenzoic acid 147 (1 mmol), thionyl chloride (2.2 mmol) and one drop DMF were

refluxed in dry dichloromethane (1.5–2 mL) for 3 h. The mixture was cooled to room

temperature, washed twice with aqueous NaHCO3 (10 %, 2 mL), water (2 mL) and

dried over MgSO4. The solvent was removed at a rotary evaporator to yield 148. The

compound was used without further purification.

X = Cl: 86-94 % of 2-Chlorobenzoyl chloride 148a as colorless oil.

X = Br: 92-98 % of 2-Bromobenzoyl chloride 148b as slightly yellow oil.

X = I: 81 % of 2-Iodobenzoyl chloride 148c as brown oil.


2-Chlorobenzoyl chloride (148a):

1H NMR (200 MHz, CDCl3): δ = 7.38–7.55 (m, 3 H, ArH), 8.08–8.13 (m, 1 H, ArH)

ppm.

2-Bromobenzoyl chloride (148b):

1H NMR (200 MHz, CDCl3): δ = 7.38–7.51 (m, 2 H, ArH), 7.67–7.76 (m, 1 H, ArH),

8.02–8.11 (m, 1 H, ArH) ppm.

2-Iodobenzoyl chloride (148c):

1H NMR (200 MHz, CDCl3): δ = 7.25 (td, 3J = 7.8, 4

J = 1.6 Hz, 1 H, ArH), 7.50 (td, 3J

= 7.8, 4J = 1.1, 1 H, ArH), 8.05 and 8.07 (both dd, 3

J = 7.9, 4J = 1.0 Hz and 3

J = 7.9, 4J

= 1.6 Hz, superimposed, 2 H, ArH) ppm.

1H NMR (200 MHz, CDCl3): 2-Chlorobenzoyl chloride (148a)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

3.17

1.00

7.38

7.55

8.08

8.13

7.47.57.67.77.87.98.08.1f1 (ppm)

3.17

1.00

7.38

7.55

8.08

8.13

Syntheses 153

1H NMR (200 MHz, CDCl3): 2-Bromobenzoyl chloride (148b)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

1.99

0.98

1.00

7.38

7.51

7.67

7.76

8.02

8.11

7.47.57.67.77.87.98.08.1f1 (ppm)

1.99

0.98

1.00

7.38

7.51

7.67

7.76

8.02

8.11

1H NMR (200 MHz, CDCl3): 2-Iodobenzoyl chloride (148c)


2.1.12 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a)

2,6-Dimethylanisole (117) (1.13 mL, 7.82 mmol), aluminium chloride (641 mg,

4.76 mmol) and 2-chlorobenzoyl chloride (148a) (678 mg, 3.87 mmol) were suspended

in dry dichloromethane (10 mL) and refluxed for 1 h 15 min. After addition of HCl

(2 N, 15 mL), the layers were separated and the aqueous layer was extracted twice with

dichloromethane (15 mL). The combined organic extracts were washed with 10 %

NaOH (15 mL), water (15 mL), dried over MgSO4 and the solvent was removed in

vacuo to yield 1.48 g of a slightly yellow liquid. The crude product was purified by

flash chromatography (silica gel, PE/EtOAc 15:1 to 5:1, Rf (10:1 PE/EtOAc) = 0.33).

After drying in vacuo (2.6 mbar, 50 °C, 35 min) 935 mg (88 %) of 149a were obtained

as slightly yellow oil which crystallized to give a colorless solid with mp 47–48 °C.

C16H15ClO2 (274.74)

calcd.: C 69.95, H 5.50

found: C 70.00, H 5.57

IR (KBr): ν~ = 3046 (w), 3034 (w), 2959 (w), 2920 (w), 2855 (w), 2835 (w), 2728 (w),

1760 (w), 1691 (w), 1665 (s), 1594 (m), 1565 (w), 1521 (w), 1481 (w), 1468 (w), 1453

(w), 1433 (m), 1417 (w), 1376 (w), 1320 (s), 1268 (w), 1237 (w), 1216 (m), 1162 (w),

1127 (s), 1062 (w), 1030 (w), 1010 (m), 978 (w), 955 (w), 906 (w), 882 (w), 844 (w),

772 (m), 751 (w), 738 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.32-7.38 (m,

2 H, Ar’H), 7.40-7.47 (m, 2 H, Ar’H), 7.49 (s, 2 H, Ar-2/6-H) ppm.

Syntheses 155

13C{

1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 126.7 (d,

Ar’CH), 129.0 (d, Ar’CH), 130.2 (d, Ar’CH), 131.0 (d, Ar’CH), 131.3 (d, ArC-2/6-H),

131.5 (s, ArC, CCH3), 132.2 (s, ArC), 139.2 (s, ArCCl), 162.1 (s, ArCO), 194.7 (s,

C=O) ppm.

MS (EI, 70 eV): m/z (%) = 274 (37) M+, 163 (100) [M– PhCl]+, 139 (8), 105 (9), 91 (8).


1H NMR (400 MHz, CDCl3): (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149a)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

6.40

3.00

2.09

2.24

1.81

2.30

3.78

7.32

7.38

7.40

7.47

7.49

7.357.407.457.50f1 (ppm)

2.09

2.24

1.81

7.32

7.38

7.40

7.47

7.49

13C NMR (100 MHz, CDCl3): (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149a)

0102030405060708090100110120130140150160170180190200f1 (ppm)

16.4

59.8

126.7

129.0

130.2

131.0

131.3

131.5

132.2

139.2

162.1

194.7

129130131132f1 (ppm)

129.0

130.2

131.0

131.3

131.5

132.2

Syntheses 157

2.1.13 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b)

2,6-Dimethylanisole (117) (1.13 mL, 7.82 mmol), aluminium chloride (620 mg, 4.60

mmol) and 2-bromobenzoyl chloride (148b) (852 mg, 3.88 mmol) were suspended in





vacuo. The crude product was purified by flash chromatography (silica gel, PE/EtOAc

15:1, Rf (10:1 PE/EtOAc) = 0.29). After drying in vacuo (2.6 mbar, 75 °C, 1 h) 1.12 g

(91 %) of 149b were obtained as slightly yellow oil which crystallized to give a

colorless solid with mp 63 °C.

C16H15BrO2 (319.19)

calcd.: C 60.21, H 4.74

found: C 60.35, H 4.75

IR (KBr): ν~ = 3057 (w), 2953 (w), 2919 (w), 2836 (w), 1757 (w), 1694 (w), 1652 (s),

1591 (s), 1481 (m), 1465 (w), 1426 (s), 1375 (w), 1320 (s), 1268 (w), 1239 (w), 1217

(s), 1160 (w), 1126 (s), 1055 (w), 1009 (s), 978 (w), 952 (w), 904 (w), 882 (w), 846

(m), 765 (s), 749 (m), 731 (w) cm-1.

UV/Vis (CH3CN): λmax (lgε) = 272 (4.2) nm.

1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.30 and 7.34

(“d” and “t”, “J” = 7.4 Hz and “J” = 7.7 Hz, 2 H, Ar’-4/6-H), 7.40 (“t”, “J” = 7.4 Hz, 1

H, Ar’-5-H), 7.48 (s, 2 H, m-Ar-2/6-H), 7.64 (d, J = 7.9 Hz, 1 H, Ar’-3-H) ppm.


13C{

1H} NMR (100 MHz, CDCl3): δ = 16.38 (q, CH3), 59.83 (q, OCH3), 119.60 (s,

Ar’C-2-Br), 127.21 (d, Ar’C-5-H), 128.90 (d, Ar’C-6-H), 131.00 (d, Ar’C-4-H), 131.46

(d, ArC-2/6-H), 131.55 (s, ArC-3/5), 131.81 (s, ArC-1), 133.28 (d, Ar’C-3-H), 141.20

(s, Ar’C-1), 162.12 (s, ArC-4-O), 195.31 (s, ArC=O) ppm.

MS (FAB): m/z (%): 343 (7) [M+Na]+, 319 (100) [M+H]+, 183 (47), 163 (33), 154 (21),

136 (18).

Syntheses 159

1H NMR (400 MHz, CDCl3): (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149b)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

6.39

3.20

1.14

0.98

1.09

2.05

1.00

2.29

3.77

7.30

7.34

7.40

7.48

7.64

7.307.357.407.457.507.557.607.65f1 (ppm)

1.14

0.98

1.09

2.05

1.00

7.30

7.34

7.40

7.48

7.64

*

13C NMR (100 MHz, CDCl3): (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149b)

0102030405060708090100110120130140150160170180190f1 (ppm)

16.4

59.8

119.6

127.2

128.9

131.0

131.5

133.3

141.2

162.1

195.3

131132133134f1 (ppm)

131.0

131.5

131.6

131.8

133.3

*


2.1.14 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c)

2,6-Dimethylanisole (117) (1.00 mL, 6.92 mmol), aluminium chloride (571 mg,

4.28 mmol) and 2-iodobenzoyl chloride (148c) (863 mg, 3.24 mmol) were suspended in





vacuo. The crude product was purified by flash chromatography (silica gel, PE/EtOAc

15:1 to 5:1, Rf (10:1 PE/EtOAc) = 0.30). After drying in vacuo (0.74 mbar, 50–100 °C

°C, 1 h) 984 mg (83 %) of 149c were obtained as slightly yellow oil which crystallized

to give a colorless solid with mp 88–90 °C.

C16H15ClO2 (366.01)

calcd.: C 52.48, H 4.13

found: C 52.59, H 4.30

IR (KBr): ν~ = 3047 (w), 2947 (w), 2919 (w), 2855 (w), 1663 (m), 1589 (w), 1481 (w),

1456 (w), 1426 (w), 1374 (w), 1313 (s), 1242 (w), 1216 (w), 1126 (m), 1006 (w), 975

(w), 949 (w), 919 (w), 885 (w), 843 (w), 768 (w), 734 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.17 (td, 3J =

7.7 Hz, 4J = 1.7 Hz, 1 H, Ar’-4-H), 7.27 (dd, 3

J = 7.1 Hz, 4J = 1.6 Hz, 1 H, Ar’-6-H),

7.43 (td, 3J = 7.5 Hz, 4J = 1.1 Hz, 1 H, Ar’-5-H), 7.48 (s, 2 H, Ar-2/6-H), 7.92 (dd, 3

J =

8.0 Hz, 4J = 0.8 Hz, 1 H, Ar’-3-H) ppm.

Syntheses 161

13C{

1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 92.4 (s, ArCI),

127.8 (d, Ar’C-5-H), 128.4 (d, Ar’C-6-H), 131.0 (d, Ar’C-4-H), 131.3 (s, ArC-1), 131.6

(s, ArCCH3), 131.7 (d, ArC-2/6-H), 139.8 (s, Ar’C-3-H), 144.9 (s, Ar’C-1), 162.1 (s,

ArCO), 196.8 (s, C=O) ppm.

MS (EI, 70 eV): m/z (%) = 366 (79) M+, 239 (14) [M–I]+, 231 (19), 203 (11), 163 (100),

105 (14), 91 (18), 76 (11).


1H NMR (400 MHz, CDCl3): (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149c)

13C NMR (100 MHz, CDCl3): (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149c)

Syntheses 163

2.1.15 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)

Procedure A:

(2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) (274 mg,

1.00 mmol) or (2-bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b)

(319 mg, 1.00 mmol), potassium carbonate (278 mg, 2.01 mmol) and

tricyclohexylphosphonium tetrafluoroborate (39 mg, 105 µmol) were suspended in

DMA (5 mL) in a screw-cap flask. The suspension was degassed with argon for 10 min

before Pd(OAc)2 (11 mg, 49 µmol) was added. The mixture was heated to 170 °C for 3

d, cooled to room temperature, hydrolyzed with water (15 mL) and extracted with

CH2Cl2 (4 x 15 mL). The organic layer was washed with HCl (2 N, 15 mL), water (15

mL), brine (15 mL) and dried over MgSO4. The solvents were removed under reduced

pressure and the residue purified by flash chromatography (silica gel, toluene, Rf =

0.30). After drying in vacuo (1.7 mbar, 50 °C) Z was obtained a yellow crystalline solid

with mp 97–99 °C.

X = Cl: 175 mg, 74 %

X = Br: 158 mg, 66 %

Procedure B:

(2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) (319 mg,

1.00 mmol), potassium carbonate (829 mg, 6.00 mmol) and pivalic acid (102 mg,

1.00 mmol) were dissolved in DMA (10 mL) and toluene (5 ml) in a screw-cap flask

under argon. After addition of Bedford catalyst 150 (47 mg, 30 µmol) the reaction

mixture was heated to 120 °C for 10 h, cooled to room temperature and hydrolyzed with

HCl (2 N, 20 mL). The mixture was extracted with CH2Cl2 (3 x 10 mL), the organic

layer was washed with water (15 mL) dried over MgSO4 and the solvents were removed


under reduced pressure. The residue was purified by flash chromatography (silica gel,

toluene, Rf = 0.30) to yield 151 (215 mg, 90 %) as a yellow solid after drying in vacuo

(2.1 mbar, 50 °C).

IR (KBr): ν~ = 3015 (w), 3000 (w), 2950 (w), 2935 (w), 2917 (w), 2884 (w), 2847 (w),

2826 (w), 1731 (w), 1707 (s), 1604 (m), 1577 (m), 1467 (w), 1448 (m), 1437 (m), 1401

(w), 1363 (m), 1301 (m), 1229 (m), 1185 (m), 1166 (w), 1127 (s), 1088 (w), 1035 (w),

1005 (s), 956 (w), 885 (w), 864 (w), 800 (w), 767 (w), 750 (m), 718 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 336 (3.4), 323 (3.4), 301 (3.6), 289 (3.5), 255 (4.5) nm.

1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 3 H, CH3), 2.50 (s, 3 H, CH3), 3.76 (s, 3 H,

OCH3), 7.25 (td, J = 7.5 Hz, J = 0.8 Hz, 1 H, ArH), 7.38 (s, 1 H, Ar-H), 7.45 (td, J = 7.6

Hz, J = 1.2 Hz, 1 H, ArH), 7.60 (d, J = 7.6 1 H, ArH), 7.63 („d“, „J“ = 7.3 Hz, 1 H,

ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 12.8 (q, CH3), 16.6 (q, CH3), 60.3 (q, OCH3),

123.1 (d, ArCH), 124.2 (d, ArCH), 125.0 (d, ArC-H), 127.6 (s, ArC), 128.3 (d, ArCH),

130.2 (s, ArC), 131.7 (s, ArC), 134.5 (d, ArCH), 135.1 (s, ArC), 142.5 (s, ArC), 145.2

(s, ArC), 162.8 (s, ArCO), 193.7 (s, C=O) ppm.

MS (EI, 70 eV): m/z (%) = 238 (100) M+, 223 (36) [M–CH3]+, 195 (10), 165 (24), 152

(15).

1H NMR data are in accord with those reported in the literature.133

Syntheses 165

1H NMR (400 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

2.96

3.01

3.00

1.20

0.88

0.96

1.00

0.85

2.29

2.50

3.76

7.25

7.38

7.45

7.60

7.63

7.27.37.47.57.6f1 (ppm)

1.20

0.88

0.96

1.00

0.85

7.25

7.38

7.45

7.60

7.63

13C NMR (100 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)

0102030405060708090100110120130140150160170180190f1 (ppm)

12.8

16.6

60.3

123.1

124.2

125.0

127.6

128.3

130.2

131.7

134.5

135.1

142.5

145.2

162.8

193.7


2.1.16 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)

To a solution of 2,6-dimethylanisole (117) (0.962 g, 6.92 mmol) and phthalic anhydride

(153) (1.13 g, 7.61 mmol) in dry dichloromethane (10 mL) was added a solution of

AlCl3 (1.19 g, 8.89 mmol) in dry nitromethane (1.7 mL) at room temperature. The

mixture was refluxed for 1 h 15 min and poured into water (10 mL). The aqueous layer

was extracted with dichloromethane (2 x 10 mL), the organic layer was washed with

hydrochlorid acid (2 N, 10 mL), water (10 mL) and brine (10 mL), dried over MgSO4

and the solvent was removed in vacuo. The residue was purified by flash

chromatography (silica gel, PE/DCM to remove unreacted starting material and then

PE/EtOAc 2:1, Rf = 0.13) and the product dried in vacuo (1.1 mbar, 75 °C, 30 min) to

yield 154 (172 mg, 9 %) as colorless solid with mp 171 °C.

HRMS (EI, 70 eV): C17H16O4 (284.31)

calcd.: 284.1049

found: 284.1046

IR (KBr): ν~ = 2984 (w), 2956 (w), 2933 (w), 2823 (w), 2667 (w), 2537 (w), 1693 (s),

1669 (s), 1593 (m), 1575 (w), 1481 (w), 1451 (w), 1418 (m), 1386 (w), 1312 (s), 1237

(w), 1210 (m), 1166 (w), 1146 (w), 1124 (m), 1088 (w), 1043 (w), 997 (w), 942 (w),

909 (w), 848 (w), 810 (w), 767 (w), 708 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.27 (s, 6 H, CH3), 3.76 (s, 3 H, OCH3), 7.34 (dd, 3J =

7.5 Hz, 4J = 0.9 Hz, 1 H, Ar’H), 7.41 (s, 2 H, Ar-2/6-H), 7.56 (td, 3

J = 7.6 Hz, 4J = 1.2

Hz, 1 H, Ar’H), 7.65 (td, 3J = 7.5 Hz, 4

J = 1.2 Hz, 1 H, Ar’H), 8.09 (dd, 3J = 7.8 Hz, 4

J

= 0.9 Hz, 1 H, Ar’H) ppm.

Syntheses 167

13C{

1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 127.9 (d,

PHCH), 128.0 (s, Ar’CCOOH), 129.5 (d, Ar’CH), 130.9 (d, ArC-2/6-H), 131.1 (d,

Ar’CH), 131.3 (s, ArCCH3), 132.6 (s, ArC), 133.1 (d, Ar’CH), 143.0 (s, Ar’C), 161.7 (s,

ArCO), 169.7 (s, COOH), 196.6 (s, C=O) ppm.

MS (EI, 70 eV): m/z (%) = 284 (37) M+, 225 (12), 209 (14), 163 (100), 149 (13), 105

(14), 91 (14), 65 (11)


1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)

13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)

Syntheses 169

2.1.17 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)

Phthaloyl dichloride (159) (0.21 mL, 1.38 mmol) and aluminium chloride (216 mg,

1.62 mmol) were dissolved in dry dichloromethane (15 mL). 2,6-Dimethylanisole (117)

(0.20 mL, 1.38 mmol) was added dropwise to the yellow solution which turned dark red

upon addition. The mixture was stirred for 18 hours at room temperature before adding

again aluminium chloride (216 mg, 1.62 mmol) and stirring for further 26 hours. It was

hydrolysed with hydrochloric acid (2 N, 7 mL) and the aqueous layer was extracted

with dichloromethane (3 x 10 mL), the combined organic layers were washed with

sodium hydrogencarbonate (10 mL), water (2 x 10 mL), dried over MgSO4 and the

solvent was removed in vacuo. The brown liquid was subjected to flash chromatography

(silica gel, PE/EtOAc 5:1 to 2:1, Rf (2:1) = 0.54) to yield 371 mg (67 %) 161 as a

colorless solid with mp 194–196 °C.

C26H26O4 (402.48)

calcd.: C 77.59, H 6.51

found: C 77.37, H 6.72

IR (KBr): ν~ = 2950 (w), 2928 (w), 2822 (w), 1769 (s), 1659 (w), 1597 (w), 1482 (w),

1463 (w), 1416 (w), 1376 (w), 1310 (w), 1290 (w), 1249 (w), 1228 (w), 1150 (w), 1110

(w), 1093 (w), 1008 (w), 979 (w), 935 (w), 912 (w), 882 (w), 859 (w), 818 (w), 797 (w),

763 (w), 746 (w), 722 (w), 695 (w) cm-1.




Ar-2/6-H), 7.54 (m, 2 H, Ar’H), 7.69 (“t”, “J” = 7.6 Hz, 1 H, Ar’H), 7.92 (d, J = 7.6 Hz,

1 H, Ar’H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 91.8 (s, ArC),

124.3 (d, Ar’CH), 125.7 (s, Ar’CC=O), 126.1 (d, Ar’CH), 127.7 (d, ArC-2/6-H), 129.3

(d, Ar’CH), 131.0 (s, ArCCH3), 134.1 (d, Ar’CH), 136.2 (s, ArC), 152.7 (s, Ar’C),

157.2 (s, ArCO), 170.1 (s, C=O) ppm.

MS (FAB): m/z (%) = 403 (100) [M+H]+, 307 (12), 267 (24).

Syntheses 171

1H NMR (400 MHz, CDCl3): 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)

13C NMR (100 MHz, CDCl3): 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)


2.1.18 4-Bromo-2,6-dimethylphenol (208)

2,6-Dimethylphenol (155) (1.22 g, 9.99 mmol) was dissolved in chloroform (40 mL)

and a solution of bromine (1.50 g, 9.96 mmol) in chloroform (25 mL) was added

dropwise. The reaction mixture was stirred 1.5 h at room temperature after complete

addition, washed with aqueous sodium sulfite (10 %, 15 mL) aqueous ammonium

chloride (1 N, 15 mL) and dried over MgSO4. The solvent was avaporated and the

resulting solid (1.93 g) was recrystallized from PE (25 mL) to yield 1.36 g (69 %) of

208 as colorless solid with mp 79 °C (lit.194 79.5 °C)

1H NMR (200 MHz, CDCl3): δ = 2.21 (s, 6 H, CH3), 4.56 (s, 1 H, OH), 7.10 (s, 2 H, m-

ArH) ppm.

MS (EI): m/z (%) = 199 (199) M+, 121 (75) [M–Br]+, 103 (13), 91(31), 77 (26).


Syntheses 173

1H NMR (200 MHz, CDCl3): 4-Bromo-2,6-dimethylphenol (208)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

6.25

1.00

1.99

2.22

4.57

7.10


2.1.19 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)

4-Bromo-2,6-dimethylphenol (208) (314 mg, 1.55 mmol) and 2-biphenylboronic acid

(190) (328 mg, 1.66 mmol) were dissolved in anhydrous THF (5 mL) in a screw-cap

flask. After addition of 2 M K2CO3 (5 mL) the solution was degassed with argon for

5 min, Pd(PPh3)4 (89 mg, 73 µmol) was added and the mixture was heated to 120 °C for

20 h. After cooling to room temperature it was extracted with dichloromethane

(2 x 10 mL), the combined organic layers were washed with brine (20 mL), dried over

MgSO4 and the solvent was removed at a rotary evaporator. The residue was purified by

flash chromatography (silica gel, PE/EtOAc 10:1, Rf = 0.25) to yield 209 as a pale

yellow highly viscous oil (282 mg, 66 %) after drying in vacuo (0.81 mbar, 50 °C, 1 h).

HRMS (EI): C20H18O



IR (ATR): ν~ = 3566 (w), 3021 (w), 2917 (w), 1659 (w), 1599 (w), 1489 (w), 1471 (w),

1448 (w), 1431 (w), 1377 (w), 1312 (w), 1235 (w), 1200 (w), 1181 (m), 1114 (w), 1080

(w), 1022 (w), 1008 (w), 985 (w), 941 (w), 913 (w), 883 (w), 869 (w), 803 (w), 760

(m), 743 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 270 nm (3.9, sh), 240 (4.2) nm.

1H NMR (400 MHz, CDCl3): δ = 2.12 ppm (s, 6 H, CH3), 4.50 (s, 1 H, OH), 6.73 (s, 2

H, m-ArH), 7.16–7.21 (m, 5 H, biphenylH), 7.35–7.42 (m, 4 H, biphenylH) ppm.

Syntheses 175

13C{

1H} NMR (100 MHz, CDCl3): δ = 15.9 ppm (q, CH3), 122.5 (d, biphenylCH ),

126.4 (s, ArC), 127.0 (s, ArC), 127.5 (d, biphenylCH), 127.9 (d, biphenylCH), 130.0 (d,

biphenylCH), 130.3 (d, m-ArCH), 130.6 (d, biphenylCH), 130.7 (d, biphenylCH), 133.6

(s, ArC), 140.5 (s, ArC), 140.6 (s, ArC), 142.0 (s, ArC), 151.0 (s, COH) ppm.

MS (FAB): m/z (%) = 274 (100) M+.


1H NMR (400 MHz, CDCl3): 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

6.52

1.00

2.04

5.19

4.42

2.12

4.50

6.74

7.15

7.23

7.35

7.42

7.17.27.37.4f1 (ppm)

5.19

4.42

7.15

7.23

7.35

7.42

13C NMR (100 MHz, CDCl3): 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)

0102030405060708090100110120130140150f1 (ppm)

15.9

122.5

126.4

127.0

127.5

127.9

130.0

130.3

130.6

130.6

133.6

140.5

140.6

142.0

151.0

126127128129130131f1 (ppm)

126.4

127.0

127.5

127.9

130.0

130.3

130.6

130.6

Syntheses 177

2.1.20 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)

Biphenylphenol 209 (190 mg, 693 µmol) were dissolved in dichloromethane (2 mL)

and 2,2,2-trifluroroethanol (6 mL) and PIFA was added (334 mg, 761 µmol). The

mixture was stirred at room temperature for 20 min. The solvents were removed at a

rotary evaporator and the residue purified by flash chromatography (silica gel,

PE/toluene 1:1, Rf = 0.15). After drying in vacuo (1.7–2.6 mbar, 60 °C, 2 h) 210

(132 mg, 70 %) was obtained as colorless solid with mp 143 °C. An analytically pure

sample was obtained by crystallization from DCM/MeOH.

C20H16O (272.34)

calcd.: C 88.20, H 5.92

found: C 88.15, H 5.85

IR (ATR):ν~ = 3011 (w), 2955 (w), 2923 (w), 1698 (w), 1662 (w), 1638 (m), 1602 (w),

1472 (w), 1446 (w), 1396 (w), 1367 (w), 1278 (w), 1234 (w), 1202 (w), 1162 (w), 1095

(w), 1036 (w), 933 w), 867 (w), 757 (m), 730 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 302 (3.8), 291 (3.7), 267 (4.2, sh), 245 (4.3, sh), 234

(4.5), 223 (4.6) nm.

1H NMR (400 MHz, CDCl3): δ = 1.98 (s, 6 H, CH3), 6.30 (s, 2 H, CH=C), 7.21 (d, J =

7.5 Hz, 2 H, ArH), 7.30 (td, J = 7.5 Hz, J = 1.1 Hz, 2 H, ArH), 7.43 (td, J = 7.5 Hz, J =

1.1 Hz, 2 H, ArH), 7.79 (d, J = 7.6 , 2 H, ArH) ppm.


13C{

1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 56.9 (s, Spiro-C), 120.7 (d,

ArCH), 125.0 (d, ArCH), 128.1 (d, ArCH), 128.7 (d, ArCH), 135.5 (s, ArC), 141.6 (s,

ArC), 143.9 (s, ArC), 144.6 (d, CH=C), 187.9 (s, C=O) ppm.

MS (FAB): m/z (%) = 273 (100) [M+H]+, 258 (14).

Syntheses 179

1H NMR (400 MHz, CDCl3): 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)

13C NMR (100 MHz, CDCl3): 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)


2.1.21 1,3-Dimethyltriphenylen-2-yl acetate (211)

Spiro compound 210 (150 mg, 551 µmol) was suspended in acetic anhydride (3 mL)

and one drop of concentrated sulfuric acid was added before heating the mixture to

100 °C for 30 min. The mixture was poured onto ice and extracted with

dichloromethane (2 x 15 mL). The combined organic layers were washed with water

(15 mL), brine (15 mL) dried over MgSO4 and the solvent was removed at a rotary

evaporator. The brown residue was purified by flash chromatography (silica gel,

PE/EtOAc 10:1, Rf = 0.25) to yield 211 (159 mg, 92 %) as a colorless solid with

mp 153 °C after drying in vacuo (1.3 mbar, 75°C). An analytically pure sample was

obtained by crystallization from DCM/PE.

C22H18O2 (314.38)

calcd.: C 84.05, H 5.77

found: C 83.85, H 5.72

IR (KBr):ν~ = 3078 (w), 3050 (w), 3002 (w), 2966 (w), 2917 (w), 1749 (s), 1607 (w),

1539 (w), 1490 (w), 1439 (m), 1422 (w), 1373 (m), 1343 (w), 1315 (w), 1218 (s), 1169

(w), 1154 (w), 1127 (m), 1082 (w), 1045 (w), 1010 (w), 996 (w), 946 (w), 923 (w), 880

(w), 857 (w), 814 (w), 757 (s), 721 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 289 nm (4.3), 280 (4.3, sh), 262 (4.9), 255 (4.9, sh) nm.

1H NMR (400 MHz, CDCl3): δ = 2.42 ppm (s, 3 H, CH3), 2.46 (s, 3 H, CH3), 2.76 (s, 3

H, C(O)CH3), 7.54 (“t”, “J” = 7.7 Hz, 1 H, ArH), 7.59–7.63 (m, 3 H, ArH), 8.37 (s, 1 H,

m-ArH), 8.41 (d, J = 8.3 Hz, 1 H, ArH), 8.52–8.58 (m, 2 H, ArH), 8.60 (d, J = 8.2 Hz, 1

H, ArH) ppm.

Syntheses 181

13C{

1H} NMR (100 MHz, CDCl3): δ = 17.4 (q, CH3), 18.4 (q, CH3), 20.8 (q, C(O)CH3),

12.9 (m-ArCH), 123.2(ArCH), 123. 5 (d, ArCH), 123.6 (d, ArCH), 125.55 (d, ArCH),

126.8 (s, ArC), 127.1 (s, ArC), 127.2 (ArCH), 127.4 (s, ArC), 128.9 (d, ArCH), 129.2

(s, ArC), 130.0 (ArC), 130.1 (s, ArC), 130.3 (s, ArC), 130.4 (s, ArC), 131.2 (s, ArC),

149.01 (s, ArCO), 169.1 (s, C=O) ppm.

MS (FAB): m/z (%) = 314 (23) M+, 272 (100) [M+–C(O)CH3], 256 (13), 239 (11).


1H NMR (400 MHz, CDCl3): 1,3-Dimethyltriphenylen-2-yl acetate (211)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

1.46

1.45

1.50

0.50

1.45

0.49

0.50

1.00

0.42

2.42

2.46

2.76

7.54

7.59

7.63

8.37

8.41

8.52

8.58

8.60

7.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)

0.50

1.45

0.49

0.50

1.00

0.42

7.54

7.59

7.63

8.37

8.41

8.52

8.58

8.60

13C NMR (100 MHz, CDCl3): 1,3-Dimethyltriphenylen-2-yl acetate (211)

0102030405060708090100110120130140150160170f1 (ppm)

17.4

18.4

20.8

31.0

122.9

123.2

123.4

123.5

125.6

126.8

127.1

127.2

127.4

128.9

129.2

130.0

130.1

130.3

130.4

131.2

149.0

169.1

122123124125126127128129130131f1 (ppm)

122.9

123.2

123.4

123.5

125.6

126.8

127.1

127.2

127.4

128.9

129.2

130.0

130.1

130.3

130.4

131.2

Syntheses 183

2.1.22 4-Methoxy-3,5-dimethylbenzaldehyde (250)

2-Methoxy-1,3-dimethylbenzene 117 (1.92 g, 13.8 mmol) and HMTA (3.96 g,

28.3 mmol) were dissolved in trifluoroacetic acid (20 mL) under argon and heated to

90 °C overnight. The resulting brownish solution was hydrolyzed with 4 N HCl (60 mL)

and stirred at room temperature for 15 min. The mixture was extracted with DCM

(4 x 30 mL) and the organic layer was washed with water (2 x 30 mL), saturated

aqueous Na2CO3 (30 mL) and dried over MgSO4. The solvent was removed at a rotary

evaporator. The obtained brown liquid (2.59 g) was submitted to flash chromatography

(silica gel, PE/DCM 1:1, Rf = 0.24) to yield colorless 250 (1.94 g, 85 %) after drying in

vacuo (2.2 mbar, rt to 50 °C).

1H NMR (200 MHz, CDCl3): δ = 2.34 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.55 (s, 2 H

ArH), 9.87 (s, 1 H, CHO) ppm.

13

C{1H} NMR (50 MHz, CDCl3): δ = 16.3 (q, CH3), 59.8 (q, OCH3), 130.8 (d, ArCH),

132.1 (s, ArCCH3), 132.4 (s, ArC), 162.5 (s, ArCO), 191.8 (s, CHO) ppm.

MS (EI, 70 eV): m/z (%) = 164 (100) M+, 149 (18) [M–CH3]+, 137 (16), 121 (12), 105

(22), 91 (25), 77 (22).

The NMR spectroscopic data are in accord with those reported in literature.172


1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzaldehyde (250)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

6.12

3.07

2.01

1.00

2.34

3.77

7.55

9.87

13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzaldehyde (250)

0102030405060708090100110120130140150160170180190f1 (ppm)

16.3

59.8

130.8

132.1

132.4

162.5

191.8

131132f1 (ppm)

130.8

132.1

132.4

Syntheses 185

2.1.23 4-Methoxy-3,5-dimethylbenzoic acid (251)

4-Methoxy-3,5-dimethylbenzaldehyde 250 (897 mg, 5.46 mmol) and sulfamic acid

(904 mg, 9.31 mmol) were suspended in water (65 mL) and acetone (6 mL). To this a

solution of sodium chlorite (739 mg, 6.54 mmol) in water (5 mL) was added dropwise

upon which a colorless solid precipitated. The mixture was stirred 1 h at room

temperature and extracted with ethyl acetate (4 x 20 mL). The organic layer was washed

with brine (30 mL), dried over MgSO4 and the solvent removed at a rotary evaporator.

After drying in vacuo (0.73 mbar, 50 °C) 251 (959 mg, 97 %) was obtained as colorless

to pale yellow solid with mp 193-194 °C (lit.173 192–194 °C).


ArH) ppm.

13


131.3 (d, ArCH), 131.4 (s, ArCCH3), 162.0 (s, ArCO), 172.4 (s, COOH) ppm.


1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoic acid (251)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

6.03

3.00

2.00

2.33

3.77

7.79

13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoic acid (251)

0102030405060708090100110120130140150160170f1 (ppm)

16.3

59.8

124.7

131.3

131.4

162.0

172.4

131.2131.3131.4f1 (ppm)

131.3

131.4

Syntheses 187

2.1.24 4-Methoxy-3,5-dimethylbenzoyl chloride (245)

4-Methoxy-3,5-dimethylbenzoic acid 251 (645 mg, 3.58 mmol) was suspended in dry

CH2Cl2 (4 mL), thionyl chloride (0.6 mL, 7.85 mmol, 95.5 %) and one drop DMF were

added and the mixture was refluxed for 3 h. The solvent was removed at a rotary

evaporator and the residue dissolved in CH2Cl2, washed with aqueous NaHCO3 (10 %,

2 x 10 mL), water (10 mL) and dried over MgSO4. The solvent was removed by rotary

evaporation and the residue distilled at a Kugelrohr oven (1.3 mbar, 150 °C) to yield

245 (643 mg, 90 %) as pale yellow liquid, which solidified with mp 38–39 °C

(lit.175 40 °C).


ArH) ppm.

13


132.0 (s, ArCCH3), 132.7 (s, ArCH), 163.4 (s, ArCO), 167.8 (s, C=O) ppm.


1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoyl chloride (245)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

6.34

3.06

2.00

2.34

3.79

7.80

13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoyl chloride (245)

0102030405060708090100110120130140150160170f1 (ppm)

16.4

59.9

128.4

132.0

132.7

163.4

167.8

Syntheses 189

2.1.25 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)

Benzoyl chloride 245 (1.69 g, 8.52 mmol) was dissolved in THF (12 mL) and cooled to

0 °C. A solution of picolinohydrazide (244) (1.10 g, 8.04 mmol) and sodium carbonate

(793 mg, 7.48 mmol) in water (10 mL) and THF (12 mL) was added dropwise and the

mixture was stirred at 0 °C for 3 h. The reaction mixture was extracted with CH2Cl2

(3 x 30 mL), the organic layer was washed with water (30 mL) and brine (30 mL), dried

over MgSO4 and the solvents were removed by rotary evaporation. The obtained solid

(2.69 g) was recrystallized from ethanol (16 mL) and methanol (4 mL) under reflux to

yield 246 (1.96 g, 82 %) as a colorless solid with mp 170 °C after drying in vacuo.

C16H17N3O3 (299.32)

calcd.: C 64.20, H 5.72, N 14.04

found: C 64.24, H 5.80, N 13.93

IR (KBr): ν~ = 3230 (w), 3051 (w), 3016 (w), 2972 (w), 2938 (w), 2822 (w), 1681 (m),

1643 (s), 1602 (w), 1589 (w), 1570 (w), 1552 (w), 1500 (m), 1485 (m), 1463 (m), 1432

(w), 1377 (w), 1334 (w), 1296 (w), 1222 (w), 1185 (w), 1166 (m), 1119 (w), 1088 (w),

1074 (w), 1042 (w), 1020 (w), 999 (w), 964 (w), 906 (w), 891 (w), 815 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.74 (s, 3 H, OCH3), 7.47 (ddd, 3J

= 7.6 Hz, 3J = 4.8 Hz, 4

J = 1.2 Hz, 1 H, PyH), 7.56 (s, 2 H, ArCH), 7.86 (“td”, 3J = 7.8

Hz, 3J = 7.7 Hz, 4J = 1.7 Hz, 1 H, PyH), 8.15 (“dt”, J = 37.8 Hz, 5J = 0.9 Hz, 1 H, PyH),

8.61 (ddd, 3J = 4.7 Hz, 4

J = 1.5 Hz, 5J = 0.8 Hz, 1 H, PyH), 9.18 (d, J = 5.1 Hz, 1 H,

NH), 10.52 (d, J = 5.9 Hz, 1 H, NH) ppm.


13C{

1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59.9 (q, OCH3), 122.6 (d, PyCH),

126.9 (d, PyCH), 127.0 (s, ArC), 128.2 (d, ArCH), 131.7 (s, ArCCH3), 137.5 (d, PyCH),

148.4 (s, PyC), 148.8 (d, PyCH), 160.68 (s, ArCO), 160.70 (s, C=O), 164.0 (s, C=O)

ppm.

MS (EI, 70 eV): m/z (%) = 299 (6) M+, 163 (100) [M–C6H6N3O]+.

Syntheses 191

1H NMR (400 MHz, CDCl3): N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

6.15

3.08

1.02

2.07

1.02

1.00

1.01

1.00

0.94

2.30

3.74

7.47

7.56

7.86

8.15

8.61

9.18

10.52

7.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)

1.02

2.07

1.02

1.00

1.01

7.47

7.56

7.86

8.15

8.61

13C NMR (100 MHz, CDCl3): N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)

0102030405060708090100110120130140150160f1 (ppm)

16.3

59.9

122.6

126.9

127.0

128.2

131.7

137.5

148.4

148.8

160.7

160.7

164.0

127.0f1 (ppm)

126.9

127.0

160.6160.7f1 (ppm)

160.68

160.70


2.1.26 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydrazonoyl

chloride (247)

Picolinohydrazide 246 (669 mg, 2.24 mmol) was dissolved in chloroform (45 mL), PCl5

(9.00 g, 42.8 mmol) was added and the supension heated to reflux for 24 h. The cooled

mixture was poured onto ice water (50 mL), the layers were separated and the aqueous

layer was extracted with DCM (3 x 30 mL). The combined organic layers were washed

with saturated aqueous NaHCO3 (2 x 25 mL), brine (30 mL) and dried over MgSO4.

The solvent was removed by rotary evaporation and the residue purified by flash

chromatography (silica gel, PE/EtOAc 5:1 to 2:1, Rf (2:1) = 0.46) to yield 247 (455 mg,

61 %) as yellow oil, which solidified upon standing. Analytically pure material was

obtained by crystallization from DCM/isopropanol as delicate colorless needles with

mp 66 °C after drying in vacuo (1.6 mbar, 75 °C, 1 h).

C16H15Cl2N3O (336.22)

calcd.: C 57.16, H 4.50, N 12.50

found: C 56.78, H 4.47, N 12.23

IR (KBr): ν~ = 3137 (w), 3055 (w), 2990 (w), 2958 (w), 2919 (w), 2857 (w), 2829 (w),

1603 (m), 1588 (m), 1565 (w), 1481 (w), 1464 (m), 1427 (w), 1374 (w), 1318 (w), 1296

(w), 1272 (w), 1233 (w), 1186 (w), 1153 (m), 1094 (w), 1049 (w), 1011 (m), 948 (w),

896 (w), 871 (w), 815 (w) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 284 (4.5), 269 (4.5, sh) nm.


= 7.5 Hz, 3J = 4.8 Hz, 4

J = 1.1 Hz, 1 H, PyH), 7.80 (s, 2 H, ArH)), 7.83 (“td”, 3J = 7.7

Hz, 4J = 1.7 Hz, 1 H, PyH), 8.24 (“dt”, 3

J = 8.0 Hz, 5J = 0.9 Hz, 1 H, PyH), 8.78 (ddd,

3J = 4.8 Hz, 4J = 1.6 Hz, 5J = 0.8 Hz, 1 H, PyH) ppm.

Syntheses 193

13C{

1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.9 (q, OCH3), 123.5 (d, PyCH),

125.8 (d, PyCH), 128.9 (s, ArC), 129.5 (d, ArCH), 131.5 (s, ArCCH3), 136.9 (d, PyCH),

143.9 (CClPy), 144.2 (s, ArCCl), 149.7 (d, PyCH), 150.9 (s, PyC), 160.6 (s, ArCO)

ppm.

MS (FAB): m/z (%) = 358 (11) [M+Na]+, 336 (100) [M+H]+, 300 (53), 196 (50), 161

(18), 137 (15), 105 (15), 78 (33).


1H NMR (400 MHz, CDCl3): N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)-picolinohydrazonoyl chloride (247)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

6.16

3.00

0.99

1.80

1.05

1.00

0.94

2.36

3.77

7.43

7.80

7.83

8.24

8.78

7.58.08.5f1 (ppm)

0.99

1.80

1.05

1.00

0.94

7.43

7.80

7.83

8.24

8.78

13C NMR (100 MHz, CDCl3): N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)-picolinohydrazonoyl chloride (247)

0102030405060708090100110120130140150160f1 (ppm)

16.4

59.9

123.5

125.8

128.9

129.5

131.5

136.9

143.9

144.2

149.7

150.9

160.6

Syntheses 195

2.1.27 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)

Picolinohydrazonoyl chloride 247 (211 mg, 0.63 mmol) was dissolved in anhydrous

acetonitrile (5 mL) and hydrazine hydrate (30 µl, 0.60 mmol) was added. The mixture

was heated to 50 °C for 1 h, then potassium carbonate (169 mg, 1.22 mmol) was added

and the mixture refluxed for 24 h. After renewed addition of hydrazine hydrate (90 µl,

1.83 mmol) it was refluxed for another hour and cooled to room temperature. The solid

was collected by filtration, washed with ethanol and purified by flash chromatography

(silica gel, PE/EtOAc 5:1 to 1:1, Rf (2:1) = 0.18). Oxadiazole 253 (50 mg, 28 %) was

obtained as pale brown solid, which was recrystallized from ethanol to yield analytically

pure material (32 mg, 18 %) after drying in vacuo (1 mbar, 50–75 °C) with

mp 157–158 °C.

C16H15N3O2 (281.31)

calcd.: C 68.31, H 5.37, N 14.94

found: C 68.24, H 5.33, N 14.90

IR (KBr): ν~ = 3094 (w), 3060 (w), 2986 (w), 2952 (w), 2938 (w), 2922 (w), 2856 (w),

2830 (w), 1608 (w), 1588 (w), 1546 (w), 1476 (m), 1462 (s), 1443 (m), 1410 (m), 1375

(w), 1310 (w), 1293 (w), 1243 (m), 1207 (m), 1171 (w)1142 (w), 1116 (m), 1092 (w),

1046 (w), 1015 (m), 989 (w), 973 (w), 955 (w), 888 (w), 803 (w) cm-1.



= 7.6 Hz, 3J = 4.8 Hz, 4

J = 1.1 Hz, 1 H, PyH), 7.90 (s and “td”, superimposed, 3J = 7.8

Hz, 4J = 1.4 Hz, 3 H, ArH, PyH), 8.32 (“dt”, 3

J = 8.0 Hz, 5J = 0.9 Hz, 1 H), 8.82 (ddd,

3J = 4.8 Hz, 4J = 1.6 Hz, 5J = 0.9 Hz, 1 H, PyH) ppm.


13C{

1H} NMR (100 MHz, CDCl3): δ = 16.2 (q, CH3), 59.9 (q, OCH3), 119.1 (s, ArC),

123.4 (d, PyCH), 125.8 (d, PyCH), 128.2 (d, ArCH), 132.2 (s, CCH3), 137.3 (d, PyCH),

144.0 (s, PyC), 150.4 (d, PyCH), 160.5 (s, ArCO), 163.8 (s, PyCC), 165.8 (s, ArCC)

ppm.

MS (EI, 70 eV): m/z (%) = 281 (100) M+, 238 (15), 210 (15), 163 (82), 78 (19).

Syntheses 197

1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

6.40

3.00

0.97

2.97

0.89

0.93

2.36

3.79

7.47

7.90

8.32

8.82

7.47.67.88.08.28.48.68.8f1 (ppm)

0.97

2.97

0.89

0.93

7.47

7.90

8.32

8.82

13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)

0102030405060708090100110120130140150160170f1 (ppm)

16.2

59.9

119.1

123.4

125.8

128.2

132.2

137.3

144.0

150.4

160.5

163.8

165.8


2.1.28 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)

Hydrazonoyl chloride 247 (220 mg, 0.65 mmol) and hydrazine dihydrochloride (310

mg, 98 %, 2.89 mmol) were dissolved in dry pyridine under argon and refluxed for 1 h.

The solvent was removed in vacuo, the residue taken up in CHCl3 (20 mL) and washed

with water (3 x 20 mL), dried over MgSO4 and the solvent was evaporated. The brown

residue was purified by flash chromatography (silica gel, PE/EtOAc 5:1 to 2:1,

Rf (2:1) = 0.24) to yield 248 as red film (~ 94 mg, 49 %) already containing traces of

tetrazine due to oxidation in air. The mixture was used without further purification.

Dihydrotetrazine 248 (80 mg, 0.27 mmol) was dissolved in conc. acetic acid (2 mL) at 0

°C and aqueous 10 % NaNO2 (2 mL) was added dropwise. Diethylether (1 mL) was

added to the highly viscous purple mixture and it was stirred for 20-30 min. The

precipitated solid was collected by filtration, purified by flash chromatography (silica

gel, PE/EtOAc 1:1, Rf = 0.23) and dried in vacuo (1.3 mbar, 75–100 °C, 2 h) to yield

tetrazine 249 (21 mg, 47 %) as purple solid with mp 154–155 °C.

HRMS: C16H15N5O (293.32)

calcd.: 293.1277

found: 293.1294

IR (KBr): ν~ = 3042 (w), 2983 (w), 2920 (w), 2830 (w), 1598 (w), 1582 (w), 1571 (w),

1491 (w), 1466 (w), 1436 (w), 1390 (s), 1326 (w), 1246 (w), 1212 (m), 1173 (w), 1118

(w), 1090 (w), 1072 (w), 1058 (w), 1040 (w), 1005 (w), 993 (w), 955 (w), 915 (w), 893

(w), 834 (w), 778 (w), 765 (w), 737 (w), 714 (w) cm-1.

Syntheses 199

UV/Vis (CH3CN): λmax (lg ε) = 538 (2.7), 310 (4.6), 303 (4.5), 235 (4.1) nm.


= 7.6 Hz, 3J = 4.8 Hz, 4J = 1.1 Hz, 1 H, PyH), 7.98 (“td”, 3J = 7.8 Hz, 4J = 1.8 Hz, 1 H,

PyH), 8.37 (s, 2 H, ArH), 8.67 (d, 3J = 7.9 Hz, 1 H, PyH), 8.96 (ddd, 3

J = 4.7 Hz, 4J =

1.6 Hz, 5J = 0.8 Hz, 1 H PyH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.5 (q, CH3), 59.9 (q, OCH3), 123.9 (d, PyCH),

126.3 (d, PyCH), 126.9 (s, ArC), 129.5 (d, ArCH), 132.4 (s, CCH3), 137.5 (d, PyCH),

150.7 (s, PyC), 151.0 (d, PyCH), 161.7 (s, ArCO), 163.3 (s, PyCC), 164.3 (s, ArCC)

ppm.

MS (FAB): m/z (%) = 316 (17) [M+Na]+, 294 (100) [M+H]+, 161 (33), 105 (46).


1H NMR (400 MHz; CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)

13C NMR (100 MHz; CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)

Syntheses 201

2.1.29 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)

Benzoyl chloride 245 (1.61 g, 8.09 mmol) was dissolved in THF (12 mL) and cooled to

0 °C. A solution of benzohydrazide (257) (1.03, 7.59 mmol) and sodium carbonate

(754 mg, 7.11 mmol) in water (10 mL) and THF (12 mL) was added dropwise and a

colorless solid precipitated. The mixture was stirred for 3 h at 0 °C and the solid

collected by filtration, washed with MTBE and dried in vacuo (2.4 mbar, 100–125 °C).

258 (2.55 g, 89 %) was obtained as colorless solid with mp 207–209 °C.

HRMS (EI, 70 eV): C17H18N2O3 (298.34)

calcd.: 298.1317

found: 298.1280

IR (KBr): ν~ = 3226 (w), 3040 (w), 3005 (w), 2939 (w), 2824 (w), 1668 (m), 1637 (s),

1604 (w), 1580 (w), 1527 (m), 1483 (m), 1451 (m), 1377 (w), 1306 (m), 1276 (w), 1245

(w), 1222 (m), 1188 (w), 1164 (w), 1115 (w), 1079 (w), 1046 (w), 1019 (w), 962 (w),

935 (w), 903 (w), 884 (w), 833 (w), 803 (w) cm-1.


1H NMR (400 MHz, DMSO-d6): δ = 2.28 (s, 6 H, CH3), 3.70 (s, 3 H, OCH3), 7.49 (t, J

= 7.3 Hz, 2 H, m-Ar’H), 7.56 (t, J = 7.3 Hz, 1 H, p-Ar’H), 7.62 (s, 2 H, ArH), 7.92 (d, J

= 7.1 Hz, 2 H, o-Ar’H), 10.38 (br s, 2 H, NH) ppm.

13

C{1H} NMR (100 MHz, DMSO- d6): δ = 15.9 (q, CH3), 59.4 (q, OCH3), 127.3 (d, p-

Ar’CH), 128.1 (d, ArCH), 128.3 (d, m-Ar’CH), 128.4 (s, ArC), 130.3 (s, CCH3), 131.4

(d, p-Ar’CH), 133.3 (s, Ar’C), 159.1 (s, ArCO), 165.0 (s, C=O), 165.3 (s, C=O) ppm.

MS (FAB): m/z (%) = 321 (67) [M+Na]+, 299 (42) [M+H]+, 163 (100).


1H NMR (400 MHz, DMSO-d6): N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

6.37

3.22

1.96

1.22

2.00

1.58

2.28

3.70

7.47

7.58

7.62

7.92

10.38

7.47.57.67.77.87.98.0f1 (ppm)

1.96

1.22

2.00

7.47

7.58

7.62

7.92

13C NMR (100 MHz, DMSO-d6): N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)

0102030405060708090100110120130140150160f1 (ppm)

15.9

59.4

127.3

128.1

128.3

128.4

130.3

131.4

133.3

159.3

165.0

165.3

127128129130131132133f1 (ppm)

127.3

128.1

128.3

128.4

130.3

131.4

133.3

Syntheses 203

2.1.30 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzo-hydrazonoyl

chloride (259) and 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-

oxadiazole (260)

Benzohydrazide 258 (700 mg, 2.35 mmol) was dissolved in dry chloroform (50 mL),

PCl5 (9.77 g, 46.4 mmol) was added and the supension heated to reflux for 24 h. The

cooled mixture was poured into ice water (50 mL), the layers were separated and the

aqueous layer was extracted with DCM (3 x 30 mL). The combined organic layers were

washed with saturated aqueous NaHCO3 (2 x 50 mL), brine (30 mL) and dried over

MgSO4. The solvent was removed by rotary evaporation, the residue purified by flash

chromatography (silica gel, PE/EtOAc 10:1 to 2:1) to yield hydrazonoyl chloride 259

(Rf (2:1) = 0.70 and oxadiazole 260 (Rf (2:1) = 0.48). Analytically pure material of 259

was obtained by crystallization from ethanol and subsequent drying in vacuo (1.4 mbar,

75–100 °C), while 260 was crystallized from DCM/Et2O in the cold and dried

(1.3 mbar, 50–75 °C).

1st fraction (Rf = 0.70): hydrazonoyl chloride 259 (510 mg, 65 %) as colorless solid with

mp 80 °C.

HRMS (EI, 70 eV): C17H16Cl2N2O (335.23)

calcd.: 334.0640

found: 334.0633

IR (KBr): ν~ = 3059 (w), 3008 (w), 2961 (w), 2919 (w), 2873 (w), 1603, (w)1579 (w),

1509 (w), 1481 (w), 1446 (w), 1416 (w), 1375 (w), 1317 (w), 1247 (w), 1236 (w), 1182

(w), 1150 (m), 1048 (w), 996 (w), 953 (w), 927 (w), 893 (w), 880, (w) 814 (w), 759 (w)

cm-1.



1H NMR (400 MHz, CDCl3): δ = 2.36 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.43–7.55

(m, 3 H, m-Ar’H, p-Ar’H ), 7.80 (s, 2 H, ArH), 8.13 (dd, J = 8.3 Hz, J = 1.2 Hz, 2 H, o-

Ar’H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.9 (q, OCH3), 128.66 (d, m-

Ar’CH), 128.69 (d, o-Ar’CH), 129.1 (s, ArC), 129.5 (d, ArCH), 131.4 (s, CCH3), 131.9

(d, p-Ar’CH), 133.9 (s, Ar’C), 144.1 (s, Ar’CCCl), 144.3 (s, ArCCCl), 160.5 (s, ArCO)

ppm.

MS (FAB): m/z (%) = 335 (100) [M+H]+, 299 (39) [M–Cl]+, 196 (88), 161 (22), 138

(49), 105 (26), 91 (15), 77 (48), 55 (22), 43 (20).

Syntheses 205

1H NMR (400 MHz, CDCl3): N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethyl-benzohydrazonoyl chloride (259)

13C NMR (100 MHz, CDCl3): N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethyl-benzohydrazonoyl chloride (259)


2nd fraction (Rf = 0.48): oxadiazole 260 (114 mg, 17 %) as colorless solid with

mp 103 °C.

C17H16N2O2 (280.32)

calcd.: C 72.84, H 5.75, N 9.99

found: C 72.67, H 5.50, N 9.88

IR (KBr): ν~ = 3074 (w), 3044 (w), 2950 (w), 2916 (w), 2851 (w), 1608 (w), 1550 (w),

1477 (m), 1412 (w), 1375 (w), 1339 (w), 1316 (w), 1300 (w), 1285 (w), 1243 (w), 1206

(w), 1175 (w), 1109 (w), 1083 (w), 1067 (w), 1015 (w), 997 (w), 959 (w), 921 (w), 887

(w), 871 (w), 776 (w), 762 (w), 727 (w), 687 (w) cm-1.



(m, 3 H, m-Ar’H, p-Ar’H), 7.81 (s, 2 H, ArH), 8.13–8.16 (m, 2 H, o-Ar’H) ppm.

13


124.3 (s, Ar’C), 127.1 (d, o-Ar’CH), 127.8 (d, ArCH), 129.2 (d, m-Ar’CH), 131.7 (d, p-

Ar’CH), 132.2 (s, CCH3), 160.3 (s, ArCO), 164.5 (s, Ar’CC), 164.8 (s, ArCC) ppm.

MS (FAB): m/z (%) = 281 (100) [M+H]+, 163 (16).

Syntheses 207

1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-oxadiazole (260)

13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-oxadiazole (260)


2.1.31 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine

(261)

Hydrazonoyl chloride 259 (439 mg, 1.31 mmol) and hydrazine hydrate (80 µl,

1.05 mmol) were dissolved in dry ethanol (8 mL) under argon to give a red reaction

mixture, which was refluxed for 30 min. The precipitate was collected by filtration and

washed with cold ethanol to yield 261 (201 mg, 52 %) as yellow solid with

mp 189–191 °C after drying in vacuo (4.2 mbar, 75 °C, 1 h). The compound was used

without further purification.

IR (KBr): ν~ = 3268 (m), 3147 (w), 3044 (w), 2949 (w), 2828 (w), 2704 (w), 2584 (w),

1641 (w), 1601 (w), 1578 (w), 1493 (w), 1449 (w), 1421 (w), 1402 (w), 1351 (m), 1312

(w), 1293 (w), 1240 (w), 1206 (w), 1172 (w), 1117 (w), 1101 (w), 1009 (w), 970 (w),

926 (w), 882 (w), 845 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 6 H, CH3), 3.74 (s, 3 H, OCH3), 7.12 (br s, 2

H, NH), 7.34 (s, 2 H, ArH), 7.41–7.47 (m, 3 H, m-Ar’H, p-Ar’H), 7.67 (dd, J = 7.8 Hz,

J = 1.6 Hz, 2 H, o-Ar’H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59 9 (q, OCH3), 125.5 (s, ArC),

126.1 (d, o-Ar’CH), 126.8 (d, ArCH), 129.0 (m-Ar’CH), 130.4 (s, Ar’C), 130.8 (d, p-

Ar’CH), 131.9 (s, CCH3), 148.8 (s, tetrazine-C), 159.5 (s, ArCO) ppm.

MS (FAB): m/z (%) = 294 (100) M+, 186 (12), 162 (12).

Syntheses 209

1H NMR (400 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine (261)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

6.12

3.01

1.81

2.00

3.28

1.99

2.31

3.74

7.12

7.34

7.41

7.47

7.67

13C NMR (100 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine (261)

0102030405060708090100110120130140150160f1 (ppm)

16.3

59.9

125.5

126.1

126.8

129.0

130.4

130.8

131.9

148.8

125127129131f1 (ppm)

125.5

126.1

126.8

129.0

130.4

130.8

131.9

34567f2 (ppm)

155

160 f1 (ppm)

{2.33,159.56}

{3.73,159.45}

{7.35,159.51}


2.1.32 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)

Dihydrotetrazine 261 (175 mg, 0.59 mmol) was dissolved in conc. acetic acid (2 mL) at

0 °C and aqueous NaNO2 (10 %, 2 mL) was added dropwise. Diethylether (1 mL) was

added to the purple mixture and it was stirred for 15 min. The precipitated solid was

collected by filtration, washed with methanol and dried in vacuo (1.6 mbar, 100 °C) to

yield tetrazine 262 (47 mg, 27 %) as purple solid with mp 124 °C. The mother liquor

was washed with water (2 x 10 mL), aqueous NaHCO3 (10 %, 2 x 10 mL) and water

(15 mL), dried over MgSO4 and the solvent was removed by rotary evaporation to yield

further 25 mg according to NMR, giving an overall yield of 41 %.

HRMS: C17H16N4O (292.34)

calcd.: 292.1324

found: 292.1348

IR (KBr): ν~ = 3061 (w), 2959 (w), 2923 (w), 2834 (w), 1600 (w), 1490 (w), 1447 (w),

1420 (w), 1293 (s), 1308 (w), 1245 (w), 1209 (m), 1174 (w), 1109 (w), 1069 (w), 1045

(w), 1005 (w), 955 (w), 914 (w), 895 (w), 848 (w), 828 (w), 797 (w), 757 (w) cm-1.



(m, 3 H, m-Ar’H, p-Ar’H), 8.33 (s, 2 H, ArH), 8.64 (dd, 3J = 7.4 Hz, 4

J = 2.0 Hz, 2 H,

o-Ar’H) ppm.

13


128.0 (s, o-Ar’CH), 129.0 (d, ArCH), 129.4 (d, m-Ar’CH), 132.1 (s, Ar’C), 132.4 (s,

CCH3), 132.6 (d, p-Ar’CH), 161.4 (s, ArCO), 163.8 (s, Ar’CC), 163.9 (s, ArCC) ppm.

Syntheses 211

MS (FAB): m/z (%) = 293 (41) [M+H]+, 161 (25).


1H NMR (400 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)

13C NMR (100 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)

Syntheses 213

2.2 Syntheses at the upper rim of calixarenes

2.2.1 Transannular cyclization-product (cone) (61)

In three parallel reactions, a suspension of calixarene 60 (124, 126 and 127 mg,

16 µmol), iodine (91–99 mg, 0.36–0.38 µmol) and potassium carbonate (1.199–1.202 g,

8.68–8.70 µmol) in benzene (200 mL) was degassed with argon (30 min) and irradiated

for 15 h (125-W medium-pressure lamp, quartz filter), while a permanent argon stream

was bubbled through the solution. Benzene was removed in vacuo and the combined

residues were suspended in dichloromethane (600 mL) and insoluble material was

filtered off. The solvent was evaporated and the black residue (~ 600 mg) was purified

by flash chromatography (silica gel, PE to PE/EtOAc 10:1, Rf (20:1) = 0.42) to yield

339 mg (90 %) of cyclization products. By HPLC (n-hexane/EtOAc 80:1,

p = 1.6–1.7 MPa, flow = 10 mL/min) and subsequent drying in vacuo (0.31 mbar, 50

°C, 1.5 h) 141 mg (37 %) of 61 were isolated as a colorless solid with mp 266–268 °C.

Crystals suitable for XRS were obtained by crystallization from DCM/MeOH. 1H NMR spectra of other HPLC fractions indicated also compounds 62 and 63 in minor

amounts and purity: approximate yields were determined from NMR spectra to be about

6 % for the desired diphenanthrene 62 and about 25 % for compound 63 (Figure 2.3).

C56H60O4 (797.07)

calcd.: C 84.38, H 7.59

found: C 83.98, H 7.22


IR (KBr): ν~ = 3056 (w), 3026 (w), 2962 (m), 2930 (m), 2874 (m), 1601 (w), 1584 (w),

1463 (s), 1383 (w), 1278 (w), 1214 (m), 1172 (w), 1128 (w), 1073 (w), 1037 (w), 1008

(m), 966 (m), 920 (w), 890 (w), 870 (w), 833 (w), 799 (w), 768 (w), 721 (w).

UV/Vis (n-hexane): λmax (lgε) = 271 (3.4), 225 (4.8, sh).

1H NMR (400 MHz, CDCl3): δ = 0.85 und 0.86 (t, superimposed, both J = 7.4 Hz, 6 H,

CH3), 1.12 (t, J = 7.4 Hz, 6 H, CH3), 1.75–1.88 (m, 8 H, CH2), 3.15 (d, J = 14.4 Hz, 2

H, ArCH2Ar), 3.21 (d, J = 14.3 Hz, 2 H, ArCH2Ar), 3.69 (t, J = 6.4 Hz, 4 H, OCH2),

3.76 („d“, AA’BB’, „J“ = 7.0 Hz, 2 H, cyclobutane-H), 3.86 („d“, AA’BB’, „J“ = 7.0

Hz, 2 H, cyclobutane-H), 3.88–3.93 (m, 4 H, OCH2), 4.45 and 4.49 (both d,

superimposed, both J = 13.9 Hz, 4 H, ArCH2Ar), 5.50 (d, 3J = 2.0 Hz, 2 H, m-ArH),

5.86 (d, 3J = 2.0 Hz, 2 H, m-ArH), 6.87–6.89 (m, 4 H, o-PhH), 6.94–7.05 (m, 8 H, PhH,

p-ArH), 7.13 (d, J = 7.3 Hz, 2 H, m-ArH), 7.21 (d, J = 7.4 Hz, 2 H, m-ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.00, 10.02, 11.1 (all q, CH3), 23.2, 23.3, 23.7

(all t, CH2), 31.4, 31.6 (both t, ArCH2Ar), 45.0 (d, cyclobutane-C-Ph), 48.7 (d,

cylclobutane-C), 76.26, 76.31, 76.34 (all t, OCH2), 121.5 (d, p-ArCH), 125.1 (d, m-

ArCH), 125.5 (d, p-PhCH), 127.7 (d, m-PhCH), 128.3 (d, o-PhCH), 128.7 (m-ArCH),

129.4 (d, m-ArCH), 129.6 (d, m-ArCH), 133.9 (s, ArCCH2Ar, p-ArC), 134.3

(ArCCH2Ar), 138.0, 138.1 (both s, ArCCH2Ar), 141.7 (PhC), 154.4, 159.4, 159.5 (all s,

ArCO) ppm.

MS (FAB): m/z (%) = 796 (100) M+.

Syntheses 215

1H NMR (400 MHz, CDCl3): Transannular cyclization-product (cone) (61)

13C NMR (100 MHz, CDCl3): Transannular cyclization-product (cone) (61)


2.2.2 cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]arene (73)

Calixarene 72 (2.89 g, 3.79 mmol) was dissolved in dry toluene (200 mL), anhydrous

AlCl3 (1.01 g, 7.52 mmol) was added at 0 °C and the mixture was stirred at 0 °C for 45

min and additional 20 min at room temperature. The reaction was quenched with HCl

(1 N, 50 mL) and the separated aqueous layer was extracted twice with dichloromethane

(40 mL). The combined organic layer was washed with water (50 mL), dried over

MgSO4 and solvents were removed in vacuo. The residue was treated with

CH2Cl2/MeOH (1:1), concentrated to 25 % of the volume, the resulting precipitate was

filtered off and dried in vacuo (0.82–1.7 mbar, 100 °C, 3 h) to give 1.88 g (85 %) of

calixarene 73 as a colorless solid with mp > 300 °C (lit.80c mp > 300 °C).

1H NMR (200 MHz, CDCl3): δ = 3.49 (br s, 4 H, ArCH2Ar), 4.18 (br s, 4 H, ArCH2Ar),

6.77 (t, J = 7.5 Hz, 2 H, p-ArH), 7.02–7.11 (m, 4 H, m-ArH), 7.14 (d, 3J = 2.4 Hz, 2 H,

BrArH), 7.19 (d, 3J = 2.4 Hz, 2 H, BrArH ), 10.04 (s, 4 H, OH) ppm.

13

C{1H} NMR (50 MHz, CDCl3): δ = 31.5, 31.6, 31.7 (all t, all ArCH2Ar), 114.1 (s),

122.7 (d), 127.4 (s), 128.3 (s), 129.2 (d), 129.5 (d), 129.6 (s), 130.6 (s), 131.6 (d), 131.9

(d), 148.2, 148.7 (both s) ppm.

NMR spectroscopic data are in accord with the literature.80c

Syntheses 217

1H NMR (200 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]-arene (73)

13C NMR (50 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]-arene (73)


2.2.3 cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene (74)

NaH (60 % in mineral oil, 2.47 g, 61.7 mol) was washed with hexane (3 x 15 mL),

suspended in dry DMF (80 mL) and the mixture was heated to 60 °C for 30 min after

addition of calixarene 73 (1.80 g, 3.09 mmol). Propyl iodide was added and after

stirring at room temperature for 30 min the reaction mixture was heated an additional

2 h at 60–70 °C. The reaction was quenched with ice cold water (110 mL) and the

aqueous layer was extracted with dichloromethane (3 x 30 mL). The organic layer was

washed with aq. ammonium chloride (1 N, 2 x 50 mL), water (50 mL), brine (50 mL),

dried over MgSO4 and the solvent was evaporated. The residue was purified by flash

chromatography (silica gel, PE/DCM 8:1, Rf in 2.5:1 PE/DCM = 0.51) and dried in

vacuo (1.4–3.9 mbar, 100 °C, 2 h). 1.66 g (94 %) of calixarene 74 were obtained as a

colorless solid with mp 80–82 °C (lit.80c 117–119 °C).

1H NMR (200 MHz, CDCl3): δ = 0.97 and 0.98 (both t, superimposed, J = 7.4 and 7.5

Hz, 12 H, OCH3), 1.77–1.97 (m, 8 H, CH2), 3.04, 3.11 and 3.17 (all d, J = 13.9 Hz, J =

13.6 Hz, J = 13.0 Hz, 4 H, ArCH2Ar), 3.75–3.86 (m, 8 H, OCH2), 4.35, 4.39 and 4.44

(all d, J = 13.6 Hz, J = 13.6 Hz, J = 13.4 Hz, 4 H, ArCH2Ar), 6.56–6.72 (m, 10 H, ArH)

ppm.

13

C{1H} NMR (50 MHz, CDCl3): δ = 10.4, 10.5 (both q, CH3), 23.27, 23.28 (both t,

CH2), 30.9, 31.0, 31.1 (all t, ArCH2Ar), 76.8, 76.9 (both t, OCH2), 114.8, 122.4, 128.1,

128.7, 130.6, 131.2, 134.4, 135.4, 136.7, 137.8, 156.0, 156.7 (both s, ArCO) ppm.

MS (FAB): m/z (%) = 750 (82) M+.

NMR spectroscopic data are in accord with literature. 80c,82

Syntheses 219

1H NMR (200 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]-arene (74)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)

11.61

8.40

4.13

8.01

4.00

9.74

0.97

0.98

1.77

1.97

3.04

3.11

3.17

3.75

3.86

4.35

4.39

4.44

6.56

6.72

13C NMR (50 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]-arene (74)


2.2.4 cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]arene (75)

To a cooled (–78 °C) solution of calixarene 74 (1.24 g, 1.65 mmol) in dry THF, nBuLi

(2.77 mL, 15 % in hexane, 4.41 mmol) was added. The reaction mixture was stirred

45 min at –78 °C and after addition of DMF (2.52 mL, 15.5 mmol) 2 h at room

temperature. The reaction was hydrolyzed with HCl (1 N, 40 mL), the aqueous layer

was extracted with dichloromethane (3 x 30 mL), the organic layer was washed with

water (3 x 30 mL), brine (30 mL) and dried over MgSO4. The solvent was evaporated

and the residue purified by flash chromatography (silica gel, PE/EtOAc 20:1 to 10:1,

Rf in PE/EtOAc 5:1 = 0.28). Diformylcalixarene 75 was obtained after drying in vacuo

(1.8 mbar, 50 °C, 2.5 h) in 632 mg (45 %) yield as a colorless solid.

1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.01 (two t, superimposed, both J = 7.4 Hz,

12 H, CH3), 1.81–1.99 (m, 8 H, CH2), 3.16 (d, J = 13.6 Hz, 1 H, ArCH2Ar), 3.25 (d, J =

14.0 Hz, 2 H, ArCH2Ar), 3.32 (d, J = 14.7 Hz, 1 H, ArCH2Ar), 3.77–4.10 (m, 8 H,

OCH2), 4.42 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.47 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 4.52

(d, J = 13.6 Hz, 1 H, ArCH2Ar), 6.47–6.61 (m, 6 H, ArH), 7.12 and 7.14 (two d, both 3J

= 1.9 Hz, 4 H, m-ArH), 9.65 (s, 2 H, ArCHO) ppm.

13

C{1H} NMR (50 MHz, CDCl3): δ = 10.4, 10.5 (both q, CH3), 23.4, 23.5 (both t, CH2),

31.1 (t, ArCH2Ar), 76.9 (t, OCH2), 122.4, 128.2, 128.8, 130.0, 130.8, 131.2, 134.3,

135.5, 135.6, 136.7, 156.6, 162.4, 191.7 ppm.

MS (FAB): m/z (%) = 671 (80) [M+Na]+, 648 (100) M+.

NMR spectroscopic data are in accord with the literature.86

Syntheses 221

1H NMR (200 MHz, CDCl3): cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]-arene (75)

13C NMR (50 MHz, CDCl3): cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]-arene (75)


2.2.5 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene

(65)

To a cooled (–78 °C) suspension of benzyltriphenylphosphonium chloride (285)

(939 mg, 2.42 mmol) in dry THF (20 mL), nBuLi (1.78 mL, 15 % in hexane, 2.85

mmol) was added. The reaction mixture was stirred 45 min at –78 °C and 30 min at

room temperature, during which the color changed from yellow to orange and finally

dark red. The reaction mixture was cooled to –78 °C and a solution of

diformylcalixarene 75 (607 mg, 0.94 mmol) in dry THF (25 mL) was added. The

reaction was allowed to warm to room temperature over night. After hydrolyzing with

water 20 mL) the aqueous layer was extracted with dichloromethane (2 x 50 mL), the

organic layer was washed with water (4 x 50 mL), once with brine (100 mL) and dried

over MgSO4. Solvents were removed in vacuo. 1.463 g of the resulting solid were

purified by flash chromatography (silica gel, PE/EtOAc 20:1, Rf = 0.35) and dried in

vacuo (1.0–5.2 mbar, 50 °C, 2.5 h). 691 mg (93 %) of distilbene 65 were obtained as a

colorless solid with mp 79–81 °C. Isomerization to the E/E isomer was achieved by

adding a crystal of iodine to the NMR sample and subsequent heating with a heat gun.

C56H60O4 (797.07)

calcd.: C 84.38, H 7.59

found: C 84.37, H 7.82

IR (KBr): ν~ = 3055 (w), 3020 (w), 2959 (s), 2930 (s), 2872 (s), 2735 (w), 1631 (w),

1594 (w), 1492 (w), 1461 (s), 1401 (w), 1383 (m), 1304 (w), 1280 (w), 1246 (m), 1216

(s), 1193 (m), 1159 (w), 1125 (m), 1083 (w), 1068 (w), 1037 (m), 1005 (s), 963 (s), 916

(w), 888 (w), 836 (w), 807 (w), 763 (s) cm-1.

Syntheses 223

UV/Vis (n-hexane): λmax (lgε) = 296 (4.5).

E/Z isomer: 1H NMR (400 MHz, CDCl3): δ = 0.96–1.04 (m, 12 H, CH3), 1.85–1.96 (m, 8 H, CH2),

2.89, 2.98, 2.99, 3.03, 3.16, 3.19 (all d, J = 13.3, 13.4, 14.0, 14.0, 13.4, 13.4 Hz, 4 H,

ArCH2Ar), 3.76–3.93 (m, 8 H, OCH2), 4.31, 4.36, 4.37, 4.39, 4.45, 4.46, 4.47 (all d, J =

13.2, 13.1, 13.3, 12.9, 13.4, 13.4, 13.4 Hz, 4 H, ArCH2Ar), 6.27–6.85 (m, 14 H, ArH,

alkene-H), 7.08–7.25 (m, 8 H, ArH), 7.32 (t, J = 7.6 Hz, 1 H, ArH), 7.42–7.54 (m, 1 H,

ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.37, 10.46, 10.48, 10.50, 10.60 (all q, CH3),

23.36, 23.38, 23.45 (all t, CH2), 31.0, 31.1, 31.2, 31.3 (all t, ArCH2Ar), 76.8 (t, OCH2),

122.0, 122.1, 122.2, 126.3, 126.4, 126.5, 126.6, 126.62, 126.66, 126.75, 126.83, 126.9,

127.06, 127.10, 128.0, 128.17, 128.22, 128.35, 128.41, 128.5, 128.6, 128.7, 128.9,

129.2, 129.4, 129.47, 129.53, 130.77, 130.81, 130.9 , 131.3, 134.5, 134.7, 134.8, 134.9,

135.0, 135.2, 135.26, 135.33, 135.38, 135.41, 135.60, 135.64, 135.7, 135.9, 137.95,

138.00, 138.12, 138.13, 156.2 (s, ArCO), 156.3 (s, ArCO), 156.55 (s, ArCO), 156.58 (s,

ArCO), 156.64 (s, ArCO), 156.8 (s, ArCO), 157.0 (s, ArCO), 157.2 (s, ArCO) ppm.

E/E isomer: 1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.00 (two t, superimposed, J = 7.3 and 7.4

Hz, 12 H, CH3), 1.82-2.01 (m, 8 H, CH2), 3.15, 3.17 and 3.19 (three d, superimposed, J

= 13.6 Hz, J = 13.5 Hz, J = 13.6 Hz, 4 H, ArCH2Ar), 3.81–3.91 (m, 8 H, OCH2), 4.46

(d, J = 13.5 Hz, 4 H, ArCH2Ar), 6.48–6.64 (m, 6 H, ArH), 6.73 and 6.77 (d, J = 16.2 Hz

and s, superimposed, 6 H, alkene-H, m-ArH), 6.87 (d, J = 16.3 Hz, 2 H, alkene H),

7.16–-7.24 (m, 2 H, p-Ar’H), 7.32 ( “t”, “J” = 7.7 Hz, 4 H, m-Ar’H), 7.45 ( “d”, “J” =

7.8 Hz, 4 H, o-Ar’H) ppm.

MS (FAB): m/z (%) = 796 (100) M+.


1H NMR (400 MHz, CDCl3): isomer mixture of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)

Syntheses 225

13C NMR (100 MHz, CDCl3): isomer mixture of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)

0102030405060708090100110120130140150160f1 (ppm)

10.4

10.5

10.5

10.5

10.6

23.4

23.4

23.4

31.0

31.1

31.2

31.3

122.0

122.1

122.1

130.8

130.8

130.9

137.9

138.0

138.1

138.1

156.2

156.3

156.5

156.6

156.6

157.0

157.2

77.077.5f1 (ppm)

76.8

134.4134.6134.8135.0135.2135.4135.6135.8136.0136.2f1 (ppm)

134.5

134.7

134.8

134.9

134.9

135.0

135.2

135.3

135.3

135.4

135.4

135.6

135.6

135.7

135.9

126.5127.0127.5128.0128.5129.0129.5f1 (ppm)

126.3

126.4

126.5

126.6

126.6

126.7

126.8

126.8

126.9

127.1

127.1

128.0

128.2

128.2

128.4

128.4

128.5

128.6

128.7

128.9

129.2

129.4

129.5

129.5

1H NMR (200 MHz, CDCl3): E isomer of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)


2.2.6 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c)

In four parallel reactions, a suspension of calixarene 65 (108, 109, 111 and 126 mg,

135-158 µmol), iodine (79–92 mg, 311–362 µmol) and potassium carbonate

(1.05–1.30 g, 76–87 µmol) in benzene (200 mL) was degassed with argon (30 min) and

irradiated for 17 h (125-W medium-pressure lamp, quartz filter). During the reaction a

permanent argon stream was bubbled through the solution. Benzene was removed in

vacuo, the combined residue was suspended in dichloromethane and insoluble material

was filtered off. The filtrate was washed with aqueous Na2S2O3 (10 %, 60 mL) and

dried over MgSO4 to give 573 mg of a brown residue. 301 mg (67 %) cyclization

products were obtained as a mixture after successive flash chromatography (silica gel,

PE/EtOAc 50:1 and PE/EtOAc 20:1, Rf = 0.32 in PE/EtOAc 20:1). 235 mg of this

mixture were subjected to HPLC (PE/EtOAc 200:1, p = 1.1–1.2 MPa) and the isolated

compounds dried in vacuo (1.1–1.8 mbar, 75–100 °C, 1.5 h).

1st Fraction: 123 mg (27 %) of 81a were isolated as a colorless solid with

mp 243–245 °C. Crystals suitable for XRS were obtained from chloroform/ethanol.

C56H56O4 (793.04)

calcd.: C 84.81, H 7.12

found: C 84.41, H 7.13

IR (KBr): ν~ = 3048 (w), 2959 (s), 2918 (m), 2872 (m), 1590 (w), 1511 (w), 1452 (s),

1442 (s), 1412 (w), 1377 (w), 1330 (w), 1285 (m), 1252 (m), 1206 (m), 1166 (w), 1137

(w), 1096 (w), 1083 (w), 1062 (w), 1033 (w), 1001 (s), 966 (s), 885 (w), 868 (w), 838

(w), 805 (m), 765 (m), 745 (m) cm-1.

UV/Vis (n-hexane): λmax (lgε) = 309 (4.0, sh), 259 (4.7), 221 (4.6, sh) nm.

Syntheses 227

1H NMR (600 MHz, CDCl3): δ = 0.79 (t, J = 7.5 Hz, 3 H, CH3), 0.94 (t, J = 7.4 Hz, 3

H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.33 (t, J = 7.4 Hz, 3 H, CH3), 1.72-2.14 (m, 8

H, CH2), 3.04 (d, J = 14.3 Hz, 1 H, ArCH2Ar), 3.25 (d, J = 13.3 Hz, 1 H, ArCH2Ar)

3.31 (d, J = 14.0 Hz, 1 H, ArCH2Ar), 3.56–3.63 (m, 2 H, OCH2), 3.90-3.97 (m, 2 H,

OCH2), 4.03–4.07 (m, 1 H, OCH2), 4.16–4.29 and 4.26 (m and d, superimposed, J =

12.9 Hz, 3 H, OCH2, ArCH2Ar), 4.49 (d, J = 13.2 Hz, 1 H, ArCH2Ar), 4.79 (d, J = 13.8

Hz, 1 H, ArCH2Ar), 5.30 (d, J = 7.3 Hz, 1 H, m-ArH), 5.71 (t, J = 7.2 Hz, 1 H, Phen-6-

H), 5.76 (d, J = 15.8 Hz, ArCH2Ar), 5.81 (d, J = 15.9 Hz, 1 H, ArCH2Ar), 6.00 (s, 1 H,

Phen-1-H), 6.16 (t, J = 7.5 Hz, 1 H, p-ArH), 6.23 (d, J = 7.2 Hz, 1 H, m-ArH), 6.80 (d, J

= 8.6 Hz, 1 H Phen-10-H), 6.84 (t , J = 7.3 Hz, 1 H, Phen-7-H), 7.04 (s, 1 H, Phen-1-H),

7.07 (d, J = 8.6 Hz, 1 H, Phen-9-H), 7.09 (t, J = 7.5 Hz, 1 H, p-ArH), 7.24-7.26 (m, 3 H,

m-ArH, Phen-8-H, Phen-10-H), 7.54 (d, J = 8.7 Hz, 1 H, Phen-9-H), 7.61 (d, J = 8.4 Hz,

1 H, Phen-5-H), 7.66 (t, J = 7.3 Hz, 1 H, Phen-7-H), 7.71 (t, J = 7.5 Hz, 1 H, Phen-8-H),

8.00 (d, J = 7.5 Hz, 1 H, Phen-8-H), 8.70 (d, J = 8.2 Hz, 1 H, Phen-5-H) ppm.

13

C{1H} NMR (150 MHz, CDCl3): δ = 9.8, 10.1, 11.0, 11.3 (all q, CH3), 22.2, 23.1,

23.7, 23.9 (all t, CH2), 30.7, 31.0, 31.5, 31.6 (all t, ArCH2Ar), 77.0, 77.2 (both t, OCH2),

122.1 (d, p-ArCH), 122.5 (d, Phen-C-6), 123.3 (d, p-ArCH), 123.9 (d, Phen-C-9), 124.3

(d, Phen-C-7), 124.6 (d, Phen-C-9), 124.9 (d, Phen-C-6), 125.8 (d, Phen-C-7), 125.9 (d,

m-ArCH), 126.6, 126.8, 127.0 (three d, Phen-C-8, Phen-C-10, m-ArCH), 127.3 (d,

Phen-C-5), 127.4 (s, Phen-C), 127.8 (d, Phen-C-5), 128.0 (d, Phen-C-1), 128.2 (d, Phen-

C-8), 128.3 (s, Phen-C), 128.5, 128.6 (both d, both Phen-C), 129.0 (s, Phen-C), 129.1

(d, m-ArCH), 129.5 (s, Phen-C), 129.8 (d, m-ArCH), 130.6 (s, PhenCCH2Phen), 131.1

(s, Phen-C), 131.5 (s, PhenCCH2Phen), 132.0 (s, Phen-C), 132.86 (s, ArCCH2Phen),

132.87 (s, ArCCH2Phen), 133.47, 133.49, 133.6 ( three s, PhenCCH2Ar, two Phen-C),

135.7 (s, PhenCCH2Ar), 137.0 (s, ArCCH2Phen), 138.3 (s, ArCCH2Ar), 155.0 (s,

ArCO), 156.9 (s, PhenCO), 158.7 (s, ArCO), 159.8 (s, PhenCO) ppm.

MS (FAB): m/z (%) = 815 (7) [M+Na]+, 792 (100) M+.


1H NMR (600 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81a)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

13C NMR (150 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81a)

Syntheses 229

2nd Fraction: 31 mg (7 %) of 81b were isolated as a colorless solid with mp 129–131

°C.

IR (KBr): ν~ = 3046 (w), 2959 (s), 2930 (m), 2872 (m), 1592 (w), 1510 (w), 1454 (s),

1441 (s), 1413 (w), 1380 (w), 1332 (w), 1288 (w),1249 (w), 1214 (m), 1201 (m), 1177

(w), 1134 (w), 1101 (m), 1082 (w), 1064 (w), 1037 (w), 1004 (s), 967 (m), 882 (w), 838

(w), 804 (m), 758 (m), 744 (m), 700 (w) cm-1.

UV/Vis (n-hexane): λmax (lgε) = 310 (4.3), 269 (5.0) nm.


H, CH3), 1.88–1.96 (m, 4 H, CH2), 1.98–2.11 (m, 4 H, CH2), 2.90 (d, J = 14.3 Hz, 1 H,

ArCH2Ar), 3.46 (d, J = 14.2 Hz, 1 H, ArCH2Ar), 3.79-3.92 (m, 4 H, OCH2), 4.03–4.09

(m, 2 H, OCH2) 4.28 (d and m, superimposed, J = 14.2 Hz, 3 H, ArCH2Ar, OCH2), 4.73

(d, J = 14.3 Hz, 2 H, ArCH2Ar), 4.94 and 4.98 (both d, superimposed, J = 14.4 Hz, J =

14.6 Hz, 3 H, ArCH2Ar), 5.84 (br s, 2 H, m-ArH), 6.07 (t, J = 7.3 Hz, 2 H, p-ArH), 6.26

(br s, 2 H, m-ArH), 7.04 (br s, 2 H, Phen-H), 7.38 (s, 2 H, Phen-H), 7.44-7.56 (m, 6 H,

Phen-H), 7.78 (d, J = 7.3 Hz, 2 H, Phen-H), 8.78 (d, J = 8.0 Hz, 2 H, Phen-5-H) ppm.

13


CH2), 30.5, 30.9, 31.3 (all d, ArCH2Ar), 76.4, 78.3 (both t, OCH2), 121.3 (d, p-ArCH),

124.3), 124.7, 125.6 (all d, Phen-C), 127.6 (d, Phen-C m-ArCH), 128.1 (d, m-ArCH,

Phen-C), 128.5 (d, m-Phen-C, Phen-C-5), 129.0, 130.5, 130.7, 133.0 (all s, Phen-C),

134.2 (s, PhenCCH2Phen), 134.5 (s, ArCCH2Phen), 134.7 (s, ArCCH2Ar), 156.3 c(s,

ArCO), 159.0 (s, PhenCO) ppm.

MS (FAB): m/z (%) = 792 (100) M+.


1H NMR (400 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81b)

13C NMR (100 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81b)

Syntheses 231

3rd Fraction: 63 mg (14 %) of 81c were isolated as a colorless solid with

mp 134–136 °C.

IR (KBr): ν~ = 3046 (w), 2959 (s), 2930 (m), 2872 (m), 2732 (w), 1590 (w), 1510 (w),

1454 (s), 1440 (s), 1413 (w), 1380 (w), 1335 (w), 1286 (w), 1248 (w), 1215 (m), 1200

(m), 1134 (w), 1101 (m), 1082 (w), 1064 (w), 1036 (w), 1003 (s), 967 (m), 881 (w), 838

(w), 805 (m), 762 (m), 744 (m) cm-1.

UV/Vis (n-hexane): λmax (lgε) = 359 (3.2), 343 (3.3), 307 (4.5, sh), 258 (4.9) nm.


H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.11 (t, J = 7.4 Hz, 3 H, CH3), 1.87–2.03 (m, 8

H, CH2), 3.04 d, J = 13.9 Hz, 1 H, ArCH2Ar), 3.41 (d, J = 13.7 Hz, ArCH2Ar), 3.74–

4.13 (m, 7 H, OCH2), 4.22–4.28 (m, 1 H, OCH2), 4.38 (d, J = 13.8 Hz, 1 H, ArCH2Ar),

4.52 (d, J = 14.8 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 15.5 Hz, ArCH2Ar), 4.73 (d, J = 13.6

Hz, 1 H, ArCH2Ar), 4.94 (d, J = 14.8 Hz, 1 H, ArCH2Ar), 5.31 (d, J = 15.5 Hz, 1 H,

ArCH2Ar), 6.18 (t, J = 7.5 Hz, 1 H), 6.39 (br s, 2 H), 6.52 (d, J = 6.9 Hz, 3 H), 6.88 (d,

J = 8.5 Hz, 1 H), 7.19 (d, J = 8.7 Hz, 1 H), 7.38–7.44 (m, 4 H), 7.49 (br s, 2 H), 7.61

and 7.62 (m, 1 H), 7.73 (br „s“, 1 H), 8.73 („d“, „J“ = 7.4 Hz, 2 H, Phen-5-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.3, 10.5, 10.75, 10.78 (all q, CH3), 23.0, 23.3,

23.5 (all t, CH2), 30.0, 30.7, 31.4, 31.5 (all t, ArCH2Ar), 76.2, 77.0, 77.4, 77.8 (all t,

OCH2), 120.9, 122.5, 123.9, 124.0, 124.8, 125.1, 125.4, 125.6, 127.5, 127.6, 127.75,

127.84, 128.1, 128.2, 128.3, 128.5, 128.7 (s), 128.76 (s), 128.83 (s), 129.2 (s), 129.8 (s),

130.4 (s), 130.5 (s), 130.6 (s), 132.8 (s, 133.2 (s), 133.8 (s), 134.5 (s), 134.87 (s), 134.89

(s), 136.2 (s), 156.4, 157.0 (both s, ArCO), 157.9 (s, PhenCO) ppm.

MS (FAB): m/z (%) = 792 (100) M+.


1H NMR (400 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81c)

13C NMR (100 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81c)

Syntheses 233

2.2.7 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-

propoxycalix[4]arene (85)

To a cooled (–78 °C) suspension of phosphonium bromide 84 (854 mg, 1.92 mmol) in

dry THF (20 mL) nBuLi (1.5 mL, 15 % in hexane, 2.39 mmol) was added. The reaction

mixture was stirred 45 min at –78°C and 30 min at room temperature. A solution of

diformylcalixaren 78 (475 mg, 733 µmol) in dry THF (10 mL) was added at –78 °C.

The reaction was allowed to warm to room temperature overnight. The suspension was

hydrolyzed with water (25 mL) and the aqueous layer was extracted with

dichloromethane (3 x 20 mL). The combined organic layer was washed twice with

water (20 mL), once with brine (30 mL) and dried over MgSO4. The solvent was

evaporated and the residue (1.37 g) purified by flash chromatography (silica gel,

PE/EtOAc 30:1 to 20:1) and dried in vacuo (0.61 mbar, 75 °C, 2 h) to yield 418 mg

(69 %) of calixarene 85 (Rf = 0.46 in PE/EtOAc 20:1) as a colorless solid.

Recrystallization from DCM/ MeOH and DCM/iPrOH gave 252 mg (42 %) crystals

with mp 229–231 °C.

C58H64O4·1/8 CH2Cl2 (835.74)

calcd.: C 83.53, H 7.75

found: C 83.41, H 7.34

IR (KBr): ν~ = 3057 (w), 3023 (w), 2958 (m), 2929 (m), 2871 (m), 1592 (w), 1492 (m),

1459 (s), 1383 (m), 1308 (m), 1287 (w), 1247 (m), 1219 (s), 1196 (m), 1169 (w), 1136

(m), 1106 (w), 1082 (m), 1037 (m), 1005 (s), 965 (m), 889 (w), 858 (w), 837 (w), 801

(w), 757 (s) cm-1.


UV/Vis (n-hexane): λmax (lgε) = 280 (4.2), 228 (4.3, sh) nm.

1H NMR (400 MHz, CD2Cl2, diagnostic signals of the minor isomer are marked with an

asterisk): δ = 0.89*, 0.95*, 0.99*, 1.03, 1.05 (all t, 12 H, J = 7.4 Hz, CH2CH3), 1.89 und

2.12* (both br s), 6 H, CH3), 1.93–2.08 (m, 8 H, CH2), 2.88*, 3.16*, 3.19 (all d, J = 13.2

Hz, J = 13.1 Hz, 4 H, ArCH2Ar), 3.78*, 3.87, 3.94 (all t, J = 7.3 Hz, J = 7.4 Hz, J = 7.6

Hz, 8 H, OCH2), 4.32*, 4.46*, 4.50 (all d, J = 13.1 Hz, J = 13.1 Hz, 4 H, ArCH2Ar),

6.23–6.84 (m, 12 H, ArH and alkene-H), 7.10-7.50 (m, 10 H, PhH) ppm.

13

C{1H} NMR (100 MHz, CD2Cl2): δ = 10.7, 10.8 (both q, CH2CH3), 17.6 (q, CH3),

23.8, 24.0 (both t, CH2), 31.6 (t, ArCH2Ar), 77.4, 77.7 (both t, OCH2), 122.6 (d, p-

Ar’CH), 126.3 (d, PhCH), 127.1 (d, PhCH), 128.1 (d, Alken-CH), 128.7 (d, PhCH),

128.8 (d, m-Ar’CH, PhCH), 129.03* (d, PhCH), 129.68* (d, m-Ar’CH), 129.81 (d, m-

ArCH), 132.4, 135.0, 135.97, 136.00, 144.7 (all s), 155.8 (s, styryl-CO), 157.2 (s,

ArCO) ppm.

MS (FAB): m/z (%) = 824 (100) M+, 751 (8).

Syntheses 235

1H NMR (400 MHz, CD2Cl2): cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (85)

13C NMR (100 MHz, CD2Cl2): cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (85)


2.2.8 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene (86a

and 86b)

In three parallel reactions, a suspension of calixarene 85 (84 mg, 102 µmol and twice

100 mg, 121 µmol), iodine (57 mg, 225 µmol; 68 mg, 269 µmol) and potassium

carbonate (759 mg, 5.49 mmol; 903 mg, 6.51 mmol) in benzene (200 mL) was degassed

with argon (30 min) and irradiated for 17 h (125 W medium-pressure lamp, quartz

filter), while a permanent argon stream was bubbled through the solution. Benzene was

removed in vacuo and the combined residues were suspended in dichloromethane

(20 mL) and insoluble material was filtered off. The solvent was evaporated and the

resulting brown solid (307 mg) was purified by flash chromatography (silica gel,

hexane/toluene 5:1 to 2:1, Rf (5:1) = 0.21; silica gel, PE/EtOAc 100:1, Rf = 0.17) to

yield 129 mg (46 %) of cyclization products. By HPLC (PE/EtOAc 200:1, p = 1.1 MPa)

and subsequent drying in vacuo (0.47 mbar, 75–80 °C, 1.5 h) 57 mg (20 %) of a

mixture of isomers 86a and 86b were obtained as a colorless solid with mp 161–163 °C.

C58H60O4 (821.09)

calcd.: C: 84.84, H: 7.37

found: C: 84.62, H: 7.12

IR (KBr): ν~ = 3066 (w), 3020 (w), 2959 (s), 2931 (s), 2872 (s), 2729 (w), 1621 (w),

1589 (w), 1518 (w), 1478 (m), 1452 (s), 1416 (m), 1382 (m), 1338 (m), 1290 (w), 1243

(s), 1196 (m), 1179 (s), 1142 (w), 1128 (w), 1083 (m), 1065 (w), 1036 (m), 1002 (s),

966 (s), 888 (w), 839 (w), 818 (w), 799 (w), 755 (s), 720 (w) cm-1.

UV/Vis (n-hexane): λmax (lgε) = 366 (3.3), 348 (3.4), 315 (4.4), 266 (5.1), 218 (4.9) nm.

Syntheses 237

Isomer 86a:

1H NMR (400 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 6 H, CH2CH3), 1.24 (t, J = 7.4 Hz,

6 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.74 (s, 6 H, CH3), 3.35 and 3.39 (two d,

superimposed, J = 14.9 Hz, J = 13.8 Hz, 2 H, ArCH2Ar), 3.76–3.86 (m, 4 H, OCH2),

4.15–4.26 (m, 2 H, OCH2), 4.32–4.44 (m, 2 H, OCH2), 4.60 (d, J = 13.4 Hz, 1 H,

ArCH2Ar), 4.62 (d, J = 13.2 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 14.9 Hz, 1 H, ArCH2Ar),

4.72 (d, J = 14.6 Hz, 1 H, ArCH2Ar), 4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar), 5.33 (d, J =

6.4 Hz, 2 H, m-ArH (86a)), 5.94 (t, J = 7.6 Hz, 2 H, p-ArH (86a)) 6.03 ( d, J = 6.7 Hz,

2 H, m-ArH (86a)), 7.52–7.62 (m, 8 H, Phen-H), 8.05 ( „t”, J = 7.5 Hz, J = 7.8 Hz, 2 H,

Phen-H), 8.60 (d, J = 7.9 Hz, 2 H, Phen-5-H) ppm.

Isomer 86b:


3 H, CH2CH3), 1.32 (t, J = 7.4 Hz, 3 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.73 (s, 6

H, CH3), 3.35 and 3.39 (two d, superimposed, J = 14.9 Hz, J = 13.8 Hz, 2 H, ArCH2Ar),

3.74 (t, J = 6.7 Hz, 2 H, OCH2), 3.87 (t, J =6.5 Hz, 2 H, OCH2), 4.15–4.26 (m, 2 H,

OCH2), 4.32–4.44 (m, 2 H, OCH2), 4.60 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.62 (d, J =

13.2 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 14.9 Hz, 1 H, ArCH2Ar), 4.72 (d, J = 14.6 Hz, 1

H, ArCH2Ar), 4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar), 5.12 (d, J = 7.5 Hz, 2 H, m-ArH

86b), 5.64 (t, J = 7.6 Hz, 1 H, p-ArH 86b), 6.23–6.31 (m, 3 H, p-ArH, m-ArH 86b),

7.52–7.62 (m, 8 H, Phen-H), 8.05 ( „t”, J = 7.5 Hz, J = 7.8 Hz, 2 H, Phen-H), 8.57 (d, J

= 8.0 Hz d, 2 H, Phen-5-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.1, 11.0, 11.2, 11.3 (all q, all CH2CH3), 19.8

(q, CH3), 23.3, 23.4, 23.8, 23.9, 24.0 (all t, all CH2), 30.2, 31.2 (both t, both ArCH2Ar),

76.5, 76.7, 77.0, 77.8, 78.0 (all t, all OCH2), 122.7, 122.8, 122.9 (all d, all p-ArCH),

124.3, 124.4 (both d, both Phen-8-C), 124.5 (d, Phen-6-C), 125.8 (d, Phen-7-C), 126.3,

126.8, 127.1(all d, all m-ArCH), 127.2 (d, Phen-1-C), 127.4 (d, Phen-C), 127.6 (d, m-

ArCH), 127.7, 128.4 (both s, both Phen-C), 128.5, 128.6 (both d, both Phen-5-C), 130.3

(s), 130.6 (s), 131.0, 131.1 ((both s, both Phen-C), 132.2, 132.7 (both s, ArCCH2Phen),


133.27 (s), 133.33 (s), 134.6, 134.9 (both s, both ArCCH2Phen), 136.91, 136.96 (both

s), 154.6, 154.9, 155.3 (all s, all ArCO), 159.6, 159.7 ( both s, both PhenCO) ppm.

MS (FAB): m/z (%) = 820 (100) M+.

Syntheses 239

1H NMR (400 MHz, CDCl3): cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-phenanthrene (86a and 86b)

13C NMR (100 MHz, CDCl3): cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-phenanthrene (86a and 86b)


2.2.9 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-


To a cooled (–78 °C) suspension of phosphonium bromide 84 (5.09 g, 11.4 mmol) in

dry THF (70 mL) nBuLi (8.55 mL, 15 % in hexane, 13.6 mmol) was added. The

reaction mixture was stirred 1 h at –78°C and 30 min at room temperature. A solution of

tetraformylcalixaren 87 (802 mg, 1.13 mmol) in dry THF (15 mL) was added at –78 °C.

The reaction was allowed to warm to room temperature overnight. The suspension was

hydrolyzed with water (80 mL), the aqueous layer was extracted with ethyl acetate

(2 x 40 mL) and the organic layer was washed with water (50 mL), brine (50 mL) and

dried over MgSO4. The solvent was evaporated and the residue (3.04 g) purified by

flash chromatography (silica gel, PE/EtOAc 20:1) and dried in vacuo (1.6–2.1 mbar,

75 °C, 1.5 h) to yield 773 mg (64 %) of calixarene 88 (Rf = 0.54 in PE/EtOAc 10:1) as a

colorless solid with mp 167–168 °C.

C76H80O4 (1057.45)

calcd.: C 86.32, H 7.63

found: C 86.33, H 7.46

IR (KBr): ν~ = 3079 (w), 3053 (w), 3020 (w), 2959 (m), 2931 (m), 2873 (m), 1597 (w),

1576 (w), 1542 (w), 1493 (m), 1465 (s), 1444 (m), 1383 (w), 1310 (w), 1288 (w), 1219

(m), 1145 (w), 1126 (w), 1106 (w), 1067 (w), 1036 (w), 1006 (m), 964 (w), 941 (w),

894 (w), 853 (w), 756 (m), 695 (m) cm-1.

UV/Vis (n-hexane): λmax (lgε) = 278 (4.5), 228 (4.4) nm.

Syntheses 241

1H NMR (400 MHz, CDCl3, diagnostic signals of the minor isomer are marked with an

asterisk): δ = 0.96* ppm, 1.00*, 1.02*, 1.05 (all t, J = 7.4, 7.3, 7.4, 7.5 Hz, 12 H,

CH2CH3), 1.83*, 1.96, 2.16* (all s, CH3) and 1.88–2.08 (m, , 20 H), 2.90*, 3.19*, 3.22

(all d, J = 13.0, 12.7, 13.0 Hz, 4 H, ArCH2Ar), 3.79* (t, J = 7.3 Hz) and 3.88–4.01* (m

with 3.94, t, J = 7.6 Hz, 8H, OCH2), 4.34*, 4.49*, 4.53 (all d, J = 12.9 and 13.0 Hz, 4H,

ArCH2Ar), 6.22-6.90 (m, 12 H, C=CH, m-ArH), 7.12-7.49 (m, 20 H, Ar’H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.35* ppm, 10.52, 10.64* (all q, CH2CH3),

17.15*, 17.29, 17.68 (all q, CH3), 23.47, 23.50* (all t, CH2), 31.22*, 31.30 (all t,

ArCH2Ar), 77.0, 77.3 (all t, OCH2), 125.9, 126.0, 126.1*, 126.7*, 126.8 (all d, m-ArCH,

Ar’CH), 127.8, 127.9* (both d, m-ArCH, C=CH), 128.2*, 128.27, 128.33*, 128.6* (all d,

Ar’CH), 129.2*, 129.5 (both d, m-ArCH), 132.1*, 132.4 (all s), 134.63 (s, ArCCH2Ar),

135.6*, 135.7 (both s), 144.2 (s), 154.8*, 155.2 (both s, ArCO) ppm.

MS (FAB): m/z (%) = 1056 (79) [M]+, 940 (17).


1H NMR (400 MHz, CDCl3): cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (88)

13C NMR (100 MHz, CDCl3): cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (88)

Syntheses 243

2.2.10 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-

calix[4]arene (132)

25,26-Dipropoxy-26,28-dihydroxy-calix[4]arene (131) (497 mg, 0.98 mmol) and

aluminium chloride (570 mg, 4.27 mmol) were dissolved in of dichloromethane (40 ml).

2-Bromophenylacetyl chloride (116) (503 mg, 2.15 mmol) was added and the solution

was stirred for 2 hours at room temperature. The mixture was treated with HCl (2 N,

30 mL) and the layers were separated. The organic layer was washed with water (2 x

20 mL), brine (20 mL), dried over MgSO4 and the solvent was evaporated. The crude

product (660 mg) was submitted to flash chromatography (silica gel, PE/EtOAc 5:1,

Rf (PE/EtOAc 1:1) = 0.83) and subsequently recrystallized from DCM/MeOH to yield

pure 132 (116 mg, 13 %) as a colorless solid.

1H NMR (200 MHz, CDCl3): δ = 1.32 (t, J = 7.5 Hz, 6 H, CH2CH3), 2.02–2.12 (m, 4

H, CH2CH3), 3.47 (d, J = 12.9 Hz, 4 H, ArCH2Ar), 3.99 (t, J = 6.2 Hz, 4 H, OCH2),

4.28 (d, J = 13.1 Hz, 4 H, ArCH2Ar), 4.38 (s, 4 H, CH2CO), 6.76 (t, J = 7.6 Hz, 2 H, p-

Ar’H), 6.92 (d, J = 6.8 Hz, 4 H, m-Ar’H), 7.08–7.23 (m, 6 H, PhH), 7.61 (d, J = 7.6 Hz,

2 H, PhH), 7.80 (s, 4 H, m-ArH) ppm.


1H NMR (200 MHz, CDCl3): 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-calix[4]arene (132)

Syntheses 245

2.2.11 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene

(133) and 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]arene (134)

Calixarene 76 (500 mg, 0.84 mmol) and aluminium chloride (108 mg, 0.81 mmol) were

suspended in dry dichloromethane (35 mL). A solution of 2-bromophenylacetyl chloride

(120) (188 mg, 0.81 mmol) in dry dichloromethane (10 mL) was added dropwise over

1 h 40 min. The resulting yellow solution was stirred for further 10 min and then

hydrolyzed with 2 N HCl (30 mL). The organic layer was separated, washed with water

(2 x 20 mL), brine (20 mL) and dried over MgSO4. The solvent was removed by rotary

evaporation and the residue purified by column chromatography (silica gel, PE/DCM

3:1 to 1:1, Rf (1:1) = 0.71, 0.42) and the isolated products were dried in vacuo

(1.8 mbar, 50 °C).

1st fraction (Rf = 0.71): Tripropoxycalix[4]arene 134 (101 mg, 22 %) as colorless solid

with mp 107-108 °C (lit.131 101–102 °C).


H, CH3), 1.82–2.00 (m, 4 H, CH2CH3), 2.19–2.38 (m, 2 H, CH2CH3), 3.23 and 3.31

(both d, superimposed, J = 13.8 Hz, J = 13.2 Hz, 4 H, ArCH2Ar), 3.75 and 3.82 (t and

“t”, superimposed, J = 6.6 Hz, “J” = 8.5 Hz, 6 H, OCH2), 4.39 and 4.43 (both d,

superimposed, J = 13.7 Hz, J = 13.1 Hz, 4 H, ArCH2Ar), 4.70 (s, 1 H, OH), 6.39 (m, 6

H, ArH), 6.79 (t, J = 7.4 Hz, 1 H, ArH), 6.98 (t, J = 7.4 Hz, 1 H, ArH), 7.11 (d, J = 7.4

Hz, 2 H, ArH), 7.19 (d, J = 7.4 Hz, 2 H, ArH) ppm.


1H NMR (200 MHz, CDCl3): 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]aren (134)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

3.39

6.31

4.21

2.07

4.02

6.23

4.00

0.86

5.96

1.00

1.25

1.94

1.90

0.94

1.13

1.82

2.00

2.19

2.38

3.23

3.31

3.75

3.78

3.86

4.39

4.43

4.70

6.39

6.79

6.98

7.11

7.19

2nd fraction (Rf = 0.42): Ethanone 133 (169 mg, 25 %) as colorless solid with

mp 69–71 °C. Recrystallization of 133 from DCM/MeOH yielded analytically pure

material.

C48H53BrO5 (789.94)

calcd.: C 72.99, H 6.76

found: C 72.97, H 6.59

IR (KBr): ν~ = 3057 (w), 3014 (w), 2960 (s), 2930 (s), 2873 (s), 2736 (w), 1684 (m),

1590 (m), 1457 (s), 1417 (w), 1383 (m), 1326 (m), 1282 (m), 1266 (m), 1245 (m), 1206

(s), 1194 (s), 1164 (m), 1134 (s), 1109 (m), 1085 (s), 1065 (m), 1037 (w), 1005 (m), 964

(s), 889 (s), 834 (w), 799 (w), 760 (s) cm-1.

UV/Vis (n-hexane): λmax (lg ε) = 272 (4.2) nm.

1H NMR (400 MHz, CDCl3): δ = 0.98 (t, J = 7.5 Hz, 6 H, CH3), 1.02 and 1.04 (both t,

superimposed both J = 7.4 Hz, 6 H, CH3), 1.86 – 1.97 (m, 8 H, CH2CH3), 3.16 (d, J =

Syntheses 247

13.5 Hz, 2 H, ArCH2Ar), 3.21 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 3.81 (t, J = 7.3 Hz, 2 H,

OCH2), 3.84–3.94 (m, 6 H, OCH2), 4.14 (s, 2 H, C(O)CH2), 4.45 (d, J = 13.5 Hz, 2 H,

ArCH2Ar), 4.48 (d, J = 13.6 Hz, 3 H, ArCH2Ar), 6.41 (dd, J = 6.1 Hz, J = 8.6 Hz, 1 H,

p-Ar’’H), 6.47(d, J = 8.1 Hz, 2 H, m-Ar’’H), 6.65 (t, J = 7.4, 2 H, p-Ar’H), 6.71 – 6.74

(m, 4 H, m-Ar’H), 7.11 (“td”, J = 7.6, Hz, J = 1.7 H, Ph-4-H), 7.18 (dd, J = 7.7, J = 1.8

Hz, 1 H, Ph-6-H), 7.21 (s, 2 H, m-ArH), 7.25 (“td”, J = 7.4, Hz, J = 1.2 Hz, , 1 H, Ph-5-

H), 7.57 (dd, J = 8.0 Hz, J = 1.1, Hz, 1 H, Ph-3-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.4, 10.5, 10.6 (all q, CH3), 23.3, 23.46, 23.53

(all t, CH2CH3, 31.1, 31.2 (both, t, ArCH2Ar), 45.3 (t, C(O)CH2), 77.0 (t, OCH2), 122.0

(d, p-Ar’’CH), 122.4 (d, p-Ar’CH), 125.3 (s, CBr), 127.5 (d, Ph-5-CH), 128.09 (d, m-

Ar’’CH), 128.5 (d, m-Ar’CH), 128.6 (d, Ph-4-CH), 128.86 (d, m-ArCH), 128.92 (both

d, m-Ar’CH), 130.8 (s, p-ArC), 131.7 (d, Ph-6-CH), 132.9 (d, Ph-3-CH), 134.9 (s,

ArCCH2Ar), 135.0 (s, ArCCH2Ar), 135.5 (s, ArCCH2Ar), 135.6 (s, PhC), 135.8 (s,

ArCCH2Ar), 156.5 (s, Ar’’CO), 156.9 (s, Ar’CO), 161.2 (s, ArCO), 195.6 (s, C=O)

ppm.

MS (FAB): m/z (%) = 789 (27) [M+H]+, 619 (100) [M-CH2C6H5Br]+.


1H NMR (400 MHz, CDCl3): 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (133)

13C NMR (100 MHz, CDCl3): 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (133)

10.36

10.54

10.58

23.34

23.46

23.53

31.13

31.20

45.32

121.97

122.35

135.83

156.46

156.93

161.23

195.55

121.97

122.35

125.28

127.50

128.09

128.49

128.55

128.86

128.92

130.81

131.73

132.85

134.88

134.95

135.49

135.62

135.83

76.98

23.34

23.46

23.53

10.36

10.54

10.58

31.13

31.20

Syntheses 249

2.2.12 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-

propoxycalixarene (136)

Acid chloride 116 (1.95 g, 8.36 mmol) and aluminium chloride (648 mg, 4.81 mmol)

were suspended in dry dichloromethane (8 mL), calixarene 76 (451 mg, 0.76 mmol)

was added and the mixture heated under reflux for 1 h 15 min. The cooled solution was

hydrolyzed with ice cold 2 N HCl (8 mL), and the aqueous layer was extracted with

dichloromethane (2 x 15 mL). The organic layer was washed with 10 % NaOH (15 mL),

water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed at a

rotary evaporator. The crude product (1.41 g) was purified by multiple flash

chromatography (silica gel, PE/DCM 2:1 and PE/EtOAc 5:1 to 1:1, Rf (2:1) = 0.56) and

dried in vacuo (1.0 mbar, 100 °C) to yield 136 (79 mg, 8 %) as colorless solid.

Analytically pure material with mp 291–293 °C was obtained by recrystallization from

DCM/MeOH.

C72H68Br4O8 (1380.92)

calcd.: C 62.62, H 4.96

found: C 62.28, H 4.99

IR (KBr): ν~ = 3056 (w), 2963 (w), 2932 (w), 2874 (w), 1682 (s), 1593 (w), 1469 (w),

1440 (w), 1415 (w), 1386 (w), 1331 (m), 1288 (w), 1268 (w), 1224 (w), 1197 (w), 1145

(s), 1047 (w), 1027 (w), 999 (w), 959 (w), 930 (w), 885 (w), 868 (w), 837 (w), 818 (w),

805 (w), 745 (m) cm-1.

1H NMR (400 MHz, CDCl3): δ = 1.02 (t, J = 7.4 Hz, 12 H, CH3), 1.88–1.97 (m, J = 7.4,

14.9 Hz, 8 H, CH2CH3), 3.33 (d, J = 13.8 Hz, 4 H, ArCH2Ar), 3.94 (t, J = 7.4 Hz, 8 H,


OCH2), 4.10 (s, 8 H, CH2), 4.50 (d, J = 13.7 Hz, 4 H, ArCH2Ar), 7.02 (“td”, J = 7.7 Hz,

J = 1.7 Hz, 4 H, Ph-4-H), 7.11 (“td”, J = 7.5 Hz, J = 1.2 Hz, 4 H, Ph-5-H), 7.21 (dd, J =

7.6 Hz, J = 1.6 Hz, 4 H, Ph-6-H), 7.38 (s, 8 H, m-ArH), 7.50 (dd, J = 7.9 Hz, J = 1.2 Hz,

4 H, Ph-3-H) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.4 (q, CH3), 23.5 (t, CH2), 31.3 (t, ArCH2Ar),

45.4 (t, CH2), 77.2 (t, OCH2), 125.0 (s, CBr), 127.6 (d, Ph-5-CH), 128.5 (d, Ph-4-CH),

129.2 (d, m-ArCH), 131.2 (s, ArC), 132.4 (d, Ph-6-CH), 132.6 (d, Ph-3-CH), 135.1 (s,

ArCCH2Ar), 135.7 (s, PhC), 161.1 (s, ArCO), 195.5 (s, C=O) ppm.

MS (FAB): m/z (%) = 1424 (3), 1403 (2) [M+Na]+, 1381 (11) [M+H]+, 1251 (3), 1211

(18).

Syntheses 251

1H NMR (400 MHz, CDCl3): 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalixaren (136)

13C NMR (100 MHz, CDCl3): 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalixaren (136)

0102030405060708090100110120130140150160170180190200f1 (ppm)

10.4

23.5

31.3

45.4

125.0

127.6

128.5

129.2

131.2

132.4

132.6

135.1

135.7

161.1

195.5

77.077.5f1 (ppm)

77.2

128130132f1 (ppm)

127.6

128.5

129.2

131.2

132.4

132.6


2.2.13 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)

To a solution of bromocalixarene 135 (1.14 g, 1.70 mmol) in dry THF (80 mL)

n-butyllithium (1.8 mL, 2.87 mmol, 1.6 M in hexane) was added at –78 °C. The solution

was stirred for 15 min, after which a solution of iodine (1.42 g, 5.60 mmol) in dry THF

(10 mL) was added. The reaction mixture was stirred at room temperature overnight.

Saturated aqueous Na2SO3 (90 mL) was added, the aqueous layer was extracted with

ethyl acetate (90 mL) and the organic layer was washed with brine and dried over

MgSO4. The solvent was removed at a rotary evaporator and the crude product (1.14 g)

was purified by flash chromatography (silica gel, 1. PE/EtOAc 15:1, Rf = 0.52;

2. PE/DCM 5:1, Rf in 4:1 = 0.39) and dried in vacuo (0.67 mbar, 50–75 °C, 30 min) to

yield 438 mg (36 %) 139a as colorless solid with mp 60–62 °C.

C40H47IO4 (718.70)

calcd.: C 66.85, H 6.59

found: C 66.98, H 6.40

IR (KBr): ν~ = 3058 (w), 3014 (w), 2960 (m), 2928 (w), 2872 (w), 2734 (w), 1566 (w),

1539 (w), 1456 (m), 1383 (w), 1291 (w), 1246 (w), 1207 (m), 1193 (m), 1159 (w), 1084

(w), 1038 (w), 1006 (m), 964 (w), 910 (w), 889 (w), 864 (w), 837 (w), 799 (w), 761 (w)

cm-1.


1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.02 and 1.03 (both t, J

= 7.4 Hz, superimposed, 1 H, CH3), 1.85–1.95 (m, 8 H, CH2CH3), 3.08 (d, J = 13.5 Hz,

2 H, ArCH2Ar), 3.16 (d, J = 13.5 Hz, 2 H, ArCH2Ar), 3.78 and 3.80 (both t, J = 7.2 Hz,

superimposed, 4 H, OCH2), 3.84–3.91 (m, 4 H, OCH2), 4.37 (d, J = 13.4 Hz, 2 H,

Syntheses 253

ArCH2Ar), 4.45 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 6.46 (d, J = 7.5 Hz, 2 H, m-Ar’’H),

6.66–6.78 and 6.73 (m and s, superimposed, 9 H, p-Ar’H, m-Ar’H, p-Ar’’H, m-ArH)

ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.3 (q, CH3), 10.58 (q, CH3), 10.64 (q, CH3),

23.3 (t, CH2CH3), 23.4 (t, CH2CH3), 23.5 (t, CH2CH3), 30.9 (t, ArCH2Ar), 31.2 (t,

ArCH2Ar), 77.0 (t, OCH2) , 86.0 (s, ArCI), 122.2 (d, p-Ar’CH), 122.5 (d, p-Ar’’CH),

128.0 (d, m-Ar’’CH), 128.4 (d, m-Ar’CH), 128.9 (d, m-Ar’CH), 134.7 and 135.0 (both

s, Ar’’CCH2Ar and Ar’CCH2Ar), 136.0 (s, Ar’’CCH2Ar’), 136.8 (d, m-ArCH), 137.6 (s,

ArCCH2Ar’), 156.3 (s, Ar’’CO), 156.5, (s, ArCO) 157.1 (s, Ar’CO) ppm.

MS (FAB): m/z (%) = 741 (12) [M+Na]+, 718 (79) M+, 648 (14), 592 (28).


1H NMR (400 MHz, CDCl3): 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)

13C NMR (100 MHz, CDCl3): 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)

Syntheses 255

2.2.14 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b)

To a solution of dibromocalixarene 138 (2.03 g, 2.70 mmol) in dry THF (120 mL)

n-butyllithium (6 mL, 9.55 mmol, 1.6 M in hexane) was added at –78 °C. The solution

was stirred for 15 min, after which a solution of iodine (4.02 g, 15.8 mmol) in dry THF

(30 mL) was added. The reaction mixture was stirred at –78 °C for 15 min and at room

temperature overnight. Saturated aqueous Na2SO3 (150 mL) was added, the aqueous

layer was extracted with ethyl acetate (150 mL) and the organic layer was washed with

brine and dried over MgSO4. The solvent was removed at a rotary evaporator and the

yellow solid (2.14 g) was recrystallized from DCM/MeOH to yield 1.57 g (69 %) 139b

as colorless crystals with mp 249–251 °C (mp84 204–209 °C) after drying in vacuo

(1.6 mbar, 100 °C, 1 h).


H, CH3), 1.80–1.95 (m, 8 H, CH2CH3), 3.09 (d, J = 13.3 , 4 H, ArCH2Ar), 3.77 (t, J =

7.3 Hz, 4 H, OCH2), 3.87 (t, J = 7.7 Hz, 4 H, OCH2), 4.37 (d, J = Hz, 4 H, ArCH2Ar),

6.44-6.55 (m, 6 H, ArH), 7.11 (s, 4 H, m-ArH) ppm.

MS (FAB): m/z (%) = 844 (18) M+, 718 (13) [M–I]+.

Data are in accord with the literature.84


1H NMR (200 MHz, CDCl3): 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b)

Syntheses 257

2.2.15 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(141a)

In a screw-cap flask iodotetrapropoxycalixarene 139a (690 mg, 0.96 mmol), copper(I)

iodide (19 mg, 98 µmol) and triphenylphosphine (25 mg, 95 µmol) were suspended in

dry triethylamine (10 mL) under argon. Palladium(II) chloride (8 mg, 45 µmol) and

1-bromo-2-ethynylbenzene (140) (268 mg, 1.48 mmol) were added and the mixture was

stirred at 80 °C for 3 d. The crude product was diluted with dichloromethane and

filtrated over Celite. The mixture was washed with water (3 x 30 mL), dried over

MgSO4 and the solvent was removed in vacuo. The residue was purified by flash

chromatography (silica gel, 1. PE/EtOAc 15:1 and 2. PE/DCM 6:1 to 2:1, Rf (6:1) =

0.29) to yield 141a (553 mg, 75 %) as colorless solid with mp 76 °C after drying in

vacuo (0.47 mbar, 50–75 °C, 30 min).

C48H51BrO4 (771.82)

calcd.: C 74.70, H 6.66

found: C 74.99, H 6.29

IR (KBr): ν~ = 3058 (w), 3015 (w), 2960 (m), 2929 (w), 2873 (w), 2210 (w, C≡C),

1586 (w), 1455 (m), 1434 (w), 1383 (w), 1337 (w), 1290 (w), 1246 (w), 1209 (m), 1194

(w), 1159 (w), 1112 (w), 1085 (w), 1066 (w), 1041 (w), 1006 (m), 965 (w), 885 (w),

837 (w), 797 (w), 755 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 312 (4.9), 295 (5.0), 271 (sh, 5.0) nm.


1H NMR (400 MHz, CDCl3): δ = 1.00 (three t, J = 7.4 Hz, superimposed, 12 H, CH3),

1.86–1.97 (m, 8 H, CH2CH3), 3.16 (two d, J = 13.5 Hz, superimposed, 4 H, ArCH2Ar),

3.80–3.92 (m, 8 H, OCH2), 4.45 and 4.46 (both d, J = 13.4 and 13.5 Hz, superimposed,

4 H, ArCH2Ar), 6.52-6.65 (m, 8 H, m-Ar’H, m-Ar’’H, p-Ar’H), 6.70 (m, 1 H, p-Ar’’H),

6.88 (s, 2 H, m-ArH), 7.13 (td, J = 7.7 Hz, J = 1.7 Hz, 1 H, PhH), 7.26 (td, J = 7.6 Hz, J

= 1.1 Hz, 1 H, PhH), 7.50 (dd, J = 7.7 Hz, J = 1.6 Hz, 1 H, PhH), 7.59 (dd, J = 8.1 Hz, J

= 1.1 Hz, 1 H, PhH) ppm.

13


CH2CH3), 31.0, 31.2 (both t, ArCH2Ar), 76.7, 76.9 (both t, OCH2), 86.5 (s, PhC≡), 95.3

(s, ArC≡), 116.2 (s, p-ArC), 122.2 (d, p-Ar’CH), 122.3 (d, p-Ar’’CH), 125.7 (s, PhCBr),

126.2 (s, PhC), 127.1 (d, PhCH), 128.3, 128.4, 128.5 (all d, m-Ar’CH, m-Ar’’CH),

128.9 (d, PhCH), 131.9 (d, m-ArCH), 132.5, 133.1 (both d, PhCH), 134.5, 135.3, 135.4,

136.0 (all s, ArCCH2Ar), 156.6 (s, Ar’CO), 156.8 (s, Ar’’CO), 157.9 (s, ArCO) ppm.

MS (FAB): m/z (%) = 772 (90) M+.

Syntheses 259

1H NMR (100 MHz, CDCl3): 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (141a)

13C NMR (100 MHz, CDCl3): 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (141a)


2.2.16 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(141b)

In a screw-capped flask diiodotetrapropoxycalixarene 139b (500 mg, 0.59 mmol),

copper(I) iodide (23 mg, 0.12 mmol) and bis(triphenylphosphine)palladium(II) chloride

(42 mg, 59 µmol) were suspended in anhydrous triethylamine (10 mL) and degassed

with argon for 10 min. 1-Bromo-2-ethynylbenzene (140) (332 mg, 1.83 mmol) was

added and the mixture was stirred at 80 °C for 3 d. The crude product was diluted with

dichloromethane and filtrated over Celite. The mixture was washed with water

(3 x 30 mL), dried over MgSO4 and the solvent was removed in vacuo. The residue was

purified by flash chromatography (silica gel, PE/EtOAC 5:1 to 2:1, Rf (2:1) = 0.18),

recrystallized from DCM/MeOH and dried in vacuo (1.1 mbar, 100 °C, 40 min) to yield

141b (396 mg, 70 %) as colorless solid with mp 220–224 °C.

C56H54Br2O4 (950.83)

calcd.: C 70.74, H 5.72

found: C 70.94, H 5.46

IR (KBr): ν~ = 3060 (w), 3020 (w), 2960 (w), 2938 (w), 2873 (w), 2211 (w, C≡C),

1588 (w), 1478 (m), 1457 (m), 1433 (w), 1384 (w), 1336 (w), 1290 (w), 1239 (w), 1210

(w), 1195 (w), 1160 (w), 1114 (w), 1083 (w), 1064 (w), 1042 (w), 1030 (w), 1003 (w),

964 (w), 888 (w), 839 (w), 752 (m) cm-1.


Syntheses 261


H, CH3), 1.86–1.92 and 1.92–1.98 (both m, 8H, CH2CH3), 3.18 (d, J = 13.4 Hz, 4 H,

ArCH2Ar), 3.71 (t, J = 6.8 Hz, 4 H, OCH2), (t, J = 8.0 Hz 4 H, OCH2), 4.44 (d, J = 13.4

Hz, 4 H, ArCH2Ar), 6.27 (d, J = 7.5 Hz, 4 H, m-Ar’H), 6.33 (t, J = 7.5 Hz, 2 H p-Ar’H),

7.14 (t, J = 7.8 Hz, 2 H, PhH), 7.24 (t, J = 7.6 Hz, 2 H, PhH), 7.31 (s, 4 H, m-ArH), 7.53

(d, J = 7.7 Hz, 2 H, PhH), 7.60 (d, J = 8.0 Hz, 2 H, PhH) ppm.

13

C{1H} NMR (150 MHz, CDCl3): δ = 10.1 (q, CH3), 10.9 (q, CH3), 23.2 (t, CH2CH3),

23.6 (t, CH2CH3), 31.0 (t, ArCH2Ar), 76.9 (t, OCH2), 77.2 (t, OCH2), 87.0 (s, PhC≡),

95.0 (s, ArC≡), 116.1 (s, p-ArC), 122.5 (d, p-Ar’CH), 125.7 (s, PhCBr), 126.1 (s, PhC),

127.1 (d, PhCH), 128.0 (d, m-Ar’CH), 129.0 (d, PhCH), 132.4 (d, m-ArCH), 132.5 (d,

PhCH), 133.0 (s, Ar’CCH2Ar), 133.2 (d, PhCH), 137.2 (s, ArCCH2Ar’), 155.5 (s,

Ar’CO), 158.9 (s, ArCO) ppm.

MS (FAB): m/z (%) = 950 (29) M+.


1H NMR (600 MHz, CDCl3): 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (141b)

13C NMR (150 MHz, CDCl3): 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (141b)

Syntheses 263

2.2.17 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a)

Calixarene 141a (647 mg, 838 µmol) and p-toluenesulfonyl hydrazide (286) (3.10 g,

16.7 mmol) were dissolved in ethylene glycol dimethyl ether (7.5 mL) and heated to

85 °C. Over a period of 8 h a solution of sodium acetate (1.38 g, 16.8 mmol) in water

(6.5 mL) was added dropwise. The solution was stirred for further 6 h at 85 °C and

cooled to room temperature. Water (30 mL) and dichloromethane (30 mL) were added,

the layers separated and the aqueous layer was extracted with dichloromethane (3 x

15 mL). The organic layer was washed with aqueous ammonium chloride (1 N, 15 mL),

water (3 x 15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed

by rotary evaporation. The residue was purified by flash chromatography (silica gel,

1. PE/EtOAc 15:1, Rf = 0.54, 2. PE/DCM 10:1, Rf = 0.09). After drying in vacuo

(0.55–0.98 mbar mbar, 50, 30 min) 137a (547 mg, 84 %) was obtained as colorless

solid with mp 47–49 °C.

C48H55BrO4 (775.85)

calcd.: C 74.31, H 7.15

found: C 74.33, H 7.10

IR (KBr): ν~ = 3059 (w), 3013 (w), 2960 (m), 2928 (w), 2872 (w), 1587 (w), 1457 (m),

1383 (w), 1343 (w), 1286 (w), 1246 (w), 1213 (w), 1195 (w), 1160 (w), 1128 (w), 1108

(w), 1085 (w), 1039 (w), 1007 (w), 965 (w), 888 (w), 836 (w), 757 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 313 (sh, 3.1), 273 (3.7) nm.


1H NMR (600 MHz, CDCl3): δ = 0.97-1.02 (m, 12 H, CH3), 1.89–1.96 (m, 8 H,

CH2CH3), 2.60 (m, 2 H, ArCH2), 2.79 (m, 2 H, CH2Ph), 3.10 (d, J = 13.3 Hz, 2 H,

ArCH2Ar’), 3.15 (d, J = 13.3 Hz, 2 H, Ar’CH2Ar’’), 3.83–3.87 (m, 8 H, OCH2), 4.43 (d,

J = 13.3 Hz, 2 H, ArCH2Ar’), 4.46 (d, J = 13.3 Hz, 2 H, Ar’CH2Ar’’), 6.49 (s, 2 H, m-

ArH), 6.52–6.59 (m, 7 H, m-Ar’H, p-Ar’H, p-Ar’’H), 6.67 (d, J = 7.5 Hz, 2 H, m-

Ar’’H), 7.04 (t, J = 7.6 Hz, 1 H, PhH), 7.12 (d, J = 7.5 Hz, 1 H, PhH), 7.19 (d, J = 7.4

Hz, 1 H, PhH), 7.53 ( d, J = 8.0 Hz, 1H, PhH) ppm.

13

C{1H} NMR (150 MHz, CDCl3): δ = 10.4 (q, CH3), 10.47 (q, CH3), 10.52 (q, CH3),

23.39 (t, CH2CH3), 23.42 (t, CH2CH3), 31.2 (t, ArCH2Ar), 35.5 (d, ArCH2), 38.6 (t,

PhCH2), 76.8 (t, OCH2), 76.9 (t, OCH2), 121.96 (d, p-Ar’’CH), 122.02 (d, p-Ar’CH),

124.6 (s, PhCBr), 127.4 (d, PhCH), 127.6 (d, PhCH), 128.2 and 128.3 (both d, m-ArCH,

m-Ar’CH, m-Ar’’CH), 130.7 (d, PhCH), 132.9 (d, PhCH), 134.6 (s, ArC), 135.07,

135.12, 135.2, 135.5 (all s, ArCCH2Ar), 141.6 (s, PhC), 155.1 (s, ArCO), 156.6 (s,

Ar’CO), 156.9 (s, Ar’’CO) ppm.

MS (FAB): m/z (%) = 774 (45) M+.

Syntheses 265

1H NMR (600 MHz, CDCl3): 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene (137a)

13C NMR (150 MHz, CDCl3): 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene (137a)


2.2.18 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(137b)

Calixarene 141b (490 mg, 515 µmol) and p-toluenesulfonyl hydrazide (286) (3.89 g,

20.9 mmol) were dissolved in ethylene glycol dimethyl ether (5 mL) and heated to

85 °C. Over a period of 8 h a solution of sodium acetate (1.71 g, 20.9 mmol) in water

(4 mL) was added dropwise. The solution was stirred for further 6 h at 85 °C and cooled

to room temperature. Water (20 mL) and dichloromethane (20 mL) were added, the

layers separated and the aqueous layer was extracted with dichloromethane (3 x 15 mL).

The organic layer was washed with aqueous ammonium chloride (1 N, 15 mL), water

(3 x 15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed by

rotary evaporation. The residue was purified by flash chromatography (silica gel,

PE/EtOAc 4:1, Rf = 0.69) and recrystallized from DCM/MeOH. After drying in vacuo

(0.57 mbar, 100 °C, 20 min) 137b (418 mg, 85 %) was obtained as colorless solid with

mp 167–168 °C.

C56H62Br2O4 (958.90)

calcd.: C 70.14, H 6.52

found: C 70.41, H 6.43

IR (KBr): ν~ = 3060 (w), 3015 (w), 2959 (m), 2930 (m), 2872 (m), 1588 (w), 1467

(m), 1456 (m), 1384 (w), 1342 (w), 1305 (w), 1288 (w), 1247 (w), 1220 (m), 1195 (w),

1166 (w), 1134 (w), 1109 (w), 1082 (w), 1066 (w), 1039 (w), 1027 (w), 1007 (m), 965

(w), 935 (w), 886 (w), 836 (w), 822 (w), 802 (w), 751 (m) cm-1.


Syntheses 267

1H NMR (600 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 6 H, CH3), 1.04 (t, J = 7.41Hz, 6

H, CH3), 1.86–1.97 (m, 8 H CH2CH3), 2.71 (m, 4 H, ArCH2CH2), 2.93 (m, 4 H,

PhCH2CH2) 3.09 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 3.76 (t, J = 7.1 Hz, 4 H, OCH2), 3.90

(dd, J = 7.9 Hz, 4 H, OCH2), 4.42 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 6.31 (d, J = 7.5 Hz, 4

H, m-Ar’H), 6.41 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.70 (s, 4 H, m-ArH), 7.03 (td, J = 7.9

Hz, J = 1.6 Hz, 2 H, PhH), 7.06 (dd, J = 7.6 Hz, J = 1.4 Hz, 2 H, PhH), 7.14 (td, J = 7.5

Hz, J = 1.0 Hz, 2 H, PhH), 7.52 (dd, J = 7.9 Hz, J = 0.9 Hz, 2 H, PhH) ppm.

13


23.5 (t, CH2CH3), 31.1 (t, ArCH2Ar), 35.5 (t, ArCH2CH2), 38.7 (t, PhCH2CH2), 76.7 (t,

OCH2), 76.9 (t, OCH2), 122.1 (d, p-Ar’CH), 124.7 (s, PhCBr), 127.3 (d, PhCH), 127.6

(d, PhCH), 127.9 (d, m-Ar’CH), 128.7 (d, m-ArCH), 130.7 (d, PhCH), 132.9 (d, PhCH),

134.3 (s, Ar’CCH2Ar), 134.5 (s, ArC), 135.9 (s, ArCCH2Ar’), 141.3 (s, PhC), 155.7 (s,

ArCO), 156.0 (s, Ar’CO) ppm.

MS (FAB): m/z (%) = 958 (13) M+, 787 (5).


1H NMR (600 MHz, CDCl3): 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137b)

13C NMR (150 MHz, CDCl3): 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137b)

Syntheses 269

2.2.19 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and 5,17-Bis-(2-

chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)

Calixarene 138 (1.50 g, 2.00) was dissolved in dry THF (80 mL) and tBuLi (5.4 mL,

15 % in pentane, 8.35 mmol) was added at –78 °C and the solution stirred for 1 h. After

addition of amide 169b (2.44 g, 12.2 mmol) the mixture was warmed to room

temperature and heated to 60 °C for further 17 h. It was hydrolyzed with HCl (2 N,

60 mL) and the aqueous layer was extracted with DCM (2 x 60 mL). The organic layer

was washed with water (100 mL) and brine (60 mL), dried over MgSO4 and the solvent

was removed at a rotary evaporator to yield 3.73 g of a yellow oil, which was purified

by multiple flash chromatography (silica gel, PE/EtOAc 25:1 to 10:1).

1st fraction: Rf (PE/EtOAC 10:1) = 0.29, Chlorobenzoylcalixarene 163 (489 mg, 33 %)

as colorless solid with mp 87 °C.

C47H51ClO5 (731.36)

calcd.: C 77.19, H 7.03

found: C 77.05, H 7.16

IR (KBr): ν~ = 3059 (w), 3014 (w), 2962 (m), 2930 (w), 2873 (w), 2737 (w), 1666 (m),

1590 (w), 1458 (m), 1436 (w), 1384 (w), 1309 (m), 1288 (m), 1246 (w), 1206 (m), 1159

(w), 1119 (w), 1085 (w), 1063 (w), 1038 (w), 1006 (m), 964 (w), 894 (w), 849 (w), 803

(w), 757 (m) cm-1.



1H NMR (400 MHz, CD2Cl2): δ = 0.99 (t, J = 7.5 Hz, 6 H, CH3), 1.03, 1.04 (both t, J =

7.5 Hz, J = 7.4 Hz, superimposed, 6 H, CH3), 1.89-2.00 (m, 8 H, CH2CH3), 3.17 and

3.18 (both d, superimposed, J =13.4 Hz, J = 13.3 Hz, 4 H, ArCH2Ar), 3.82 (t, J = 7.4

Hz, 2 H, OCH2), 3.86–3.96 (m, 6 H, OCH2), 4.46 and 4.47 (both d, superimposed, J =

13.2 Hz, J = 13.4 Hz, 4 H, ArCH2Ar), 6.48 (“t”, “J” = 7.5 Hz, p-Ar’’H), 6.59 (d, J = 7.5

Hz, 2 H, m-Ar’’H), 6.62 (t, J = 7.3 Hz, p-Ar’H), 6.65 and 6.66 (both d, superimposed, J

= 7.5 Hz, 2 H, m-Ar’H), 6.75 and 6.76 (both d, superimposed, J = 7.0 Hz, m-Ar’H),

6.92 (dd, J = 7.6 Hz, J = 1.0 Hz, 1 H, Ph-6-H), 7.01 (s, 2 H, m-ArH), 7.26 („t“, „J“ =

7.2 Hz, 1 H, PhH), 7.38–7.44 (m, 2 H, PhH) ppm.

13C{

1H} NMR (100 MHz, CD2Cl2): δ = 10.6, 10.78, 10.84 (all q, CH3), 23.8, 23.95,

24.01 (all t, CH2CH3), 31.4, 31.5 (both t, ArCH2Ar), 77.4, 77.6, 77.7 (all t, OCH2),

122.4 (d, p-Ar’’CH ), 122.7 (d, p-Ar’CH ), 126.7 (d, PhCH), 128.6 (d, m-Ar’’CH),

128.8 (d, m-Ar’CH ), 129.2 (d, m-Ar’CH), 130.0 (d, Ph-6-CH), 130.5 (d, PhCH), 130.8

(s, ArC), 131.1 (d, PhCH), 131.3 (d, m-ArCH), 131.7 (s, ArC), 135.4 (s, ArCCH3),

136.0 (s, ArC), 136.3 (s, ArC), 156.9 (s, Ar’’CO), 157.3 (s, Ar’CO), 162.2 (s, ArCO),

194.2 (s, C=O) ppm.

MS (FAB): m/z (%) = 753 (8) [M+Na]+, 731 (38) [M+H]+.

Syntheses 271

1H NMR (400 MHz, CD2Cl2): 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163)

13C NMR (100 MHz, CD2Cl2): 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163)


2nd fraction: Rf (PE/EtOAc 10:1) = 0.10, Bis(chlorobenzoyl)calixarene 166 (481 mg,

28 %) as colorless solid with mp 244 °C.

C54H54Cl2O6 (869.91)

calcd.: C 74.56, H 6.26

found: C 74.51, H 6.34

IR (KBr): ν~ = 3059 (w), 3027 (w), 2961 (w), 2931 (w), 2874 (w), 2740 (w), 1666 (s),

1594 (m), 1462 (m), 1434 (m), 1385 (w), 1316 (m), 1291 (m), 1234 (w), 1208 (m),

1161 (w), 1119 (m), 1079 (w), 1061 (w), 1036 (w), 1008 (w), 961 (w), 892 (w), 852

(w), 837 (w), 809 (w), 758 (m) cm-1.



H, CH3), 1.88 – 1.98 (m, 8 H, CH2CH3), 3.19 (d, J = 13.4 Hz, 4 H, ArCH2Ar), 3.82 (t, J

= 7.4 Hz, 4 H, OCH2), 3.97 (t, J = 7.6 Hz, 4 H, OCH2), 4.46 (d, J = 13.3 Hz, 4 H,

ArCH2Ar), 6.49 (s, 6 H, m-Ar’H, p-Ar’H), 6.99 (d, J = 6.9 Hz, 2 H, Ph-6-H), 7.29 and

7.30 (td, J = 7.1, J = 1.8 Hz, and s, superimposed, 6 H, Ph-5-H and m-ArH), 7.37 and

7.40 (td, J = 8.0 Hz, J = 1.6 Hz, and dd, J = 8.0 Hz, J = 1.6 Hz, superimposed, 4 H, Ph-

3-H and Ph-4-H) ppm.

13


CH2CH3) , 31.2 (t, ArCH2Ar), 77.0, 77.3 (both t, OCH2), 122.8 (d, p-Ar’CH), 126.6 (d,

Ph-5-CH), 128.4 (d, m-Ar’CH), 129.5 (d, Ph-6-CH), 130.0 (d, Ph-3-CH), 130.5 (d, Ph-

4-CH), 130.8 (s, ArC), 131.3 (d, m-ArCH), 131.4 (s, PhC), 134.1 (s, Ar’CCH3), 136.0

(s, ArCCH3), 138.7 (s, PhC), 156.1 (s, Ar’CO), 162.2 (s, ArCO), 194.3 (s, C=O) ppm.

MS (FAB): m/z (%) = 869 (9) [M+H]+.

Syntheses 273

1H NMR (400 MHz, CDCl3): 5,17-Bis-(2-Chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)

13C NMR (100 MHz, CDCl3): 5,17-Bis-(2-Chlorobenzoyl)-tetra-n-propoxycalix[4]-arene (166)

0102030405060708090100110120130140150160170180190f1 (ppm)

10.3

10.5

23.4

23.5

31.1

122.8

126.6

128.4

134.1

136.0

138.7

156.1

162.2

194.3

77.077.5f1 (ppm)

77.0

77.3

129.5130.0130.5131.0131.5f1 (ppm)

129.5

130.0

130.5

130.8

131.3

131.4


2.2.20 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and

5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172)

Dipropoxycalixarene 131 (2.09 g, 4.11 mmol), aluminium chloride (2.49 g, 18.7 mmol)

and 2-bromobenzoyl chloride (148b) (1.91 g, 8.71 mmol) were dissolved in dry

dichloromethane (45 mL) and stirred for 10 min at room temperature. The mixture was

hydrolyzed with hydrochloric acid (2 N, 45 mL), the layers were separated and the

aqueous layer was extracted with dichloromethane (25 mL). The combined organic

layers were washed with water (25 mL) and brine (25 mL), dried over MgSO4 and the

solvent was removed in vacuo. The crude product (4.99 g) was purified by flash

chromatography (silica gel, PE/EtOAc 8:1 to 2:1) and the products were dried in vacuo

(0.56 mbar, 100 °C, 40 min).

1st Fraction: Rf (5:1 PE/EtOAc) = 0.13, Bis(bromobenzoyl)dipropoxycalixarene 171

(2.00 g, 57 %) as colorless solid with mp 165–169 °C.

C48H42Br2O6 (874.65)

calcd.: C 65.91, H 4.84

found: C 66.02, H 4.86

IR (KBr): ν~ = 3243 (br, m), 3060 (w), 2963 (w), 2929 (m), 2874 (w), 1733 (w), 1659

(s), 1587 (s), 1481 (w), 1459 (s), 1429 (s), 1386 (w), 1317 (s), 1289 (s), 1214 (w), 1160

(w), 1126 (s), 1078 (w), 1056 (w), 1027 (w), 1001 (w), 958 (s), 916 (w), 857 (w), 837

(w), 815 (w), 751 (m) cm-1.


Syntheses 275

1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.06 (m, 4 H,

CH2CH3), 3.43 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 3.99 (t, J = 6.1 Hz, 4 H, OCH2), 4.27

(d, J = 13.1 Hz, 4 H, ArCH2Ar), 6.81 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.92 (d, J = 7.6 Hz, 4

H, m-Ar’H), 7.29 (d, J = 7.5 Hz, 2 H, PhH), 7.32–7.37 (t, J = 7.4 Hz, 2 H, PhH), 7.41 (t,

J = 7.5 Hz, 2 H, PhH), 7.59 (s, 4 H, m-ArH), 7.66 (d, J = 8.0 Hz, 2 H, PhH), 9.25 (s, 2

H, OH) ppm.

13

C{1H} NMR (150 MHz, CDCl3): δ = 11.1 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,

ArCH2Ar), 78.7 (t, OCH2), 119.7 (s, PhCBr), 125.8 (d, p-Ar’CH), 127.2 (d, PhCH),

127.6 (s, p-ArC), 128.3 (s, ArCCH2Ar’), 129.0 (d, PhCH), 129.6 (d, m-Ar’CH), 130.8

(d, PhCH), 131.8 (d, m-ArCH), 132.6 (s, Ar’CCH2Ar), 133.2 (d, PhCH), 141.7 (s, PhC),

151.9 (s, Ar’CO), 159.4 (s, ArCO), 194.6 (s, C=O) ppm.

MS (FAB): m/z (%) = 875 (29) [M+H]+, 183 (100).


1H NMR (600 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-arene (171)

13C NMR (150 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-arene (171)

Syntheses 277

2nd Fraction: Rf (5:1 PE/EtOAc) = 0.04, Tris(bromobenzoyl)dipropoxycalixarene 172

(137 mg, 3 %) as colorless solid with a melting range of 154–162 °C.

IR (KBr): ν~ = 3283 (br, w), 3057 (w), 2963 (w), 2931 (w), 2875 (w), 1661 (s), 1589

(s), 1563 (w), 1481 (w), 1461 (m), 1429 (m), 1387 (w), 1316 (s), 1292 (s), 1249 (w),

1214 (m), 1159 (w), 1128 (m), 1079 (w), 1053 (w), 1026 (w), 1009 (w), 957 (w), 916

(w), 856 (w), 838 (w), 825 (w), 770 (w), 749 (m) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 299 (4.7), 271 (sh, 4.7) nm.

1H NMR (400 MHz, CDCl3): δ = 1.296 and 1.298 (both t, J = 7.4 Hz, superimposed, 6

H, CH3), 2.02–2.11 (m, 4 H, CH2CH3), 3.42 and 3.46 (both d, J = 13.5 Hz, J = 13.4 Hz,

superimposed, 4 H, ArCH2Ar), 4.00 and 4.03 (both t, J = 6.3 Hz, superimposed, 4 H,

OCH2), 4.27 and 4.30 (both d, J = 12.9 Hz, J = 13.0 Hz, superimposed, 4 H, ArCH2Ar),

6.81 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.93 (d, J = 7.5 Hz, 2 H, m-Ar’’H), 7.10–7.13 (m, 1

H, Ph’H), 7.27–7.36 and 7.30 (m and s, 8 H, PhH, Ph’H, m-Ar’H), 7.41 (td, J = 7.4 Hz,

J = 0.9 Hz, 2 H, PhH), 7.48 (d, J = 2.1 Hz, 2 H, m-ArH), 7.52–7.54 (m, 1 H, Ph’H),

7.65 and 7.67 (dd, J = 8.1 Hz, J = 1.0 Hz and d, J = 2.2 Hz, superimposed, 4 H, PhH, m-

ArH), 8.77 (s, 2 H, OH) ppm.

13


31.3 (t, ArCH2Ar), 31.4 (t, ArCH2Ar), 78.7 (t, OCH2), 78.9 (t, OCH2), 119.7 (s, PhCBr),

120.1 (s, Ph’CBr), 125.7 (p-Ar’’CH), 127.3 (d, PhCH, Ph’CH), 127.7 (s), 127.8 (s),

128.4 (s, ArCCH2Ar), 129.1 (d, PhCH), 129.6 (d, m-Ar’’CH), 129.7 (d, Ph’CH), 130.9

(d, PhCH), 131.5 (d, Ph’CH), 131.8 (d, m-ArCH), 131.96 (d, m-Ar’CH), 132.00 (d, m-

ArCH) , 132.5 (s, Ar’’CCH2Ar), 133.3 (d, PhCH), 133.4 (d, Ph’CH), 140.0 (s, Ph’C),

141.4 (s, PhC), 151.9 (s, Ar’’CO), 156.7 (s, Ar’CO), 159.1 (s, ArCO), 194.4 (s,

ArC=O), 194.6 (s, Ar’C=O) ppm.

MS (FAB): m/z (%) = 1059 (17) [M+3]+, 183 (100).


1H NMR (400 MHz, CDCl3): 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxy-calix[4]arene (172)

13C NMR (100 MHz, CDCl3): 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxy-calix[4]arene (172)

Syntheses 279

2.2.21 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) and 5,17-Bis(2-

bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171)

Dipropoxycalixarene 131 (1.00 g, 1.97 mmol), aluminium chlorid (1.18 g, 8.85 mmol)

and 2-bromobenzoyl chloride (148b) (0.916 g, 4.17 mmol) were dissolved in dry

dichloromethane (25 mL) and stirred for 35 min at 0 °C. The mixture was hydrolyzed

with hydrochloric acid (2 N, 25 mL), the layers were separated and the aqueous layer

was extracted with dichloromethane (15 mL). The combined organic layers were

washed with water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was

removed in vacuo. The crude product (4.99 g) was purified by flash chromatography

(silica gel, PE/EtOAc 8:1 to 2:1) and the products were dried in vacuo (0.61 mbar,

100 °C, 30 min).

1st Fraction: Rf (5:1 PE/EtOAc) = 0.31, Bromobenzoyldipropoxycalixarene 170

(344 mg, 25 %) as colorless solid with mp 144–146 °C.

IR (KBr): ν~ = 3305 (br w), 3060 (w), 2961 (w), 2927 (w), 2873 (w), 1658 (w), 1589

(w), 1542 (w), 1521 (w), 1461 (m), 1431 (w), 1386 (w), 1317 (m), 1290 (w), 1214 (w),

1160 (w), 1127 (w), 1085 (w), 1058 (w), 1027 (w), 1005 (w), 961 (w), 914 (w), 858

(w), 836 (w), 815 (w), 756 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.03–2.11 (m, 4 H,

CH2CH3), 3.39 and 3.41 (both d, J = 13.0 Hz and J = 13.1 Hz, superimposed, 4 H,

ArCH2Ar), 3.94–4.03 (m, 4 H, OCH2), 4.29 and 4.31 ( both d, J = 13.1 Hz and J = 12.9

Hz, superimposed, 4 H, ArCH2Ar), 6.65 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.77 (t, J = 7.5


Hz, 2 H, p-Ar’H), 6.89 (dd, J = 7.6 Hz, J = 1.4, Hz, 2 H, m-Ar’H), 6.95 (dd, J = 7.5 Hz,

J = 1.4 Hz, 2 H, m-Ar’H), 7.06 (d, J = 7.5 Hz, 2 H, m-Ar’’H), 7.28-7.35 (m, 2 H, PhH),

7.40 (td, J = 7.4 Hz, J = 1.1 Hz, 1 H, PhH), 7.58 (s, 2 H, m-ArH), 7.65 (dd, J = 7.9 Hz, J

= 0.9 Hz, 1 H, PhH)), 8.26 (s, 1 H, OH), 9.28 (s, 1 H, OH) ppm.

13


ArCH2Ar), 31.6 (t, ArCH2Ar), 78.6 (t, OCH2), 119.2 (d, p-Ar’’CH), 119.7 (s, PhCBr),

125.6 (d, p-Ar’CH), 127.2 (d, PhCH), 127.5 (s, p-ArC), 128.1 (s, Ar’’CCH2Ar’), 128.5

(s, ArCCH2Ar’), 128.6 (d, m-Ar’’CH), 129.1 (d, PhCH), 129.2 (d, m-Ar’CH), 129.5 (d,

m-Ar’CH), 130.8 (d, PhCH), 131.8 (d, m-ArCH), 132.6 (s, Ar’CCH2Ar/Ar’’), 133.2 (d,

PhCH), 133.7 (s, Ar’CCH2Ar/Ar’’), 141.7 (s, PhC), 152.0 (s, Ar’CO), 153.5 (s,

Ar’’CO), 159.6 (s, ArCO), 194.6 (s, C=O) ppm.

MS (FAB): m/z (%) = 715 (14) [M+Na]+, 691 (100) M+, 183 (92).

2nd Fraction: Rf (5:1 PE/EtOAc) = 0.13, Bis(bromobenzoyl)dipropoxycalixarene 171

(973 mg, 58 %) as colorless solid with mp 165–169 °C. NMR data are in accord with

those mentioned before.

Syntheses 281

1H NMR (400 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)

13C NMR (100 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)


2.2.22 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162), 5-(2-Bromo-

benzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and paco-5-(2-

Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)

Sodium hydride (60 %, 897 mg, 22.4 mmol, washed with hexane (2 x 10 mL) prior to

use) was suspended in dry DMF (40 mL), calixarene 170 (1.18 g, 1.71 mmol) were

added and the suspension was heated to 80 °C for 30 min before adding propyl iodide

(6.35 mL, 65.1 mmol). The mixture was stirred at 80 °C overnight, cooled to room

temperature and poured into ice water (80 mL). It was extracted with dichloromethane

(3 x 20 mL), the organic layer was washed with aqueous ammonium chloride (1 N,

2 x 20 mL), water (20 mL) and brine (20 mL), dried over magnesium sulfate and the

solvent was removed in vacuo. The brown residue (1.22 g) was submitted to multiple

flash chromatography (silica gel, 1. PE/EtOAc 5:1 to 2:1; 2. PE/EtOAc 12:1 to 10:1;

3. PE/DCM 2:1 to 1:1) to yield:

1st Fraction: (Rf: 0.37 in PE/EtOAc 10:1), After drying in vacuo (75–100 °C, 0.38 mbar,

40 min) 78 mg (6 %) paco-bromobenzoylcalixarene 180 as a colorless solid with

mp 186–189 °C.

C47H51BrO5 (775.81)

calcd.: C 72.76, H 6.63

found: C 72.42, H 6.26

IR (KBr):ν~ = 3061 (w), 3028 (w), 2961 (w), 2930 (w), 2871 (w), 2738 (w), 1666 (m),

1587 (w), 1457 (m), 1429 (w), 1384 (w), 1312 (m), 1289 (w), 1248 (w), 1201 (m), 1160

(w), 1121 (w), 1085 (w), 1068 (w), 1043 (w), 1004 (w), 961 (w), 906 (w), 848 (w), 804

(w), 766 (w) cm-1.

Syntheses 283


1H NMR (400 MHz, CDCl3): δ = = 0.76 (t, J = 7.5 Hz, 3 H, CH3), 1.02 and 1.06 (both t,

J = 7.4 Hz, superimposed, 9 H, CH3), 1.36–1.46 (m, 2 H, CH2CH3), 1.74–1.83 (m, 4 H,

CH2CH3), 1.89–1.99 (m, 2 H, CH2CH3), 3.06 (d, J = 13.3 Hz, 4 H, ArCH2Ar), 3.33–

3.37 (m, 2 H, OCH2), 3.49–3.55 (m, 2 H, OCH2), 3.64–3.72 (m, 6 H, OCH2, ArCH2Ar),

3.82 (t, J = 7.3 Hz, 2 H, OCH2), 4.07 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 6.32 (dd, J = 7.6

Hz, J = 0.9 Hz, 2 H, m-Ar’H), 6.45 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.91 (m, 3 H, m-Ar’H,

p-Ar’’H), 7.09 (d, J = 7.4 Hz, 2 H, m-Ar’’H), 7.36 (td, J = 7.6 Hz, J = 1.8 Hz, 1 H, m-

PhH), 7.44 (td, J = 7.5 Hz, J = 1.0 Hz, 1 H, m-PhH), 7.50 (dd, J = 7.5 Hz, J = 1.7 Hz, 1

H, o-PhH), 7.68 (dd, J = 7.9 Hz, J = 0.9 Hz, 1 H, p-PhH), 7.75 (s, 2 H, m-ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.0

(t, CH2CH2), 23.9 (t, CH2CH2), 24.2 (t, CH2CH2), 30.7 (t, ArCH2Ar), 36.2 (t,

ArCH2Ar), 74.8 (t, OCH2), 75.5 (t, OCH2), 76.5 (t, OCH2), 120.0 (s, CBr), 121.7 (d, p-

Ar’CH), 122.5 (d, p-Ar’’CH), 126.9 (d, m-PhH), 128.9 (d, m-Ar’CH), 129.0 (d, o-PhH),

129.1 (d, m-Ar’’CH), 129.4 (d, m-Ar’CH), 129.9 (s, ArC), 130.7 (d, p-PhH), 131.4 (s,

Ar’CCH2Ar), 133.1 (d, m-ArCH), 133.4 (s, m-PhC), 133.7 (s, Ar’CCH2Ar’’), 134.6 (s,

ArCCH2Ar’), 137.1 (s, Ar’’CCH2Ar), 141.9 (s, PhC), 155.7 (s, Ar’CO), 156.9 (s,

Ar’’CO), 163.1 (s, ArCO), 195.1 (s, C=O) ppm.

MS (FAB): m/z (%) = 799 (7) [M+Na]+, 775 (40) [M+H]+, 733 (8), 185 (66).


1H NMR (400 MHz, CDCl3): paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)

13C NMR (100 MHz, CDCl3): paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)

Syntheses 285

2nd fraction: (Rf: 0.31 in PE/EtOAc 10:1) After drying in vacuo (75–100 °C,

0.42–0.86 mbar, 30 min) 433 mg (33 %) of cone-Bromobenzoyltetrapropoxycalixarene

162 as a colorless solid with mp 83–86 °C.

C47H51BrO5 (775.81)

calcd.: C 72.76, H 6.63

found: C 72.91, H 6.77

IR (KBr): ν~ = 3058 (w) , 3014 (w), 2961 (w), 2930 (w), 2873 (w), 1666 (w), 1589 (w),

1560 (w), 1540 (w), 1521 (w), 1507 (w), 1457 (m), 1433 (w), 1384 (w), 1309 (w), 1288

(w), 1246 (w), 1208 (m), 1159 (w), 1115 (w), 1086 (w), 1065 (w), 1037 (w), 1006 (w),

964 (w), 891 (w), 848 (w), 802 (w), 759 (w) cm-1.


1H NMR (400 MHz, CDCl3): δ = 0.99, 1.00 and 1.01 (each t, J = 7.1, 7.5 and 7.5 Hz,

superimposed, 12 H, CH3), 1.87–1.98 (m, 8 H, CH2CH3), 3.16 and 3.17 (both d, J =

13.5 and 13.3 Hz, superimposed, 4 H, ArCH2Ar), 3.81–3.87 (m, 4 H, OCH2), 3.89–3.94

(m, 4 H, OCH2), 4.45 (d, J = 13.3 Hz, 4 H, ArCH2Ar), 6.52–6.59 (m, 5 H, p-ArH, m-

ArH), 6.63–6.68 (m, 4 H, m-ArH), 6.95 (m, 1 H, PhH), 7.11 (s, 2 H, m-ArH), 7.27–7.31

(m, 2 H, PhH), 7.61 (m, 1 H, PhH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.4 (q, CH3),10.47 (q, CH3),10.51 (q, CH3),

23.37 (t, CH2CH3), 23.44 (t, CH2CH3), 23.5 (t, CH2CH3), 31.08 (t, ArCH2Ar), 31.13 (t,

ArCH2Ar), 77.0 (t, OCH2), 120.1 (s, PhCBr), 122.1 (d, p-Ar’’CH), 122.5 (d, p-Ar’CH),

126.7 (d, m-ArCH), 128.3 (d, m-ArCH), 128.4 (d, m-ArCH), 128.7 (d, m-ArCH), 129.7

(d, PhCH), 130.1 (s, ArC), 130.8 (d, PhCH), 131.2 (d, m-ArCH), 133.3 (d, PhCH),

134.6 (s, ArCCH2Ar), 135.1 (s, ArCCH2Ar), 135.5 (s, ArCCH2Ar), 135.6 (s,

ArCCH2Ar), 140.8 (s, PhC), 156.58 (s, Ar’CO), 156.64 (s, Ar’’CO), 161.9 (s, ArCO),

194.8 (s, C=O) ppm.

MS (FAB): m/z (%) = 799 (7) [M+Na]+, 775 (36) [M+H]+, 183 (100), 149 (32), 119

(58).


1H NMR (400 MHz, CDCl3): cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162)

13C NMR (100 MHz, CDCl3): cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162)

Syntheses 287

3rd fraction: (Rf: 0.18 in PE/EtOAc 10:1). Bromobenzoyltripropoxycalixarene 179

(344 mg, 27 %) was obtained as a colorless solid with mp 97–103 °C after drying in

vacuo (100 °C, 0.71–0.89 mbar, 1 h 15 min).

C44H45BrO5 (733.73)

calcd.: C 72.03, H 6.18

found: C 71.94, H 5.89

IR (KBr): ν~ = 3522 (w), 3443 (w), 3059 (w), 3016 (w), 2962 (w), 2930 (w), 2873 (w),

1659 (w), 1590 (w), 1560 (w), 1541 (w), 1521 (w), 1507 (w), 1458 (m), 1431 (w), 1386

(w), 1320 (m), 1289 (w), 1248 (w), 1208 (w), 1160 (w), 1127 (w), 1086 (w), 1065 (w),

1042 (w), 1004 (w), 963 (w), 909 (w), 858 (w), 840 (w), 799 (w), 762 (w) cm-1.



H, CH3), 1.83–1.97 (m, 4 H, CH2CH3), 2.21–2.31 (m, 2 H, CH2CH3), 3.22 (d, J = 13.1

Hz, 2 H, ArCH2Ar), 3.35 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 3.70-3.79 (m, 4 H, OCH2),

3.82–3.86 (m, 2 H, OCH2), 4.34 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 4.40 (d, J = 13.1 Hz, 2

H, ArCH2Ar), 5.99 (s, 1 H, OH), 6.40 (m, 6 H, p-Ar’H, m-Ar’H), 6.97 (t, J = 7.4 Hz, 1

H, p-Ar’’H), 7.18 (d, J = 7.5 Hz, 1 H, m-Ar’’H), 7.32–7.37 (m, 1 H, PhH), 7.40–7.46

(m, 2 H, PhH), 7.60 (s, 2 H, m-ArH), 7.66 (d, J = 7.8 Hz, 1 H, PhH) ppm.

13


23.6 (t, CH2CH3), 30.8 (t, ArCH2Ar), 30.9 (t, ArCH2Ar), 76.6 (t, OCH2), 77.8 (t,

OCH2), 119.8 (s, PhCBr), 123.2 (d, p-Ar’’CH), 123.4 (d, p-Ar’CH), 127.3 (d, m-PhCH),

127.5 (s, p-ArCH), 127.8 (d, m-Ar’CH), 128.5 (d, m-Ar’CH), 129.2 (d, o-PhCH), 129.3

(d, m-Ar’’CH), 130.3 (s, ArCCH2Ar), 130.8 (d, p-PhCH), 131.6 (d, m-ArCH), 131.7 (s,

ArCCH2Ar), 133.3 (d, m-PhCh), 133.7 (s, ArCCH2Ar), 137.1 (s, ArCCH2Ar), 141.8 (s,

PhC), 154.4 (s, Ar’CO), 157.0 (s, Ar’’CO), 159.3 (s, ArCOH), 195.1 (s, C=O) ppm.

MS (FAB): m/z (%) = 757 (10) [M+Na]+, 733 (40) [M+H]+, 183 (100), 149 (21), 119

(63).


1H NMR (400 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]-arene (179)

13C NMR (100 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]-arene (179)

Syntheses 289

2.2.23 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),


5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176)

Sodium hydride (60 % dispersion in paraffin, 497 mg, 12.4 mmol) was washed with

hexane (2 x 5 mL) under argon and suspended in DMF (32 mL) with calixarene 171

(1.09 g, 1.25 mmol). The suspension was stirred 30 min at 60 °C, 1-iodopropane

(1.85 mL, 19.0 mmol) was added at room temperature and the mixture was stirred 10

min at room temperature and further 2 h at 70–80 °C. After cooling to room temperature

ice water (60 mL) was added and the mixture was extracted with dichloromethane

(3 x 20 mL), the organic layer was washed with aqueous ammonium chloride (1 N,

15 mL), water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was

removed in vacuo. The residue was purified by flash chromatography (silica gel,

1. PE/EtOAc 6:1 to 2:1; 2. PE/DCM 2:1) and the products were dried in vacuo

(0.6 mbar, 100 °C).

1st fraction: Rf (4:1 PE/EtOAc) = 0.38, Rf (2:1 DCM/PE) = 0.15. 252 mg (21 %) of

cone-Bis(bromobenzoyl)calixarene 165 were obtained as colorless crystals with

mp 273–276 °C after crystallization from DCM/MeOH.

C54H54Br2O6 (958.81)

calcd.: C 67.64, H 5.68

found: C 67.59, H 5.88

IR (KBr): ν~ = 2961 (w), 2930 (w), 2873 (w), 1664 (s), 1592 (w), 1461 (w), 1430 (w),

1384 (w), 1316 (m), 1291 (m), 1237 (w), 1207 (m), 1161 (w), 1118 (w), 1078 (w), 1036

(w), 1007 (m), 961 (w), 894 (w), 836 (w), 808 (w), 756 (w) cm-1.




H, CH3), 1.88–198 (m, 8 H, CH2CH3), 3.19 (d, J = 13.4 Hz, 4 H, ArCH2Ar), 3.82 (t, J =

7.4 Hz, 4 H, OCH2), 3.97 (t, J = 7.5, 4 H, OCH2), 4.45 (d, J = 13.3 Hz, 4 H, ArCH2Ar),

6.49 (m, 6 H, m-Ar’H, p-Ar’H), 6.97 (dd, J = 7.31 Hz, J = 1.13 Hz, 2 H, PhH), 7.29,

7.30 and 7.35 (td, J = 7.6 Hz, J = 1.90 Hz, s and td, J = 7.5 Hz, J = 1.1 Hz,

superimposed, 8 H, PhH, m-ArH), 7.59 (dd, J = 7.9 Hz, J = 1.0 Hz, 2 H, PhH) ppm.

13


23.5 (t, CH2CH3), 31.1 (t, ArCH2Ar), 77.0 (t, OCH2), 77.3 (t, OCH2), 119.7 (s, PhCBr),

122.8 (d, p-Ar’CH), 127.2 (d, PhCH), 128.4 (d, m-Ar’CH), 129.4 (d, PhCH), 130.2 (s,

p-ArC), 130.9 (d, PhCH), 131.4 (d, m-ArCH), 133.1 (d, PhCH), 134.1 (s, Ar’CCH2Ar),

136.1 (s, ArCCH2Ar’), 140.8 (s, PhC), 156.1 (s, Ar’CO), 162.3 (s, ArCO), 195.0 (s,

C=O) ppm.

MS (FAB): m/z (%) = 959 (14) [M+H]+, 185 (54).

2nd fraction: Rf (2:1 DCM/PE) = 0.40, 431 mg (34 %) of paco-Bis(bromobenzoyl)-

calixarene 175 were obtained as colorless solid with mp 125–127 °C.

C54H54Br2O6 (958.81)

calcd.: C 67.64, H 5.68

found: C 67.84, H 5.78

IR (KBr): ν~ = 3062 (w), 3027 (w), 2960 (m), 2931 (m), 2873 (m), 1664 (s), 1559 (m),

1456 (m), 1429 (w), 1385 (w), 1313 (s), 1248 (w), 1208 (m), 1198 (m), 1160 (w), 1122

(m), 1082 (w), 1065 (w), 1049 (w), 1040 (w), 1028 (w), 1003 (m), 961 (w), 907 (w),

889 (w), 867 (w), 850 (w), 802 (w), 752 (m) cm-1.


Syntheses 291


6 H, CH2CH3), 1.08 (t, J = 7.5 Hz, 3 H, CH2CH3), 1.38-1.48 (m, 2 H, CH2CH3), 1.73–

1.82 (m, 4 H, CH2CH3), 1.91–2.01 (m, 2 H, CH2CH3), 3.10 (d, J = 13.5 Hz, 2 H,

ArCH2Ar), 3.41–3.45 (m, 2 H, OCH2), 3.47–3.53 (m, 2 H, OCH2), 3.64–3.72 and 3.67

(m and s, superimposed, 6 H, OCH2, ArCH2Ar), 3.84 (t, J = 7.3 Hz, 2 H, OCH2), 4.09

(d, J = 13.4 Hz, ArCH2Ar), 6.28 (dd, J = 7.7 Hz, J = 1.1 Hz, 2 H, m-Ar’H), 6.47 (t, J =

7.6 Hz, 2 H, p-Ar’H), 6.94 (dd, J = 7.5 Hz, J = 1.5 Hz, 2 H, m-Ar’H), 7.33–7.38 (m, 2

H, PhH), 7.40–7.48 (m, 4 H, PhH), 7.57 (s, 2 H, m-Ar’’H), 7.66-7.69 (m, 2 H, PhH),

7.75 (s, 2 H, m-ArH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH2CH3), 10.7 (q, CH2CH3), 10.9 (q,

CH2CH3), 22.1 (t, CH2CH3), 23.9 (t, CH2CH3), 24.2 (t, CH2CH3), 30.7 (t, ArCH2Ar),

36.0 (t, ArCH2Ar), 75.0 (t, OCH2), 75.6 (t, OCH2), 76.5 (t, OCH2), 119.8 (s, PhCBr),

120.0 (s, PhCBr), 121.9 (d, p-Ar’CH), 126.9 (d, PhCH), 127.3 (d, PhCH), 128.9 (d, m-

Ar’CH), 129.0 (d, PhCH), 129.2 (d, PhCH), 129.7 (d, m-Ar’CH), 130.0 (s, ArC), 130.6

(s, ArC), 130.8 (d, PhCH), 131.0 (d, PhCH), 131.5 (d, m-Ar’’CH, ArCCH2Ar)), 132.8

(s, ArCCH2Ar), 133.0 (s, m-ArCH), 133.3 (d, PhCH), 133.4 (d, PhCH), 134.5 (s,

ArCCH2Ar), 137.6 (s, ArCCH2Ar), 141.5 (s, PhC), 141.8 (s, PhC), 155.7 (s, Ar’CO),

162.3 (s, Ar’’CO), 163.0 (s, ArCO), 195.1 (s, C=O), 195.5 (s, C=O) ppm.

MS (FAB): m/z (%) = 959 (12) [M+H]+, 183 (100).

3rd fraction: Rf (4:1 PE/EtOAc) = 0.27, Rf (2:1 DCM/PE) = 0.24.140 mg (12 %)

Bis(bromobenzoyl)tripropoxycalixarene 176 according to NMR. Data were collected

from another experiment, where 176 was obtained as colorless solid with mp 142 °C.

C51H48Br2O6 (916.73)

calcd.: C 66.82, H 5.28

found: C 66.54, H 5.26

IR (KBr): ν~ = 3521 (w), 3442 (w), 2962 (w), 2930 (w), 2873 (w), 1662 (s), 1589 (m),

1458 (m), 1430 (w), 1386 (w), 1319 (s), 1249 (w), 1208 (m), 1161 (w), 1125 (m), 1081

(w), 1028 (w), 999 (w), 962 (w), 909 (w), 854 (w), 804 (w), 753 (w) cm-1.





Hz, 2 H, ArCH2Ar), 3.36 (d, J = 14.0 Hz, 2 H, ArCH2Ar), 3.74 (t, J = 6.7 Hz, 4 H,

OCH2), 3.91–3.95 (m, 2 H, OCH2), 4.32 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 4.41 (d, J =

13.2 Hz, 2 H, ArCH2Ar), 6.07 (s, 1 H, OH), 6.37–6.45 (m, 6 H, m-Ar’H, p-Ar’H), 7.33–

7.48 (m, 6 H, PhH), 7.60 (s, 2 H, m-ArH), 7.65 (s, 2 H, m-Ar’’H), 7.66 and 7.68 (two d,

J = 8.6 and 8.0 Hz, 2 H, PhH) ppm

13


23.6 (t, CH2CH3), 30.8 (t, ArCH2Ar), 30.9 (t, ArCH2Ar), 76.7 (t, OCH2), 77.9 (t,

OCH2), 119.8 (s, PhCBr), 123.6 (s, p-Ar’CH), 127.3 (d, PhCH), 127.4 (d, PhCH), 127.6

(s, p-ArC), 128.2 (d, m-Ar’CH), 128.5 (d, m-Ar’CH), 129.15 (d, PhCH), 129.23 (d,

PhCH), 130.1 (s, ArCCH2Ar’), 130.8 (d, PhCH), 131.2 (d, PhCH), 131.3 (s, p-Ar’’C),

131.6 (d, m-ArCH), 131.7 (d, m-Ar’CH), 131.9 and 132.8 (both s Ar’CCH2Ar,

Ar’CCH2Ar’’), 133.3 (d, PhCH), 133.4 (d, PhCH), 137.7 (s, Ar’’CCH2Ar’), 141.4 (s,

PhC), 141.7 (s, PhC), 154.4 (s, Ar’CO), 159.2 (s, ArCO), 162.3 (s Ar’’CO), , 195.1(s,

C=O), 195.4 (s, C=O) ppm.

MS (FAB): m/z (%) = 917 (26) [M+H]+, 183 (100).

Syntheses 293

1H NMR (400 MHz, CDCl3): cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (165)

13C NMR (100 MHz, CDCl3): cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (165)


1H NMR (400 MHz, CDCl3): paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (175)

13C NMR (100 MHz, CDCl3): paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (175)

Syntheses 295

1H NMR (400 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxy-calix[4]arene (176)

13C NMR (100 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxy-calix[4]arene (176)


2.2.24 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165)

To a mixture of calixarene 171 (460 mg, 0.53 mmol and sodium carbonate (1.46 g, 13.8

mmol) in acetonitrile (23 mL), 1-iodopropane (1.43 mL, 14.7 mmol) was added and the

suspension was refluxed for 3 d. The mixture war poured into cold HCl (2 N, 50 mL),

extracted with dichloromethane (3 x 15 mL) and dried over MgSO4. The solvent was

removed at a rotary evaporator and the resulting crystalline solid (468 mg), which was

treated with methanol in an ultrasonic bath. After drying in vacuo (1.1 mbar, 100 °C,

30 min) 386 mg (77 %) of 165 were obtained as colorless solid with mp 273–276 °C.

NMR data are in accord with those mentioned above (2.2.21).

Syntheses 297

2.2.25 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and 5,17-Bis(2-

chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174)

Dipropoxycalixarene 131 (1.40 g, 2.76 mmol), aluminium chloride (1.66 g, 12.4 mmol)

and 2-chlorobenzoyl chloride 148a (1.02 g, 5.81 mmol) were dissolved in dry

dichloromethane (30 mL) and stirred for 35 min at 0 °C. The mixture was hydrolyzed

with hydrochloric acid (2 N, 30 mL), the layers were separated and the aqueous layer

was extracted with dichloromethane (15 mL). The combined organic layers were

washed with water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was

removed in vacuo. The crude product was purified by flash chromatography (silica gel,

PE/EtOAc 6:1 to 2:1) and the products were dried in vacuo (1 mbar, 100 °C, 30 min).

1st Fraction: Rf (2:1 PE/EtOAc) = 0.63, Chlorobenzoyldipropoxycalixarene 173 (616

mg, 35 %) as colorless solid with mp 134–136 °C.

C41H39ClO5 (647.20)

calcd.: C 76.09, H 6.09

found: C 75.77, H 5.97

IR (KBr): ν~ = 3322 (br w), 3061 (w), 2962 (w), 2927 (w), 2873 (w), 1657 (w), 1591

(w), 1541 (w), 1461 (m), 1433 (w), 1385 (w), 1317 (m), 1290 (w), 1214 (w), 1160 (w),

1127 (w), 1085 (w), 1060 (w), 1036 (w), 1003 (w), 961 (w), 915 (w), 859 (w), 836 (w),

815 (w), 757 (w), 702 (w) cm-1.



1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.04–2.10 (m, 4 H,

CH2CH3), 3.39 and 4.41 (both, d, J = 12.3 Hz, and J = 11.7 Hz, 4 H, ArCH2Ar),

3.95–4.02 (m, 4 H, OCH2), 4.29 and 4.31 (both d, J = 13.0 Hz and J = 12.9 Hz, 4 H,

ArCH2Ar), 6.65 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.78 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.88 (d,

J = 7.4 Hz, 2 H, m-Ar’H), 6.95 (d, J = 7.4 Hz, 2 H, m-Ar’H), 7.06 (d, J = 7.5 Hz, 2 H,

m-Ar’’H), 7.32 (d, J = 7.3 Hz, 1 H, PhH), 7.35 (d, J = 7.4 Hz, 1 H, PhH), 7.41 (t, J = 7.5

Hz, 1 H, PhH), 7.47 (d, J = 8.0 Hz, 1 H, PhH), 7.59 (s, 2 H, m-ArH), 8.26 (s, 1 H, OH),

9.27 (s, 1 H, OH) ppm.

13


ArCH2Ar), 31.6 (t, ArCH2Ar), 78.6 (t, OCH2), 119.2 (d, p-Ar’’CH), 125.6 (d, p-

Ar’CH), 126.7 (d, PhCH), 127.8 (s, p-ArC), 128.1 (s, Ar’’CCH2Ar’), 128.5 (s,

ArCCH2Ar’), 128.6 (d, m-Ar’’CH), 129.1 (d, m-Ar’CH), 129.2 (d, PhCH), 129.5 (d, m-

Ar’CH), 130.1 (d, PhCH), 130.7 (d, PhCH), 131.4 (s, PhCCl), 131.7 (d, m-ArCH),

132.6 (s, Ar’CCH2Ar), 133.7 (s, Ar’CCH2Ar’’), 139.6 (s, PhC), 152.0 (s, Ar’CO), 153.5

(s, Ar’’CO), 159.5 (s, ArCO), 194.0 (s, C=O) ppm.

MS (FAB): m/z (%) = 647 (59) [M+H]+, 139 (100).

Syntheses 299

1H NMR (600 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173)

13C NMR (150 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173)


2nd Fraction: Rf (2:1 PE/EtOAc) = 0.46, Bis(chlorobenzoyl)dipropoxycalixarene 174

(1.15 g, 53 %) as colorless solid with mp181-184 °C.

IR (KBr): ν~ = 3322 (br w), 3061 (w), 2962 (w), 2927 (w), 2873 (w), 1657 (w), 1591

(w), 1541 (w), 1461 (m), 1433 (w), 1385 (w), 1317 (m), 1290 (w), 1214 (w), 1160 (w),

1127 (w), 1085 (w), 1060 (w), 1036 (w), 1003 (w), 961 (w), 915 (w), 859 (w), 836 (w),

815 (w), 757 (w), 702 (w) cm-1.


1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.05-2.10 (m, 4 H,


(d, J = 13.1 Hz, 4 H, ArCH2Ar), 6.81 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.92 (d, J = 7.5 Hz, 4

H, m-Ar’H), 7.32 (d, J = 7.5 Hz, 2 H, PhH), 7.35 (t, J = 7.4 Hz, 2 H, PhH), 7.42 (t, J =

7.6 Hz, 2 H, PhH), 7.48 (d, J = 8.0 Hz, 2 H, PhH), 7.59 (s, 4 H, m-ArH), 9.23 (s, 2 H,

OH) ppm.

13


ArCH2Ar), 78.7 (t, OCH2), 125.8 (d, p-ArCH), 126.7 (d, PhCH), 128.0 (s, p-ArC),

128.3 (s, ArCCH2Ar’), 129.1 (d, PhCH), 129.6 (d, m-Ar’CH), 130.1 (d, PhCH), 130.7

(d, PhCH), 131.3 (s, PhCCl), 131.7 (d, m-ArCH), 132.7 (s, Ar’CCH2Ar), 139.6 (s, PhC),

151.9 (s, Ar’CO), 159.4 (s, ArCO), 193.9 (s, C=O) ppm.

MS (FAB): m/z (%) = 785 (31) [M+H]+, 139 (100).

Syntheses 301

1H NMR (600 MHz, CDCl3): 5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]-arene (174)

13C NMR (150 MHz, CDCl3): 5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]-arene (174)


2.2.26 cone-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163),

5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181) and

paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)

Sodium hydride (60 % dispersion in mineral oil, 1.38, 34.5 mmol, washed with hexane

(2 x 15 mL) prior to use) was suspended in dry DMF (60 mL), calixarene 173 (1.69 g,

2.62 mmol) were added and the suspension was heated to 80 °C for 30 min before

adding propyl iodide (10.0 mL, 102 mmol). The mixture was stirred at 80 °C overnight,

cooled to room temperature and poured into ice water (120 mL). It was extracted with

dichloromethane (3 x 20 mL), the organic layer was washed with aqueous ammonium

chloride (1 N, 2 x 20 mL), water (20 mL) and brine (20 mL), dried over magnesium

sulfate and the solvent was removed in vacuo. The brown residue (1.31 g) was

submitted to multiple flash chromatography (silica gel, 1. PE/EtOAc 6:1 to 2:1; 2.

PE/EtOAc15:1; 3. PE/DCM 2:1) to yield:

1st Fraction: Rf (10:1 PE/EtOAc): 0.29, Rf (2:1 PE/EtOAc): 0.83. After drying in vacuo

(1.1 mbar, 50–75 °C, 40 min) 454 mg (24 %) of cone-Chlorobenzoylcalixarene 163 as a

colorless solid with mp 87 °C.

NMR data are in accord with those mentioned above (2.2.19).

2nd Fraction: Rf (2:1 PE/EtOAc): 0.80. According to NMR about 293 mg (16 %) of

Chlorobenzoyltripropoxycalixarene 181 were formed. The compound was not further

characterized.



Hz, 2 H, ArCH2Ar), 3.35 (d, J = 14.0 Hz, 2 H, ArCH2Ar), 4.33 and 4.40 (both d,

Syntheses 303

superimposed, J = 12.5 Hz and J = 12.8 Hz, 4 H, ArCH2Ar), 5.99 (s, 1 H, OH), 6.40 (m,

6 H, m-ArH, p-ArH), 6.97 (t, J = 7.4 Hz, 1 H, p-ArH), 7.18 (d, J = 7.3 Hz, 2 H, m-ArH),

7.36–7.47 (m, 4 H, PhH), 7.61 (s, 2 H, m-ArH) ppm.

3rd Fraction: Rf (10:1 PE/EtOAc): 0.42. 46 mg (2 %) of paco-Chlorobenzoylcalixarene

182 as a colorless solid with mp 168–171 °C after drying in vacuo (0.71 mbar, 50–75

°C, 30 min).

C47H51ClO5·1/16 CH2Cl2 (736.67)

calcd.: C 76.73, H 7.00

found: C 76.63, H 7.00

IR (KBr): ν~ = 3063 (w), 3028 (w), 2961 (w), 2931 (w), 2873 (w), 2742 (w), 1665 (w),

1590 (w), 1457 (m), 1431 (w), 1384 (w), 1312 (m), 1293 (w), 1248 (w), 1200 (m), 1150

(w), 1121 (w), 1086 (w), 1064 (w), 1040 (w), 1005 (w), 962 (w), 907 (w), 888 (w), 849

(w), 804 (w), 758 (w) cm-1.



H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.35- 1.45 (m, 2 H, CH2CH3), 1.73-1.82 (m, 4

H, CH2CH3), 1.90-1.99 (m, 2 H, CH2CH3), 3.05 (d, J = 13.3 Hz, 2 H, ArCH2Ar), 3.33-

3.37 (m, 2 H, OCH2), 3.49-3.55 (m, 2 H, OCH2), 3.64-3.72 (m, 6 H, OCH2, ArCH2Ar),

3.82 (t, J = 7.3 Hz, 2 H, OCH2), 4.07 (d, J = 13.2 Hz, 2 H, ArCH2Ar), 6.32 (d, J = 6.7

Hz, 2 H, m-Ar’H), 6.45 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.91 (d, J = 6.8 Hz, t, J = 7.3 Hz,

superimposed, 3 H, m-Ar’H and p-Ar’’H), 7.09 (d, J = 7.4 Hz, 2 H, m-Ar’’H), 7.38 (td,

J = 7.3 Hz, J = 1.2 Hz, 1 H, m-PhH), 7.44 (td, J = 7.6 Hz, J = 1.7 Hz, 1 H, p-PhH),

7.48-7.52 (m, 2 H, o-PhH, m-PhH), 7.76 (s, 2 H, m-ArH) ppm.

13C{

1H} NMR 100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.0

(t, CH2CH3), 23.9 (t, CH2CH3), 24.2 (t, CH2CH3) 30.7 (t, ArCH2Ar), 36.2 (t, ArCH2Ar),

74.8 (t, OCH2), 75.5 (t, OCH2), 76.5 (t, OCH2), 121.7 (d, p-Ar’CH), 122.5 (d, p-


Ar’’CH), 126.4 (d, m-PhH), 128.9 (d, m-ArCH), 129.07 (d, m-ArCH), 129.11 (d, PhH),

129.4 (d, m-ArCH), 130.2 (d, PhH), 130.3 (s, PhC), 130.6 (d, p-PhH), 131.4 (s,

ArCCH2Ar), 131.6 (s, ArC), 133.1 (d, m-ArCH), 133.7 (s, ArCCH2Ar), 134.6 (s,

ArCCH2Ar), 137.2 (s, ArCCH2Ar), 139.9 (s, PhC), 155.8 (s, Ar’CO), 156.9 (s, Ar’’CO),

163.1 (s, ArCO), 194.5 (s, C=O) ppm.

MS (FAB): m/z (%) = 731 (21) [M+H]+, 139 (100).

1H NMR (200 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181)

Syntheses 305

1H NMR (400 MHz, CDCl3): paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)

13C NMR (100 MHz, CDCl3): paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)


2.2.27 cone-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (166), paco-

5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) and 5,17-Bis(2-

chloro-benzoyl)-25,26,27-tri-n-propoxcalix[4]arene (178)

Sodium hydride (60 %, 600 mg, 15.0 mmol) was wahed with hexane (2 x 5 mL) under

argon and suspended in DMF (25 mL) with calixarene 174 (896 mg, 1.14 mmol). The

suspension was stirred 30 min at 80 °C, 1-iodopropane (4.30 mL, 44.1 mmol) was

added at room temperature and the mixture was stirred at 80 °C overnight. After cooling

to room temperature ice water (50 mL) was added and the mixture was extracted with

dichloromethane (3 x 20 mL), the organic layer was washed with aqueous ammonium

chloride (1 N, 20 mL), water (20 mL) and brine (20 mL), dried over MgSO4 and the

solvent was removed in vacuo. The obtained solid was crystallized from DCM/MeOH

and dried in vacuo (0.91 mbar, 125 °C, 30 min) to yield 394 mg (40 %) of calixarene

166 as colorless crystals with mp 247 °C. The remaining residue was submitted to flash

chromatography (silica gel, PE/EtOAc 5:1, Rf in PE/EtOAc 5:1: 0.54 (177), 0.42 (178).

The first fraction was treated with methanol in an ultrasonic bath, filtrated and dried in

vacuo (0.35 mbar, 100 °C, 30–45 min). paco-Bis(chlorobenzoyl)calixarene 177 283 mg

(29 %) was isolated as a colorless solid with mp 184 °C. The second fraction contained

traces of still impure trialkylated calixarene 178.

Data for 166 are in accord with those mentioned above (2.2.19).

1st Fraction: Rf (5:1 PE/EtOAc): 0.54. paco-Bis(chlorobenzoyl)calixarene 177.

C54H54Cl2O6 (869.91)

calcd.: C 74.56, H 6.26

found: C 74.61, H 6.46

Syntheses 307

IR (KBr): ν~ = 3062 (w), 3025 (w), 2961 (w), 1932 (w), 1874 (w), 1663 (s), 1591 (w),

1456 (m), 1432 (w), 1286 (w), 1314 (s), 1292 (w), 1247 (w), 1207 (m), 1199 (m), 1160

(w), 1121 (m), 1083 (w), 1061 (w), 1038 (w), 1004 (w), 962 (w), 908 (w), 889 (w), 867

(w), 852 (w), 803 (w), 756 (m) cm-1.


1H NMR (400 MHz, CDCl3): δ = 0.76 (t, J = 7.5 Hz, 3 H, CH3), 1.01 (d, J = 7.5 Hz, 6

H, CH3), 1.08 (t, J = 7.5 Hz, 3 H, CH3), 1.37–1.47 (m, 2 H, CH2CH3), 1.72–1.81 (m, 4

H, CH2CH3), 1.91–2.01 (m, 2 H, CH2CH3), 3.10 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 3.42

(„t“, J = 8.3 Hz, 2 H, OCH2), 3.49 (t, J = 7.2 Hz, 2 H, OCH2), 3.51 (t, J = 7.2 Hz, 2 H,

OCH2), 3.63-3.73 (m with s at 3.67, superimposed, 6 H, OCH2, ArCH2Ar), 3.84 (t, J =

7.3 Hz, 2 H, OCH2), 4.08 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 6.27 (dd, J = 7.7 Hz, J = 1.0

Hz, 2 H, m-Ar’H), 6.47 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.94 (dd, J = 7.4 Hz, J = 1.5 Hz, 2

H, m-Ar’H), 7.36-7.50 (m, 8 H, PhH), 7.57 (s, 1 H, m-Ar’’H), 7.75 (s, 1 H, m-ArH)

ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.1

(t, CH2CH3), 23.8 (t, CH2CH3), 24.3 (t, CH2CH3), 30.8 (t, ArCH2Ar), 36.0 (t,

ArCH2Ar), 75.0 (t, OCH2), 75.6 (t, OCH2), 76.5 (t, OCH2), 122.0 (d, p-Ar’CH), 126.4,

126.8, 128.9 (d, m-ArCH), 129.12, 129.31, 129.7 (d, m-Ar’CH), 130.21, 130.24, 130.3,

130.7, 130.9, 130.97, 131.4 (d, m-ArCH), 131.5, 131.57 (s, ArCCH2Ar), 131.64, 132.8

(s, ArCCH2Ar), 133.0 (d, m-ArCH), 134.5 (s, ArCCH2Ar), 137.6 (s, ArCCH2Ar), 139.4

(s, PhC), 139.8 (s, PhC), 155.7 (s, Ar’CO), 162.3 (s, Ar’’CO), 163.0 (s, ArCO), 194.5

(s, C=O), 194.9 (s, C=O) ppm.

MS (FAB): m/z (%) = 869 (10) [M+H]+, 139 (100).


1H NMR (400 MHz, CDCl3): paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]-arene (177)

13C NMR (100 MHz, CDCl3): paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]-arene (177)

Syntheses 309

2.2.28 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184)

Calixarene 165 (253 mg, 264 µmol), pivalic acid (53 mg, 461 µmol) and potassium

carbonate (429 mg, 3.10 mmol) were suspended in DMA (5 ml) in a screw-cap flask.

Bedford catalyst 150 (28 mg, 17 µmol) was added under argon and the mixture was

heated to 120 °C for 10 h. After cooling to room temperature it was quenched with HCl

(2 N, 15 ml) and extracted with DCM (3 x 10 ml). The organic layer was washed with

water (10 ml) and dried over MgSO4. The solvent was removed in vacuo and the

residue was submitted to flash chromatography (silica gel, PE/toluene 50:1, Rf = 0.27)

and subsequently crystallized from DCM/EtOH to yield 184 (119 mg, 57 %) as a

yellow crystalline solid with mp > 300 °C after drying in vacuo (100 °C, 0.57 mbar,

20 min).

Mixture of steroisomers:

IR (KBr): ν~ = 3061 (w), 3017 (w), 2961 (w), 2932 (w), 2874 (w), 1707 (s), 1666 (w),

1572 (w), 1453 (w), 1435 (w), 1417 (w), 1382 (w), 1363 (w), 1307 (w), 1244 (w), 1187

(m), 1111 (w), 1087 (w), 1064 (w), 1038 (w), 1001 (w), 965 (w), 947 (w), 909 (w), 892

(w), 863 (w), 757 (w), 722 (w) cm-1.

UV/Vis (CH3CN): λmax (lg ε) = 349 (3.5), 302 (3.9), 273 (sh, 4.5), 263 (4.6) nm.

1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.12, 1.15 and 1.17

(three t, J = 7.4, superimposed, 6 H, CH3), 1.86–2.13 (m, 8 H, CH2CH3), 3.19, 3.24 and

3.26 (three d, J = 13.7, 13.7, 13.6 Hz, superimposed, 4 H, ArCH2Ar), 3.65–3.84 (m, 4

H, OCH2), 3.95–4.08 (m, 4 H, OCH2, ArCH2Ar), 4.20–4.30 (m, 2 H, OCH2), 4.41, 4.43,

4.45, 4.49 and 4.50 (five d, J = 13.5, 13.5, 13.3, 14.0, 13.9 Hz, superimposed, 4 H,


ArCH2Ar), 6.15–6.26 (m, 6 H, m-Ar’H, m-Ar’’H, p-Ar’H, p-Ar’’H), 7.25–7.30 (m, 2

H, fluorenoneH), 7.40–7.45 (m, 2 H, fluorenoneH), 7.56 (2 s, 2 H, fluorenoneH), 7.70

(d, J = 7.3 Hz, 2 H, fluorenoneH), 7.83 and 7.85 (two d, J = 8.1, J = 7.9 Hz,

superimposed, 2 H, fluorenoneH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.0 and11.0 (both q, CH3), 23.4, 23.71, 23.74,

23.8 (all t, CH2CH3), 25.5, 25.6, 31.2, 31.3 (all t, ArCH2Ar), 77.2 and77.3 (both t,

OCH2), 122.6 and 122.7 (both d, fluorenoneCH), 122.8, 122.9, 123.0 (all, d, p-Ar’CH,

p-Ar’’CH), 124.2 and 124.3 (both d, fluorenoneCH), 125.6 and 125.7 (both d,

fluorenoneCH), 127.3, 127.5, 127.8, 128.0 (all d, m-Ar’CH, m-Ar’’CH), 128.5 (d,

fluorenoneCH), 129.27, 129.29 (both s, fluorenoneC), 131.8, 131.9, 132.3, 132.5 (all s,

Ar’CCH2Ar, Ar’’CCH2Ar), 134.27 and 134.30 (both s, ArCCH2Ar’), 134.56 and 134.58

(both d, fluorenoneCH), 135.95 and 135.99 (both s, fluorenoneC), 137.3 (s,

ArCCH2Ar’’), 142.2 and 142.3 (both s, fluorenoneC), 145.31 and 145.33 (both s,

fluorenoneC), 155.0, 155.3, 155.6 (all s, Ar’CO, Ar’’CO), 165.1 (s, ArCO), 193.6 (s,

C=O) ppm.

MS (FAB): m/z (%) = 819 (26) [M+Na]+, 797 (100) [M+H]+.

Isomer 184a:


H, CH3), 1.85–2.30 (m, 8 H, CH2CH3), 3.26 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 3.68–3.79

(m, 4 H, OCH2), 3.98–4.04 and 4.00 (m and d, J = 13.7 Hz, 4 H, ArCH2Ar), 4.27 (m, 2

H, OCH2), 4.43 (d, J = 13.5 Hz, 2 H, ArCH2Ar), 4.49 (d, J = 14.0 Hz, 2 H, ArCH2Ar),

6.18–6.23 (m, 6 H, m-Ar’H, p-Ar’H), 7.26 (t, J = 7.2 Hz, 2 H, fluorenoneH), 7.42 (td, J

= 7.6 Hz, J = 1.2, Hz, 2 H, fluorenoneH), 7.56 (s, 2 H, fluorenoneH), 7.69 (dd, J = 7.3

Hz, J = 0.7 Hz, 2 H, fluorenoneH), 7.83 (d, J = 7.7 Hz, 2 H, fluorenoneH) ppm.

13


23.7 (t, CH2CH3), 25.5 (t, ArCH2Ar), 31.3 (t, ArCH2Ar), 77.3 (t, OCH2), 122.7(d,

fluorenoneCH), 122.9 (d, p-Ar’CH), 124.2 (d, fluorenoneCH), 125.6 (d, fluorenoneCH),

127.3 (d, m-Ar’CH), 128.0 (d, m-Ar’CH), 128.5 (d, fluorenoneCH), 129.3 (s,

fluorenoneC), 131.8 (s, Ar’CCH2Ar), 132.5 (s, Ar’CCH2Ar), 134.3 (s, ArCCH2Ar’),

Syntheses 311

134.6 (d, fluorenoneCH), 135.9 (s, fluorenoneC), 137.3 (s, ArCCH2Ar’),, 142.3 (s,

fluorenoneC), 145.3 (s, fluorenoneC), 155.3 (s, Ar’CO), 165.1 (s, ArCO), 193.6 (s,

C=O) ppm.


1H NMR (400 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184), mixture of stereoisomers

13C NMR (100 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184), mixture of stereoisomers

Syntheses 313

1H NMR (400 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184a)

13C NMR (100 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184a)


2.2.29 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene

(212)

Calixarene 188 (500 mg, 0.66 mmol), boronic acid 190 (327 mg, 1.65 mmol) and

tetrakis(triphenylphosphine)palladium(0) (90 mg, 77 µmol) were suspended in toluene

(11 mL) and methanol (3 mL). The mixture was stirred at 100 °C for 15 min, then 2 M

aqueous Na2CO3 (1.8 mL) was added and it was heated to 100 °C for another 4 h. After

cooling to room temperature, the suspension was diluted with CH2Cl2 (20 mL), washed

with 2 M aqueous Na2CO3 (10 mL) containing ammonia (25 %, 0.6 mL), water (10 mL)

and dried over magnesium sulfate. The solvent was removed at a rotary evaporator and

the residue purified by flash chromatography (silica gel, PE/DCM 2:1, Rf = 0.24).

Recrystallization from DCM/MeOH and subsequent drying in vacuo (0.77 mbar,

100 °C, 1 h) yielded 212 (202 mg, 34 %) as colorless crystals with mp 243–244 °C.

C66H52O4 (909.12)

calcd.: C 87.20, H 5.77

found: C 87.32, H 5.84

IR (KBr): ν~ = 3392 (m), 3056 (w), 3025 (w), 2923 (w), 2861 (w), 1594 (w), 1487 (w),

1467 (s), 1433 (m), 1373 (w), 1320 (w), 1249 (m), 1210 (m), 1184 (m), 1156 (w), 1112

(w), 1082 (w), 1009 (w), 978 (w), 913 (w), 887 (w), 823 (w), 761 (s), 742 (s), 699 (s)

cm-1.


1H NMR (400 MHz, CDCl3): δ = 3.16 (d, J = 13.2 Hz, 2 H, ArCH2Ar), 4.23 (d, J =

13.1 Hz, 2 H, ArCH2Ar), 5.00 (s, 2 H, OCH2), 6.50 (d, J = 7.6 Hz, 2 H, m-Ar’H), 6.68

Syntheses 315

(t, J = 7.6 Hz, 1 H, p-Ar’H), 6.87 (s, 2 H, m-ArH), 7.15–7.26 (m, 10 H, biphenyl-H),

7.33–7.45 (m, J = 49.2 Hz, 14 H, m-BnH, p-BnH, biphenyl-H), 7.56 (s, 2 H, OH), 7.62

(dd, J = 7.3 Hz, J = 2.1 Hz, 4 H, o-BnH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 31.4 (t, ArCH2Ar), 78.4 (t, OCH2), 125.3 (d, p-

Ar’CH), 126.2 (d, biphenyl-CH), 127.0 (d, biphenyl-CH), 127.4 (o-BnCH), 127.5 (d,

biphenyl-CH), 127.7 (s, ArCCH2Ar’), 128.1 (d, p-BnCH), 128.2 (d, biphenyl-CH),

128.9 (d, m-BnCH), 129.2 (d, m-Ar’CH), 130.0 (d, biphenyl-CH), 130.3 (d, m-ArCH),

130.6 (d, biphenyl-CH), 130.8 (d, biphenyl-CH), 132.1 (s, p-ArC), 133.0 (s,

Ar’CCH2Ar), 137.0 (s, BnC), 140.6 (s, biphenyl-C), 140.7 (s, biphenyl-C), 142.3 (s,

biphenyl-C), 151.9 (s, ArCO), 152.4 (s, ArCOH) ppm.

MS (FAB): m/z (%) = 908 (36) M+, 817 (9) [M-Bn]+.


1H NMR (400 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyl-oxycalix[4]arene (212)

13C NMR (100 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene (212)

Syntheses 317

2.2.30 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene

(214)

Calixarene 213 (500 mg, 0.75 mmol), boronic acid 190 (371 mg, 1.87 mmol) and

tetrakis(triphenylphosphine)palladium(0) (102 mg, 87 µmol) were suspended in toluene

(11 mL) and methanol (3 mL). The mixture was stirred at 100 °C for 15 min, then 2 M

aqueous Na2CO3 (1.8 mL) was added and it was heated to 100 °C for another 4 h. After

cooling to room temperature, the suspension was diluted with DCM (20 mL), washed

with 2 M aqueous Na2CO3 (10 mL) containing ammonia (25 %, 0.6 mL), water (10 mL)

and dried over magnesium sulfate. The solvent was removed at a rotary evaporator. The

residue was purified by flash chromatography (silica gel, PE/DCM 4:1 to 2:1,

Rf (2:1) = 0.36). Recrystallization from DCM/MeOH and subsequent drying in vacuo

(0.7 mbar, 100 °C, 1.5 h) yielded 214 (467 mg, 77 %) as colorless crystals with

mp 248–249°C.

C58H52O4 · 1/8 CH2Cl2 (823.65)

calcd.: C 84.76, H 6.39

found: C 84.53, H 6.47

IR (KBr): ν~ = 3312 (s br), 3056 (w), 3020 (w), 2961 (m), 2922 (s), 2871 (m), 1594

(w), 1485 (m), 1466 (s), 1432 (s), 1384 (w), 1319 (m), 1251 (m), 1201 (s), 1157 (s),

1109 (m), 1080 (w), 1039 (m), 1002 (m), 963 (s), 911 (w), 886 (w), 830 (w), 762 (s),

744 (s) cm-1.



1H NMR (400 MHz, CDCl3): δ = 1.27 (t, J = 7.4 Hz, 6 H, CH3), 1.96 – 2.06 (m, 4 H,


(d, J = 13.0 Hz, 4 H, ArCH2Ar), 6.54 (d, J = 7.5 Hz, 4 H, m-Ar’H), 6.66 (t, J = 7.5 Hz, 2

H, p-Ar’H), 6.87 (s, 4 H, m-ArH), 7.16–7.25 (m, 10 H, biphenyl-H), 7.36–7.45 (m, 8 H,

biphenyl-H), 8.04 (s, 2 H, OH) ppm.

13


ArCH2Ar), 78.3 (t, OCH2), 125.2 (d, p-Ar’CH), 126.2 (d, biphenyl-CH), 126.9 (d,

biphenyl-CH), 127.5 (d, biphenyl-CH), 127.8 (s, ArCCH2Ar’), 128.2 (d, biphenyl-CH),

129.1 (d, m-Ar’CH), 130.0 (d, biphenyl-CH), 130.2 (d, m-ArCH), 130.7 (d, biphenyl-

CH), 130.9 (d, biphenyl-CH), 132.0 (s, p-ArC), 133.2 (s, Ar’CCH2Ar), 140.6 (s,

biphenyl-C), 140.7 (s, biphenyl-C), 142.3 (s, biphenyl-C), 152.0 (s, ArCO), 152.5 (s,

ArCOH) ppm.

MS (FAB): m/z (%) = 812.3 (100) M+.

Syntheses 319

1H NMR (400 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene (214)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

*

*

13C NMR (100 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene (214)


2.2.31 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218)

Dibromocalixarene 138 (1.10 g, 1.47 mmol) was dissolved in dry THF (35 mL) and

cooled to –78 °C. After addition of nBuLi (6.40 mL, 10.2 mmol, 1.6 M in hexane) the

solution was stirred for 25 min before addition of trimethyl borate (3.11 mL, 99 %,

27.1 mmol) and the mixture was stirred at room temperature overnight. Hydrochloric

acid (4 N, 8 mL) was added and the solution was stirred for 90 min. It was with water

(2 x 20 mL), the aqueous layer was washed with ethyl acetate (20 mL), dried over

MgSO4 and the solvent removed in vacuo. The viscous residue was treated with hexane

(80 mL), sonicated for 10 min, filtrated and dried in vacuo (1 mbar, 100 °C, 30 min) to

yield 533 mg (53 %) of 218 as a colorless powder with mp 254–256 °C

(lit.85 249–251 °C). The product was used without further purification.

1H NMR data are in accord with those reported in the literature.85 A signal

superimposed by the HDO peak is marked by an asterisk. The signal at 3.97–4.09 ppm

indicates impurity as it should integrate to only 4 H and appear as a triplet.

Syntheses 321

1H NMR (200 MHz, DMSO-d6): 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218)


2.2.32 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(220)

Calixarene 218 (360 mg, 529 µmol) and 2,2'-dibromobiphenyl (219) (362 mg,

1.16 mmol) were dissolved in methanol (2.1 ml) and toluene (7.8 ml) and heated to 100

°C. The mixture was degassed with argon for 10 min before addition of Pd(PPh3)4

(84 mg, 72 µmol), stirred for 15 min, then aqueous Na2CO3 (2 M, 1.2 mL) was added

and the mixture was stirred for another 5 h. After cooling to room temperature, the

suspension was diluted with CH2Cl2 (20 mL), washed with aqueous Na2CO3 (2 M,

10 ml) containing ammonia (25 %, 0.6 mL), water (10 ml) and dried over magnesium

sulfate. The solvent was removed at a rotary evaporator. The residue was purified by

flash chromatography (silica gel, PE/DCM 6:1 to 1:1, Rf (3:1) = 0.38). Recrystallization

from DCM/MeOH and subsequent drying in vacuo (1.0 mbar, 100 °C, 30 min) yielded

220 (141 mg, 25 %) as colorless crystalline solid with mp 136 °C.

1H NMR (400 MHz, CD2Cl2): δ = 0.86 and 0.87 (both t, superimposed, J = 7.5 and 7.4

Hz, 6 H, CH2CH3), 1.07 (t, J = 7.4 Hz, 6 H, CH2CH3), 1.77-1.98 (m, 8 H, CH2CH3),

2.91, 2.97 and 2.98 (three d, superimposed, J = 12.7 Hz, 13.2 Hz and “J” = 14.9 Hz, 4

H, ArCH2Ar), 3.57 (t, J = 6.6. Hz, 4 H, OCH2), 3.93–3.99 (m, 4 H, OCH2), 4.31 and

4.33 (both d, superimposed, J = 13.3 and 13.2 Hz, 4 H, ArCH2Ar), 5.50–5.55 (m, 4 H,

m-Ar’H), 5.97–6.26 (m, 2 H, p-Ar’H), 6.86-6.90 (m, 2 H, m-ArH), 6.96–6.98 (m, 2 H,

m-ArH), 7.19–7.24 (m, 2 H, biphenyl-H), 7.30–7.34 (m, 6 H, biphenyl-H), 7.39–7.49

(m, 6 H, biphenyl-H), 7.65 (d, J = 7.9 Hz, biphenylH)

13

C{1H} NMR (100 MHz, CD2Cl2): δ = 10.2 (q, CH2CH3), 11.3 (q, CH2CH3), 23.7 (t,

CH2CH3), 24.1 (t, CH2CH3), 31.4 (t, ArCH2Ar), 77.0 (t, OCH2), 77.4 (t, OCH2), 122.3

(d, p-ArCH), 124.5 (s, CBr), 127.0 (d, biphenylCH), 127.5 (d, biphenylCH), 127.9,

Syntheses 323

127.96, 128.2, 128.3 (all d, m-Ar’CH), 128.5 (d, biphenylCH), 129.0 (d, biphenylCH),

130.6 (d, biphenylCH), 130.7 (d, m-ArCH), 130.8 (d, m-ArCH),, 131.1 (d,

biphenylCH), 133.1 (d, biphenylCH), 133.15 (d, biphenylCH), 133.24, 133.3 (both s),

133.4 (s, ArCCH2Ar), 134.97, 136.97, 137.00 (all s), 137.3 and 137.4 (s, ArCCH2Ar),

140.6, 142.3, 143.8 (all s), 155.5 (s, ArCO), 157.7 (s, ArCO) ppm.

MS (FAB): m/z (%) = 1054 (50) M+, 976 (23) [M-Br]+.


1H NMR (400 MHz, CD2Cl2): 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene (220)

13C NMR (100 MHz, CD2Cl2): 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene (220)

Syntheses 325

2.2.33 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes (217a and

217b)

Biphenyldipropoxycalixarene 214 (164 mg, 202 µmol) was dissolved in dry

dichloromethane (2 mL) and 2,2,2-trifluoroethanol (2 mL) and PIFA (200 mg,

456 µmol) was added. The mixture was stirred at room temperature for 15 min and the

solvent was removed at a rotary evaporator. The brown residue (352 mg) was dissolved

in acetic anhydride (1.5 mL) and one drop of concentrated sulfuric acid was added. The

mixture was heated to 100 °C for 30 min and warmed to room temperature. The next

day it was poured onto ice, extracted with dichloromethane (2 x 10 ml), dried over

MgSO4 and the solvent was removed by rotary evaporation. Methanol was added to the

brown liquid residue and the precipitated solid was collected by filtration and washed

with methanol. After purification by flash chromatography (silica gel, toluene,

Rf = 0.29) about 57 % of 216 were obtained according to the NMR spectrum.

Calixarene 216 (50 mg, 56 µmol) was dissolved in THF (3.5 mL) and NaOH (490 mg)

and water (0.3 mL) were added. The mixture was stirred in a screw-capped flask for 3 d

at room temperature. Water (10 mL) and dichloromethane (10 mL) were added, the

layers separated and the aqueous layer was extracted with DCM (10 mL). The organix

layer was wasches with water (10 mL) and HCl (1 N, 10 mL), dried over MgSO4 and

the solvents was removed at a rotary evaporator. The yellow residue was submitted to

flash chromatography (silica gel, PE/EtOAc 10:1, Rf = 0.15) and recrystallized from


DCM/MeOH to yield 217 (18 mg, 40 %) as colorless solid after drying in vacuo

(0.77 mbar, 100 °C, 45 min). According to the NMR spectra it is a 1:1 mixture of both

stereoisomers.

1H NMR (400 MHz, CDCl3): δ = 1.27–1.36 (m, CH2CH3), 2.05–2.15 (m, CH2CH3),

3.64 and 3.68 (both d, “J” = 14.9 and 14.4 Hz, superimposed, ArCH2Ar), 3.99-4.13 (m,

OCH2), 4.46 and 4.49 (both d, “J” = 12.4 and 12.9 Hz, superimposed, ArCH2Ar), 4.75-

4.90 (m, ArCH2Ar), 5.69 (d, J = 7.6 Hz, 2 H, m-ArH (217b)), 5.86–5.89 (m, 2 H, m-

ArH (217a), 1 H, p-ArH (Zb)), 6.24 (t, J = 7.6 Hz, 2 H, p-ArH (217a)), 6.62–6.68 and s

(m and s, 2 H, m-ArH (217a), 1 H, p-ArH (Zb), OH), 6.78 (s, OH), 6.91 (d, J = 7.6 Hz,

2 H, m-ArH (217b)), 7.50–7.66 (m, triphenyleneH), 8.31–8.37 with 8.32 and 8.38 (m

and 2 s, superimposed, triphenyleneH), 8.54-8.61 (m, triphenyleneH) ppm.

13

C{1H} NMR (100 MHz, CDCl3): δ = 10.9, 10.96, 11.03 (all q, CH2CH3), 23.6, 23.7,

23.8 (all t, CH2CH3), 29.0, 29.2, 31.6, 31.7 (all t, ArCH2Ar), 77.8, 78.1, 78.5 (all t,

OCH2), 122.4 (d, triphenyleneH), 122.5 (d, triphenyleneH), 122.9, 123.2 (d,

triphenyleneH), 123.6, 123.66, 123.68, 123.74 (d, p-ArH (217b)), 124.3 (d,

triphenyleneH), 124.9 (d, p-ArH (217b)), 125.3, 125.36, 125.38, 125.40, 126.0 (d,

triphenyleneH), 126.6, 127.4 (d, triphenyleneH), 127.5 (d, triphenyleneH), 127.8 (d, m-

ArH (217b)), 128.0(d, m-ArH (217a)), 128.8 (d, m-ArH (217a)), 128.9 (s), 129.0 (d, m-

ArH (217b)), 129.1 (s), 129.3 (s), 129.5 (d, triphenyleneH), 129.6 (d, triphenyleneH),

129.98 (s), 130.01 (s), 130.78 (s), 130.79 (s), 130.9 (s), 131.3 (s), 131.45 (s), 131.48 (s),

132.4 (s), 133.8 (s), 134.7 (s), 152.8, 153.2, 153.6 (all s, ArCO), 154.90, 154.94 (both s,

triphenyleneCO) ppm.

MS (FAB): m/z (%) = 808 (27) M+.

Syntheses 327

1H NMR (200 MHz, CDCl3): 50,51-Diacteyl-49,51-di-n-propoxycalix[4]di-triphenylenes (216a and 216b)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

0.90

1.19

1.28

1.29

2.03

2.27

2.36

2.38

2.92

3.26

3.42

4.27

4.52

4.74

5.24

5.34

5.67

5.76

6.21

6.34

6.53

7.04

7.16

7.23

7.41

7.70

8.17

8.35

8.36

8.43

8.57

8.63

*

1H NMR (200 MHz, CDCl3): 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]-ditriphenylenes (217a and 217b)


13C NMR (100 MHz, CDCl3): 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]-ditriphenylenes (217a and 217b)

Syntheses 329

2.2.34 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)

Biphenylcalixaren 220 (260 mg, 246 µmol), triphenylphosphine (26 mg, 99 µmol) and

DBU (0.154 mg, 990 µmol, 98 %) were dissolved in DMA (10 mL) in a screw-capped

flask. The mixture was degassed with argon for 10 min, palladium(II) chloride

(9 mg, 51 µmol) was added and the mixture was stirred for 18 h at 160 °C. After

addition of dichloromethane (20 mL), it was washed with water (15 mL), brine (15 mL)

and dried over MgSO4. The solvent was removed in vacuo and the brown residue

(275 mg) was submitted to flash chromatography (silica gel, PE/EtOAc 15:1, Rf = 0.31).

30 mg (ca. 17 %) of slightly impure 221 was isolated as a mixture of both steroisomers

in a ratio of about 1:1.4 221a:221b. Other fractions did also show product signals in the

NMR spectra, but it was not possible to estimate an overall yield due to the complex

mixture obtained.

1H NMR (400 MHz, CDCl3): δ = 1.00 (t, J = 7.5 Hz, CH2CH3), 1.18 (t, J = 7.4 Hz,

CH2CH3), 1.26 (t, J = 7.4 Hz, CH2CH3), 1.33 (t, J = 7.4 Hz, CH2CH3), 1.87–2.24 (m,

CH2CH3), 3.41 and 3.47 (both d, J = 13.5 and 13.3 Hz, superimposed, ArCH2Ar),

3.74–3.84 (m, OCH2), 4.19–4.31 (m , OCH2), 4.41–4.53 and 3.53 (m and d, J = 15.2

Hz, superimposed, OCH2, ArCH2Ar), 4.61, 4.64 and 4.68 (three d, J = 14.3 Hz, J = 13.5

Hz and J = 13.2 Hz, superimposed, ArCH2Ar), 4.85 and 4.87 (both d, J = 14.5 Hz, J =

14.2 Hz, superimposed, ArCH2Ar), 5.04 (d, J = 7.6 Hz, 2 H, m-ArH (221b), 5.28 (d, J =

7.4 Hz, 2 H, m-ArH (221a)), 5.57 (t, J = 7.6 Hz, 1 H, p-Ar’H (221b), 5.91 (t, J = 7.6 Hz,

2 H, p-ArH (221a)), 6.06 (d, J = 7.0 Hz, 2 H, m-ArH (221a), 6.27 („t“, „J“ = 7.5 Hz, 1

H, p-ArH (221b)), 6.38 (d, J = 7.5 Hz, 2 H, m-ArH (221b)), 7.51–7.70 (m,

triphenyleneH), 8.30–8.36 and 8.36 (m and s, triphenylene H), 8.42 (s, triphenylene H),

8.58–8.69 (m, triphenyleneH) ppm.


13C{

1H} NMR (100 MHz, CDCl3): δ = 10.1, 10.2, 11.0, 11.2, 11.3 (all q, CH2CH3),

23.4, 23.5, 23.8, 23.9, 24.0 (all t, CH2CH3), 30.9, 31.0, 31.4, 31.5 (all t, ArCH2Ar), 76.5,

77.7, 78.0 (all t, OCH2), 122.8 (d, p-ArCH (221b)), 122.88 (d, p-ArCH (221a)), 122.91

(d, triphenyleneCH), 123.0 (d, p-ArCH (221b)), 123.2 (d, triphenyleneCH), 123.3,

123.36, 123.38, 123.5, 123.6, 125.49 (d, triphenyleneCH), 125.52 (d, triphenyleneCH),

126.3 (d, m-ArCH (221b), 126.4 (d, triphenyleneCH), 126.5 (d, triphenyleneCH), 126.6

(d, triphenyleneCH), 126.9 (d, m-ArCH (221a)), 127.2 (d, m-ArCH (221a)), 127.5 (d,

triphenyleneCH), 127.7 (d, m-ArCH (221b)), 129.7 (s), 129.8 (d, triphenyleneCH),

129.9 (s), 130.1 (s), 130.8 (s), 131.09 (s), 131.11 (s), 131.90 (s), 131.94 (s), 132.0 (s),

132.5 (s), 134.0 (s), 134.2 (s), 134.6 (s), 134.9 (s), 136.7 (s), 136.8 (s), 154.3, 154.7,

155.4 (all s, ArCO), 160.8, 160.9 (all s, triphenyleneCO) ppm.

MS (FAB): m/z (%) = 892 (29) M+.

Syntheses 331

1H NMR (400 MHz, CDCl3): 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)

13C NMR (100 MHz, CDCl3): 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)


2.2.35 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)

Diformylcalixarene 78 (247 mg, 0.381 mmol) was dissolved in acetone (2 mL) and

chloroform (2 mL). After addition of sulfamic acid (128 mg, 1.32 mmol) in water

(1 mL) a solution of sodium chlorite (106 mg, 0.938 mmol) in water (1 mL) was added

dropwise and the mixture was stirred at room temperature overnight. The reaction was

quenched with hydrochloric acid (1 N, 15 mL), the aqueous layer was extracted with

chloroform (3 x 15 mL) and dried over MgSO4. The solvent was removed in vacuo to

yield (191 mg, 74 %) of 263 as colorless solid with mp > 300 °C (lit. 271–273 °C184, >

280 °C85 (dec)).


H, CH3), 1.77–2.02 (m, 8 H, CH2CH3), 3.16 (d, J = 13.7 Hz, 4 H, ArCH2Ar), 3.67 (t, J =

6.6 Hz, 4 H, OCH2), 4.00 (“t”, “J” = 8.2 Hz, 4 H, OCH2), 4.43 (d, J = 13.5 Hz, 4 H,

ArCH2Ar), 6.77 (m, 4 H, m-ArH), 7.04 (t, J = 7.3 Hz, 2 H, p-Ar’H) , 7.18 (d, J = 7.0

Hz, 4 H, m-Ar’H), 12.89 (br s, 2 H, OH) ppm.

13


CH2CH3), 31.1 (t, ArCH2Ar), 77.0 (t, OCH2), 123.0, 123.3, 129.6, 129.9, 133.8, 136.7,

157.7, 159.9, 172.2 (s, C=O) ppm.

NMR data are in accord with those reported in literature.85,184

Syntheses 333

1H NMR (200 MHz, CDCl3): 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)

13C NMR (50 MHz, CDCl3): 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)


2.2.36 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-dicarbonyl chloride (264)

Carboxycalixarene 263 (1.10 g, 1.61 mmol) was dissolved in anhydrous

dichloromethane (15 mL) and thionyl chloride (5 mL, 65.4 mmol) was added. The

mixture was heated to 50 °C for 3 h, the solvent was removed in vacuo and the residue

was taken up in dichloromethane (15 mL). It was washed with aqueous NaHCO3 (10 %,

2 x 10 mL) and water (15 mL), dried over MgSO4 and the solvent was removed by

rotary evaporation to yield 264 (847 mg, 73 %) as yellow solid. The crude product

contained at least 90 % of the acid chloride according to 1H NMR data, which are in

accord with the literature.187

335

III. Appendix

1 Cross-peak tables

1.1 General Remarks

The numbering of the molecules depicted with each cross-peak table does not follow

official guidelines. However, the numbering of the parent calixarene (see Chapter

I.1.1.4) was adopted for the calixarene framework. Further numbering includes first all

the lower rim substituents then those at the upper rim, always starting from the smallest

number at the calixarene framework. The system was adapted accordingly to

calixarenes with anellated subunits treating the fused rings as part of the parent

skeleton. The same system has been used for the numbering of the crystal structures.

Tentative assignments of peaks to a certain position are marked in italics. The

correlations between proton and carbon signal for these cases were deduced from the

spectra as good as possible. In addition, peak intensities as well as shifts of comparable

structures were considered. If the cross-peaks could not be correlated to a certain carbon

atom or those could not be assigned to a certain position, the respective cells in the table

are marked with ‘n.b.’ for ‘not determinable’.

336 Appendix

1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone

(118)

1

2

3

4

5

6

O

7 8

10

11

12

O

13

14

15

16

17

9

Br

C atom δ [ppm] HMQC cross peaks

[ppm]

7/8 16.43 2.34

11 45.78 4.40

9 59.81 3.77

13 125.26 -

16 127.63 7.28

15 128.77 7.15

2/6 129.57 7.73

3/5 131.43 -

17 131.80 7.24

1 132.49 -

14 132.92 7.60

12 135.42 -

4 161.61 -

10 195.80 -

Cross-peak tables 337

1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol

(124)

1

2

3

4

5

6

O

7 8

10

11

12

HO

13

14

15

16

17

9

Br18


[ppm]

7,8 16.3 2.30

11 46.3 3.05, 3.19

9 59.8 3.72

10 73.3 4.92

13 125.0 -

2,6 126.3 7.06

n.d. 127.5 7.24

n.d. 128.5 7.11

n.d. 131.0 -

n.d. 132.2 7.24

14 133.1 7.58

n.d. 138.1 -

12 139.3 -

4 156.6 -

338 Appendix

1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)-

trimethylsilane (125)

1

2

3

4

5

6

O

7 8

10

11

12

O

13

14

15

16

17

9

Br

Si

18

20

19


[ppm]

HMBC cross peaks

[ppm]

18,19,20 -0.24 -0.19 -0.19

7,8 16.3 2.28 7.01 (2,6)

11 47.8 2.89, 3.12 4.86 (10), 7.01 (2,6),

7.17 (17), 7.55 (16)

9 59.8 3.72 2.28 (7,8), 7.01 (2,6)

10 73.4 4.86 2.89 (11), 3.12 (11),

7.01 (2,6)

13 124.9 - 2.89 (11), 3.12 (11), 7.08

(15), 7.17 (17), 7.55 (14)

2,6 126.0 7.01 2.28 (7,8), 4.86 (10),

7.01 (2,6)

16 127.0 7.19 7.55 (14)

15 128.1 7.08 7.17 (17)

3,5 130.4 - 2.28 (7,8), 7.01 (2,6)

14 132.6 7.55 7.19 (16)

17 133.2 7.17 2.89 (11), 3.12 (11),

7.08 (15), 7.55 (14)

12 138.8 -

2.89 (11), 3.12 (11), 4.86

(10), 7.08 (15), 7.19 (16),

7.55 (14)



[ppm]

HMBC cross peaks

[ppm]

1 140.3 - 2.89 (11), 3.12 (11),

4.86 (10)

4 156.1 - 2.28 (7,8), 3.72 (9),

7.01 (2,6)

340 Appendix

1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-

dimethyl-phenyl)methanone) (120a) and Phenanthrene-9,10-

diylbis((4-methoxy-3,5-dimethylphenyl)methanone) (120b)

43

2

1 10a

10 9

8a 8

7

65

4b4a

10'

1'

O6'5' O4'

3' 2'

8'

9'

7'

10'

1'

6' 5'

4'

3'2'

O

8'

9'

7'

O


[ppm]

HMBC cross peaks

[ppm]

7’,8’ 16.4 2.30 7.77 (2’/6’)

9,10 48.9 5.47 5.47 (9/10), 6.95 (1/8)

9’ 59.8 3.77 -

4,5 124.5 7.83 6.95 (1/8), 7.17 (2/7),

7.37 (3/6)

1,8 127.0 6.95 5.47 (9/10)

3,6 127.9 7.37 7.17 (2/7)

2,7 128.2 7.17 6.95 (1/8), 7.83 (4/5)

2’,6’ 130.0 7.77 7.77 (2’/6’)

3’,5’ 131.7 - 2.30 (7’/8’)

1’ 133.8 - -

4a,4b 134.4 - 6.95 (1/8), 7.37 (3/6)

8a,10a 136.4 - 5.47 (9/10), 7.17 (2/7),

7.83 (4/5)

4’ 162.0 - 2.30 (7’/8’), 3.77 (9’),

7.77 (2’/6’)

10’ 201.7 - 5.47 (9/10), 7.77 (2’/6’)


43

2

1 10a

10 9

8a 8

7

65

4b4a

10'

1'

O6'5' O4'

3' 2'

8'

9'

7'

10'

1'

6' 5'

4'

3'2'

O

8'

9'

7'

O

C atom δ

[ppm]

HMQC cross peaks

[ppm] HMBC cross peaks [ppm]

7’,8’ 16.3 2.18 7.44 (2’/6’)

9’ 59.7 3.72 -

4,5 123.1 8.81 7.53 (2/7)

2,3,6,7 127.5 7.53, 7.69 7.73 (1/8)

1,8 127.9 7.73 7.69 (3/6)

8a,10a 128.9 - 7.53 (2/7), 8.81 (4/5)

4a,4b 130.6 - 7.53 (2/7), 7.69 (3/6),

7.73 (1/8), 8.81 (4/5)

3’/5’ 131.3 - -

2’,6’ 131.4 7.44 2.18 (7’/8’), 7.44 (2’/6’)

1’ 133.6 - -

9,10 135.5 - 7.69 (3/6)

4’ 162.0 - 2.18 (7’/8’), 3.72 (9’),

7.44 (2’/6’)

10’ 197.6 - 7.44 (2’/6’)

342 Appendix

1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and

1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)

1

2

3

4

5

6

O

7 8

10

11

12

O

13

14

15

16

17

9


[ppm]

HMBC cross peaks

[ppm]

7/8 16.4 2.32 7.69 (2/6)

11 45.4 4.23 7.28 (13/17)

9 59.8 3.75 -

15 126.9 7.24 7.28 (13/17)

14,16 128.8 7.32 7.32 (14/16)

13,17 129.6 7.28 4.23 (11), 7.24 (15)

2,6 129.9 7.69 7.69 (2/6)

3,5 131.4 - 2.32 (7/8)

1 132.5 - -

12 135.1 - 4.23 (11), 7.32 (14/16)

4 161.5 - 2.32 (7/8), 3.75 (9),

7.69 (2/6)

10 197.2 - 4.23, 7.69 (2/6)


1

2

3

4

5

6

OH

7 8

10

11

12

O

13

14

15

16

17

9


[ppm]

7/8 16.0 2.27

11 45.3 4.21

3/5 123.1 -

15 126.8 7.23

14,16 128.7 7.31

1 129.4 -

13,17 129.5 7.27

2/6 130.1 7.69

12 135.3 -

4 156.9 -

10 196.8 -

7/8 16.0 2.27

344 Appendix

1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)

1

2

3

4

5

6

O

7 8

10

11

12

14

15

16

17

9

Br

13


[ppm]

HMBC cross peaks

[ppm]

7,8 16.2 2.29 6.89 (4/6)

10 35.8 2.80 6.89 (4/6)

11 38.7 3.00 7.20 (17)

9 59.9 3.73 -

13 124.6 - 3.00 (11), 7.07 (15),

7.20 (17), 7.56 (14)

16 127.5 7.22 7.56 (14)

15 127.8 7.07 7.20 (17)

4,6 128.9 6.89 2.80 (10), 6.89 (4/6)

17 130.6 7.20 3.00 (11)

1,3 130.7 - 2.29 (7/8)

14 133.0 7.56 7.22 (16)

5 136.9 - 2.80 (10), 3.00 (11)

12 141.3 - 2.80 (10), 3.00 (11),

7.22 (16), 7.56 (14)

2 155.4 - 2.29 (7/8), 3.73 (9),

6.89 (4/6)


1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)

1

2

3

4

4a

10a

4b

8a

9

10

5

6

7

8

13

O

11

12


[ppm]

HMBC cross peaks

[ppm]

13 15.8 2.55 -

11 16.2 2.32 6.95 (1)

9 30.3 2.71 2.71 (10), 7.26 (8)

10 30.4 2.71 2.71 (9), 6.95 (1)

12 59.9 3.79 2.32 (11), 2.55 (13)

6 or 8 125.8 7.28 -

7 126.6 7.20 7.63 (5)

6 or 8 127.6 7.27 -

1 127.9 6.95 2.71 (10)

4 128.0 - 2.55 (13)

5 128.5 7.63 2.32 (11), 7.20 (7)

2 129.4 - -

4a 133.8 - 2.55 (13), 6.95 (1), 7.63 (5)

4b 135.0 - 7.27-7.28 (6/8)

10a 135.3 - 2.71 (9)

-

8a 139.9 - 2.71 (10), 7.20 (7), 7.63 (5)

3 156.9 - 2.32 (11), 2.55 (13), 3.79

(12), 6.95 (1)

346 Appendix

1.9 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone

(149a)

2

3

4

5

6

1

10

O

O

9

87

11

12

13

14

15

16

Cl


[ppm]

HMBC cross peaks

[ppm]

7,8 16.4 2.30 7.49 (2/6)

9 59.8 3.78 -

126.7 7.35 7.44

129.0 7.35 -

130.2 7.44 7.42

7.35

13,14,

15,16

131.0 7.42 7.35

2,6 131.3 7.49 2.30 (7/8), 7.49 (2/6)

131.5 - n.d. 1,3,5,11

132.2 - indetetminable

12 139.2 - 7.35, 7.42, 7.44

4 162.1 - 2.30 (7/8), 3.78 (9),

7.49 (2/6)

10 194.7 - 7.35 (16), 7.49 (2/6)


1.10 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone

(149b)

2

3

4

5

6

1

10

O

O

9

87

11

12

13

14

15

16

Br


[ppm]

HMBC cross peaks

[ppm]

7,8 16.38 2.29 7.48 (2,6)

9 59.83 3.77 -

12 119.60 - 7.30 (16), 7.64 (13)

15 127.21 7.40 7.64 (13)

16 128.90 7.30 7.34 (14)

14 131.00 7.34 7.30 (16)

2,6 131.46 7.48 2.29 (7,8), 7.48 (2,6)

3,5 131.55 - -

1 131.81 - -

13 133.28 7.64 7.40 (15)

11 141.20 - 7.40 (15), 7.64 (13)

4 162.12 - 2.29 (7,8), 3.77 (9),

7.48 (2,6)

10 195.31 - 7.30 (16), 7.48 (2,6)

348 Appendix

1.11 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c)

2

3

4

5

6

1

10

O

O

9

87

11

12

13

14

15

16

I


[ppm]

HMBC cross peaks

[ppm]

7,8 16.4 2.30 7.48 (2,6)

9 59.8 3.78 -

12 92.4 - 7.17 (14),.7.27 (16),

7.43 (15), 7.92 (13)

15 127.8 7.43 7.92 (13)

16 128.4 7.27 7.17 (14)

14 131.0 7.17 7.27 (16), 7.43 (15)

1 131.3 - -

3,5 131.6 - -

2,6 131.7 7.48 2.30 (7,8), 7.48 (2,6)

13 139.8 7.92 7.43 (15)

11 144.9 - 7.43 (15), 7.92 (13)

4 162.1 - 2.30 (7,8), 3.78 (9),

7.48 (2,6)

10 196.8 - 3.78 (9), 7.27 (16),

7.48 (2,6)


1.12 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)

1

2

3

4

4a

9a4b

8a9

5

6

78

1012

O

O

11

C atom δ

[ppm]

HMQC cross peaks

[ppm]

10 12.8 2.50

12 16.6 2.29

11 60.3 3.76

8 123.1 7.60

5 124.2 7.63

1 125.0 7.38

n.d. 127.6 -

7 128.3 7.25

n.d. 130.2 -

n.d. 131.7 -

6 134.5 7.45

n.d. 135.1 -

n.d. 142.5 -

n.d. 145.2 -

3 162.8 -

9 193.7 -

350 Appendix

1.13 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)

2

3

4

5

6

1

10

O

O

9

87

11

16

15

14

1312

17HO18

O


[ppm]

HMBC cross peaks

[ppm]

7,8 16.4 2.27 7.41 (2/6)

9 59.8 3.76 -

16 127.9 7.34 7.56 (14)

12 128.0 - 7.65 (15)

14 129.5 7.56 7.34 (16)

-

2,6 130.9 7.41 2.27 (7/8), 7.41 (2/6)

13 131.1 8.09 7.65 (15)

3,5 131.3 - -

1 132.6 - -

15 133.1 7.65 8.09 (13)

11 142.9 - 7.65 (15), 8.09 (13)

4 161.7 - 2.27 (7/8), 3.76 (9),

7.41 (2/6)

17 169.7 - 8.09 (13)

10 196.6 - 7.34 (16), 7.41 (2/6)


1.14 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one

(161)

12

1116

15

14

13

17

O10

1

O

23

4

56

7

O

9

8

O


[ppm]

HMBC cross peaks

[ppm]

7,8 16.4 2.20 6.94 (2/6)

9 59.8 3.70 -

10 91.8 - 6.94 (2/6), 7.55 (16),

7.68 (15)

16 124.3 7.55 7.54 (14)

12 125.7 - 7.55 (14 and 16), 7.92

(13)

13 126.1 7.92 7.69 (15)

2,6 127.7 6.94 2.20 (7/8), 6.94 (2/6)

14 129.3 7.54 7.55 (16)

3,5 131.0 - 2.20 (7/8), 6.94 (2/6)

15 134.1 7.69 7.92 (13)

1 136.2 - -

11 152.7 - 7.54 (14), 7.69 (15),

7.92 (13)

4 157.2 - 2.20 (7/8), 3.70 (9),

6.94 (2/6)

17 170.1 - 7.54 (14), 7.92 (13)

352 Appendix

1.15 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)

2

3

4

5

6

1

OH

8 7

9

10

11

12

13

14

15

16

17

18

1920


[ppm]

7,8 15.9 2.12

n.d. 122.5 7.20

n.d. 126.4 -

n.d. 127.1 -

n.d. 127.5 7.38

n.d. 127.9 7.22

n.d. 130.0 7.17

3,5 130.3 6.74

n.d. 130.6 7.40

n.d. 130.7 7.40

n.d. 133.6 -

n.d. 140.5 -

n.d. 140.6 -

n.d. 142.0 -

1 151.0 -


1.16 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)

3

2 1 6

54

O

8 7

1514

9 20

1312

11

10 19

18

1716


[ppm]

7,8 16.4 1.98

1 56.9 -

120.7 7.79

125.0 7.21

128.1 7.30

10,11,12,13,

16,17,18,19

128.7 7.43

n.d. 135.5 -

n.d. 141.6 -

n.d. 143.9 -

2,6 144.6 6.30

6 187.9 -

354 Appendix

1.17 1,3-Dimethyltriphenylen-2-yl acetate (211)

6

1

2

3

4

5

7

1213

18

8

9

10

11

14

15

16

17

1920

O21

22

O


[ppm]

HMBC cross peaks

[ppm]

20 17.4 2.42 8.37 (6)

19 18.4 2.76 -

22 20.8 2.46 -

6 122.9 8.37 2.42 (20), 2.76 (19)

n.d. 123.2 8.54 7.62

n.d. 123. 5 8.60 7.53

n.d. 123.6 8.54 -

n.d. 125.6 7.54 8.60

n.d. 126.8 - 8.42

n.d. 127.1 - 2.76 (19)

n.d. 127.2 7.61 8.54

n.d. 127.4 - 2.42 (20), 8.57

n.d. 128.9 8.41 7.61

n.d. 129.2 - 2.42 (20)

n.d. 130.0 - -

n.d. 130.1 - -

n.d. 130.3 -

n.d. 130.4 -

2.76, 8.37,

8.41, 8.53

8.60

7.53

n.d. 131.2 - 7.62, 8.42

2 149.0 - 2.42 (20), 2.76 (19), 8.37 (6)

21 169.1 - 2.46 (22)


1.18 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)

3

4

56

12

7

10

9

O

NH11

O

8

HN

12

1314

O

N15

16

17

18

C atom δ [ppm] HMQC cross peaks [ppm]

7,9 16.3 2.30

8 59.9 3.74

18 122.6 8.15

16 126.9 7.47

1 127.0 -

2,6 128.2 7.56

3,5 131. 7 -

17 137.5 7.86

14 148.4 -

15 148.8 8.61

4 160.68 -

13 160.70 -

10 164.0 -

356 Appendix

1.19 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolino-

hydrazonoyl chloride (247)

3

4

56

12

7

10

9

O

N

Cl

8

N11

12

Cl

N13

1415

16


[ppm]

HMBC cross peaks

[ppm]

7,9 16.4 2.36 7.80 (2/6)

8 59.9 3.77 -

16 123.5 8.24 7.43 (14)

14 125.8 7.43 8.24 (16), 8.78 (13)

1 128.9 - -

2,6 129.5 7.80 2.36 (7/9), 7.80 (2/6)

3,5 131.5 - 2.36 (7/9)

15 136.9 7.83 8.78 (13)

11 143.9 - 8.24 (16)

10 144.2 - 7.80 (4/6)

13 149.7 8.78 7.43 (14)

12 150.9 - 7.83 (15), 8.78 (13)

4 160.6 - 2.36 (7/9), 3.77 (8),

7.80 (4/6)


1.20 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-

oxadiazole (253)

3

4

56

12

7

10

9

O

8

O11

NN12

N13

14

1516


[ppm]

HMBC cross peaks

[ppm]

7,9 16.2 2.36 7.90 (2/6)

8 59.9 3.79 -

1 119.1 - 2.36 (7/9)

16 123.4 8.32 7.47 (14), 7.90 (15),

8.82 (13)

14 125.8 7.47 8.32 (16), 8.82 (13)

2,6 128.2 7.90 2.36 (7/9), 7.90 (2/6)

3,5 132.2 - 2.36 (7/9), 7.90 (2/6)

15 137.3 7.90 8.82 (13)

12 144.0 - 7.90 (15), 8.32 (16),

8.82 (13)

13 150.4 8.82 7.47 (14), 7.90 (15)

4 160.5 - 2.36 (7/9), 3.79 (8),

7.90 (2/6)

11 163.8 - 8.32 (16)

10 165.8 - 7.90 (2/6)

358 Appendix

1.21 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-

tetrazine (249)

N N

11NN

10

1 12

23

4

5 6N

13

14

1516

9

O

8

7


[ppm]

HMBC cross peaks

[ppm]

7,9 16.5 2.43 8.37 (2/6)

8 59.9 3.83 -

16 123.9 8.67 7.55 (14), 7.98 (15),

8.96 (13)

14 126.3 7.55 8.67 (16), 8.96 (13)

1 126.9 - 8.37 (2/6)

2,6 129.5 8.37 8.37 (2/6)

3,5 132.3 - 8.37 (2/6)

15 137.5 7.98 8.96 (13)

12 150.7 - 7.98 (15), 8.96 (13)

13 151.0 8.96 7.55 (14), 7.98 (15)

4 161.7 - 2.43 (7/9), 3.83 (8),

8.37 (2/6)

11 163.3 - 8.67 (16)

10 164.3 - 8.37(2/6)


1.22 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)

3

4

56

12

7

10

9

O

NH11

O

8

HN

12

1314

O15

16

1718

19


[ppm]

HMBC cross peaks

[ppm]

7,9 15.9 2.28 7.60 (2/6)

8 59.4 3.70 -

15,19 127.3 7.92 7.54 (17), 7.92 (15/19)

2,6 128.1 7.62 2.28 (7/9), 7.62 (2/6)

16,18 128.3 7.48 7.48 (16/18)

1 128.4 - -

3,5 130.3 - 2.28 (7/9)

17 131.4 7.54 7,92 (15/19)

14 133.3 - 7.48 (16/18)

4 159.3 - 2.28 (7/9), 3.70 (8),

7.62 (2/6)

10 165.0 - 7.62 (2/6)

13 165.3 - 7.92 (15/19)

360 Appendix

1.23 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzo-

hydrazonoyl chloride (259) and 2-(4-Methoxy-3,5-dimethyl-

phenyl)-5-phenyl-1,3,4-oxadiazole (260)

3

4

56

12

7

10

9

O

N

Cl

8

N11

12

Cl13

14

15

16

17


[ppm]

HMBC cross peaks

[ppm]

7,9 16.4 2.36 7.80 (2/6)

8 59.9 3.78 -

14,16 128.66 7.48 7.48 (14/16), 7.53 (15)

13,17 128.69 8.13 7.52, 8.13 (13/17)

1 129.1 - -

2,6 129.5 7.80 2.36 (7/9), 7.80 (2/6)

3,5 131.4 - 2.36 (7/9), 7.80 (4/6)

15 131.8 7.53 8.13 (13/17)

12 133.9 - 7.48 (14/16)

11 144.1 - 8.13 (13/17)

10 144.3 - 7.80 (4/6)

4 160.5 - 2.36 (7/9), 3.78 (8),

7.80 (4/6)


3

4

56

12

7

10

9

O

8

O11

NN12

13 14

15

1617


[ppm]

HMBC cross peaks

[ppm]

7,9 16.3 2.38 7.81 (2/6)

8 60.0 3.79 -

1 119.5 - -

12 124.3 - 7.54 (14/16)

13,17 127.1 8.14 7.54 (15), 8.14 (13/17)

2,6 127.8 7.81 2.38 (7/9), 7.81 (2/6)

14,16 129.2 7.54 7.54 (14/16)

15 131.7 7.54 8.14 (13/17)

3,5 132.2 - 2.38 (7/9)

4 160.3 - 2.38 (7/9), 3.79 (8),

7.81 (2/6)

11 164.5 - 8.14 (13/17)

10 164.7 - 7.81 (2/6)

362 Appendix

1.24 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-

tetrazine (261)

N N

13NH

12

HN11

10

1 14

23

4

5 6 15 16

17

1819

9

O

8

7


[ppm]

HMBC cross peaks

[ppm]

7,9 16.3 2.31 7.34 (2/6)

8 59.9 3.74 -

1 125.5 - -

15,19 126.1 7.67 7.45 (17), 7.67 (15/19)

2,6 126.8 7.34 2.31 (7/9), 7.34 (2/6)

16,18 129.0 7.43 7.43 (16/18), 7.45 (17)

14 130.4 - 7.43 (16/18)

17 130.8 7.45 7.67 (15/19)

3,5 131.9 - 2.31 (7/9)

10,13 148.8 - 7.34 (2/6), 7.67 (15/19)

4 159.5 - 2.31 (7/9), 3.74 (8),

7.34 (2/6)


1.25 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine

(262)

N N

11NN

10

1 12

23

4

5 6 13 14

15

1617

9

O

8

7


[ppm]

HMBC cross peaks

[ppm]

7,9 16.5 2.43 8.33 (2/6)

8 60.0 3.83 -

1 127.2 - -

13,17 128.0 8.64 7.63 (15), 8.64 (13/17)

2,6 129.0 8.33 2.43 (7/9), 8.33 (2/6)

14,16 129.4 7.61 7.61 (14/16), 7.63 (15)

12 132.1 - 7.61 (14/16)

3,5 132.4 - 2.43 (7/9)

15 132.6 7.63 8.64 (13/17)

4 161.4 - 2.43 (7/9), 3.83 (8),

8.33 (2/6)

11 163.8 - 8.64 (13/17)

10 163.9 - 8.33 (2/6)

364 Appendix

1.26 Transannular cyclization-product (cone) (60)

20

2119

OO O

17

16

15

23

22 24

26

4

25

1

14

18

5

828

6

7

32 3829

30

31

2

3

O

11

10

9

12

27

13

35

36

37

33

34

39

40

4441

4243

51

45

46

47 48

49

5052

53

54 55

56

C atom1

δ

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

10.00 31,37

10.02 0.85 1.81 (30/36), 3.90 (29/35)

34,40 11.05 1.12 1.81 (33/39), 3.69 (32/38)

23.24 30,36

23.26 0.85 (31/37), 3.90 (29/35)

33,39 23.72

1.75-1.88 („1.81“)

1.12 (34/40), 3.69 (32/38)

8,14 31.38 3.15, 4.45 5.50 (6/16), 7.13 (10/12)

2,20 31.63 3.21, 4.49 5.86 (4/18), 7.21 (22/24)

42,43 44.97 3.86 3.76 (41/44),

6.89 (46/50/52/56)

41,44 48.69 3.76 3.86 (32/43), 5.50 (6/16),

5.86 (4/18)

76.26 29,35

76.31 3.90 0.85 (31/37), 1.81 (30/36)

32,38 76.34 3.69 1.12 (34/40), 1.81 (33/39)

11,23 121.51 6.94-7.05 7.21 (22/24)

1 For the assignment to the unsubstituted phenyl rings the shift of the bridging methylene groups were

compared with those of other calixarenes, especially tetrapropoxycalixarene, concluding that protons “under” the cyclobutane ring experience a downfield shift.


C atom1

δ

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

(„6.98“, „7.02“)

4,18 125.13 5.86 3.21 (2/20), 3.76 (41/44),

4.49 (2/20), 5.50 (6/16)

48/54 125.53 6.98 6.89 (46/50/52/56)

47/49/53/55 127.74 7.04 7.04 (47/49/53/55)

46/50/52/56 128.29 6.89 3.86 (42/43), 6.89

(46/50/52/56), 6.98 (48/54)

6,16 128.74 5.50 3.76 (41/44), 5.86 (4/18)

10,12 129.38 7.13 7.13

(10/12)

22,24 129.63 7.21

3.15 (8/14),

3.21 (2/20),

4.45 (8/14),

4.49 (2/20)

7.21

(22/24)

3,19,5,17 133.92 -

3.21 (2/20), 3.76 (41/44),

3.86 (42/43), 4.49 (2/20),

5.50 (6/16)

7,15 134.27 - 3.15 (8/14), 4.45 (8/14),

5.86 (4/18)

138.03 -

1,9,13,21 138.05 -

3.15 (8/14), 3.21 (2/20),

4.45 (8/14), 4.49 (2/20),

6.94-7.05 (11,23),

7.13 (10/12), 7.21 (22/24)

45,51 141.67 - 3.76 (41/44), 3.86 (42/43),

7.04 (47/49/53/55)

26,28 154.37 -

3.15 (8/14), 3.21 (2/20),

3.69 (32/38),

4.45(8/14), 4.49 (2/20),

5.50 (6/16), 5.86 (4/18)

25 159.44 7.13

(10/12)

27 159.49

-

3.15 (8/14),

3.21 (2/20),

3.90 (29/35),

4.45 (8/14),

4.49 (2/20)

7.21

(22/24)

366 Appendix

1.27 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxy-

calix[4]arene (65)

22

2125

1

24

23

2

328 7

6

5

4

20

OO

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

1211

O35

36

37

38

39

40

5049 4241

51

52

5354

55

5643

44

4546

47

48

8

E/Z E/Z


[ppm]

HMBC cross peaks

[ppm]

10.37

10.46

10.48

10.50

31,34,37,40

10.60

0.96-1.02 1.85-1.96, 4.31-4.47

23.36

23.38 30,33,36,39

23.45

1.85-1.96 0.96-1.02, 4.31-4.47

31.04

31.10

31.21 2,8,14,20

31.27

2.89-3.19, 4.31-4.47 6.27-6.85

29,32,35,48 76.78 3.76-3.93 0.96-1.02, 1.85-1.96

122.04

122.13 17,23

122.15

6.27-6.85

6.27-6.85

n.d. 126.32

n.d. 126.36

6.27-6.85, 7.08-7.23,

7.44

2.89-3.19, 4.31-4.47,

6.27-6.85, 7.08-7.23,



[ppm]

HMBC cross peaks

[ppm]

n.d. 126.50

n.d. 126.60

n.d. 126.62

n.d. 126.66

n.d. 126.75

n.d. 126.83

n.d. 126.87

n.d. 127.06

n.d. 127.10

n.d. 127.96

n.d. 128.17

n.d. 128.22

n.d. 128.35

n.d. 128.41

n.d. 128.50

n.d. 128.63

n.d. 128.71

n.d. 128.86

n.d. 129.22

n.d. 129.41

n.d. 129.47

n.d. 129.53

6.27-6.85, 7.08-7.23,

7.32

7.32, 7.44

n.d. 130.77

n.d. 130.81

n.d. 130.90

6.27-6.85

n.d. 131.28 -

6.27-6.85

n.d. 134.52 -

n.d. 134.73 -

n.d. 134.78 -

n.d. 134.90 -

2.89-3.19, 4.31-4.47,

6.27-6.85

368 Appendix


[ppm]

HMBC cross peaks

[ppm]

n.d. 135.04 -

n.d. 135.15 -

n.d. 135.26 -

n.d. 135.33 -

n.d. 135.38 -

n.d. 135.41 -

n.d. 135.60 -

n.d. 135.64 -

n.d. 135.71 -

n.d. 135.91 -

n.d. 137.95 -

n.d. 138.00 -

n.d. 138.12 -

n.d. 138.13 -

6.27-6.85, 7.08-7.23,

7.32, 7.44

156.18 -

156.27 -

156.55 -

156.58 -

156.64 -

156.76 -

157.01 -

25,26,27,28

157.18 -

2.89-3.19, 3.76-3.93 ,

4.31-4.47, 6.27-6.85


1.28 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c)

1.28.1 proximal cone-Calix[4]diphenanthrene (81a)

4

3 44

15

14

5

16

17

43 29

28

27

18

302

OO

1

54

55

56

38

37 41

40

39

O45

46

47

35

32

31 42

34

33

O48

49

50

36

51

52

53

13

87

6

12

11

10

9

26

2524

19

23

22

21

20

C atom δ

[ppm]

HMQC cross peaks


56 9.77 0.79 1.75 & 2.02 (55), 4.18 & 4.27 (54)

50 10.11 0.94 1.92 & 1.96 (49), 3.96 & 4.24 (48)

47 10.98 1.06 1.81 (46), 3.60 (45)

53 11.34 1.33 2.11 (52), 3.92 & 4.05 (51)

55 22.23 1.75, 2.02 0.79 (56), 4.18 & 4.27 (54)

49 23.13 1.92, 1.96 0.94 (50), 3.96 & 4.24 (48)

46 23.67 1.81 1.06 (47), 3.60 (45)

52 23.94 2.11 1.33 (53), 3.92 & 4.05 (51)

16 30.76 5.76, 5.81 -

30 31.02 3.31, 4.79 6.00 (28), 7.25 (32)

2 31.50 3.04, 4.26 5.30 (40), 7.04 (4)

36 31.61 3.25, 4.49 6.23 (38), 7.29 (34)

45 „76.95“ 3.60 1.06 (47), 1.81 (46)

„77.16“ 3.94, 4.05

„77.16“ 4.18, 4.25 48,51,54

„77.16“ 3.94, 4.25

0.79 (56), 0.94 (50), 1.33 (53),

1.75 & 2.02 (55), 1.92 & 1.96 (49),

2.11 (52)

33 122.11 7.09 -

21 122.51 5.71 7.25 (23)

39 123.29 6.16 -

25 123.90 7.07 -

22 124.31 6.84 7.61 (20)

370 Appendix

C atom δ

[ppm]

HMQC cross peaks


7 124.56 7.54 -

11 124.88 7.71 8.00 (9)

10 125.83 7.66 8.70 (12)

40 125.86 5.30 3.04 & 4.26 (2), 6.23 (38)

23 126.56 7.25 5.71 (21), 7.07 (25)

6 126.80 7.25 7.04 (4)

38 126.96 6.23 3.25 & 4.49 (36)

20 127.25 7.61 6.84 (22)

5 127.38 - 7.54 (7)

12 127.84 8.70 7.66 (10)

4 127.95 7.04 3.04 & 4.26 (2)

9 128.15 8.00 7.71 (11)

18 128.25 - 6.00 (28), 7.61 (20)

26 128.52 6.80 -

28 128.58 6.00 3.31 & 4.79 (30)

19 129.01 -

34 129.09 7.29

3.25 & 4.49 (36), 5.71 (21),

7.25 (32)

27 129.54 - 7.07 (25)

32 129.76 7.25 3.31 & 4.79 (30), 7.29 (32)

17 130.56 - 5.76 & 5.81 (16), 6.00 (28)

13 131.10 - 7.54 (7), 7.71 (11), 8.00 (9)

15 131.51 - 5.76 (16)

24 131.97 - 6.80 (26), 6.84 (22), 7.61 (20)

1,37 132.87 - 3.04 & 4.26 (2), 3.25 & 4.49 (36),

5.30 (40), 6.16 (39), 6.23 (38)

133.47 -

133.49 - 8,14,29

133.54 -

3.31 & 4.79 (30), 7.04 (4), 7.25

(6), 7.54 (7), 7.66 (10), 8.70 (12)

3 135.65 - 3.04 & 4.26 (2)

31 137.01 - 3.31 & 4.79 (30), 7.09 (33)

35 138.29 - 3.25 & 4.49 (36), 7.09 (33)

41 154.99 - 3.04 & 4.26 (2), 3.25 & 4.49 (36),

3.60 (45), 5.30 (40), 6.16 (39),


C atom δ

[ppm]

HMQC cross peaks


6.23 (38)

43 156.90 - 3.31 & 4.79 (30), 3.92 & 4.05 (51),

5.76 & 5.81 (16), 6.00 (28)

42 158.70 -

3.25 & 4.49 (36), 3.31& 4.79 (30),

3.96 & 4.24 (48),

7.09 (33), 7.25-7.29 (32/34)

44 159.83 - 3.04 & 4.26 (2), 4.18 & 4.27 (54),

7.04 (4), 5.76 & 5.81 (16)

H

atom

δ

[ppm]

H-H COSY

cross peaks

[ppm]

NOESY

cross peaks

[ppm]

ROESY

cross peaks

[ppm]

56 0.79 1.75, 2.02 1.33, 1.75 1.75, 2.20

50 0.94 1.92, 1.96 1.06 1.92, 1.96

47 1.06 1.81 0.94, 1.81 1.81

53 1.33 2.11 0.79, 2.11 2.11

55 1.75 4.27 0.79, 2.02, 4.18,

4.27

2.02, 4.23-4.29

46 1.81 3.60 1.06, 3.60 1.06, 3.60

49 1.92 3.96, 4.24 3.94, 4.24 3.94, 4.23-4.29

49 1.96 3.96, 4.24 3.94, 4.24 3.94, 4.23-4.29

55 2.02 4.18 1.75, 4.25 1.75, 4.23-4.29

52 2.11 3.92, 4.05 1.33, 3.92, 4.05 1.33, 3.94, 4.05, 4.25

2 3.04 4.26 3.31, 4.26, 5.30,

7.04

3.31, 3.60, 4.26, 5.30,

7.04

36 3.25 4.49 4.49, 6.23, 7.29 4.49, 6.23, 7.29

30 3.31 4.79 3.04, 3.94, 4.79,

6.00, 7.25

4.79, 6.00, 7.25

45 3.60 3.60 1.81, 3.94, 4.26 ,

4.49

1.06, 1.81, 3.04, 4.25,

4.49

48,51 3.90-

3.97

4.05, 4.24 2.11, 3.31, 3.60,

4.05, 4.18, 4.25,

0.94, 1.33, 1.92, 1.96,

2.11, 4.25, 4.49, 4.79

372 Appendix

H

atom

δ

[ppm]

H-H COSY

cross peaks

[ppm]

NOESY

cross peaks

[ppm]

ROESY

cross peaks

[ppm]

4.49, 4.79

51 4.05 3.92 2.11, 4.25, 5.80 1.33 (+), 2.11 (+), 3.94,

5.80 (+)

54 4.18 4.27 5.80 0.79, 1.75, 2.02, 5.80

48,54 4.23-

4.29

3.96, 4.18 0.79, 0.94, 1.88-

2.05, 3.94, 4.05

0.79, 1.88-2.05, 3.94

2 4.26 3.04 3.04, 4.23-4.29 3.04

36 4.49 3.25 3.25, 3.94 3.25, 3.60, 3.94, 4.25

30 4.79 3.31 3.31, 4.25 3.31, 3.94

40 5.30 6.16 6.16, 7.04, 7.25 6.16

21 5.71 6.84, 7.61 6.84, 7.61, 7.71 7.61, 6.84

16 5.76 5.81

16 5.81 5.76

4.05, 4.18, 7.61,

8.70

3.94, 4.05, 4.18, 4.25,

7.61, 8.70

28 6.00 - 6.80, 7.04 3.31, 4.79, 6.80

39 6.16 6.23, 5.30 5.30, 6.23, 7.09 5.30

38 6.23 6.16 7.29 3.25 (+), 5.30

26 6.80 7.07 6.00, 7.07, 7.25 6.00, 7.25

22 6.84 5.71, 7.25 5.71, 7.25 5.71, 7.25

4 7.04 - 3.04, 6.00 3.04, 7.25-7.29

25 7.07 6.80 6.80, 7.54 6.80

33 7.09 7.25, 7.29 6.16 6.80, 7.25-7.29

6,32

7.24-

7.26

7.09, 7.54, 3.31, 5.30, 6.80,

6.84, 7.04, 7.07,

7.54, 8.00

3.31, 6.00, 6.84, 7.04,

7.07-7.10, 7.54

34 7.29 7.09 3.25, 6.23 3.25, 7.09

7 7.54 7.25 7.25, 8.00 7.25, 8.00

20 7.61 5.71 5.71, 5.76, 5.81,

8.70

5.71, 5.76, 5.81

10 7.66 7.71, 8.00 8.00 8.00

11 7.71 7.66, 8.70 5.71, 8.70 8.70

9 8.00 7.66 7.25, 7.54, 7.66 7.54, 7.66

12 8.70 7.71 5.76, 5.81, 7.61, 5.76, 5.81, 7.71


H

atom

δ

[ppm]

H-H COSY

cross peaks

[ppm]

NOESY

cross peaks

[ppm]

ROESY

cross peaks

[ppm]

7.71

1.28.2 proximal cone-Calix[4]diphenanthrene (81b)

4

3

44 15

14

13

16

17 43

29

28

19

18

302

OO

1

54

55

56

38

37 41

40

39

O45

46

47

35

32

3142

34

33

O48

49

50

36

51

52

53

12

1110

5 27

2221

20

26

25

24

239

8

7

6

C atom δ

[ppm]

HMQC cross peaks


47,50 10.50 1.02 1.93 (46/49), 3.86 (45/48)

53,56 10.65 1.08 2.03(22/55), 4.06 (51/54)

46,49 23.25 1.93 1.02 (47/50), 3.86 (45/48)

52,55 23.66 2.03 1.08 (53/56), 4.06 (51/54)

16 30.54 3.46, 4.94 -

2/30 30.89 4.73, 4.98 -

36 31.33 2.90, 4.28 -

45,48 76.36 3.86 1.02 (47/50), 1.93 (46/49)

51,54 78.31 4.06, 4.28 1.08 (53/56), 2.03 (52/55)

33,39 121.28 6.07 -

PhenCH 124.31 7.44-7.56 („7.55“)

PhenCH 124.67 7.44-7.56 („7.45“) 7.78 (11/21)

PhenCH 125.64 7.44-7.56 („7.51“) 8.78 (6/26)

32,40;

PhenCH 127.64 5.84, 7.38 2.90 & 4.28 (36)

34,38;

11,21 128.10 6.26, 7.78

4.73 & 4.98 (2/14),

7.55

374 Appendix

C atom δ

[ppm]

HMQC cross peaks


14,18;

6,26 128.48 7.06, 8.78

3.46 & 4.94 (16),

7.51

129.04 - 7.45

130.45 - 7.55, 7.78

(11/21)

130.70 -

4.73 & 4.98

(2/30) 7.51, 8.78

(6/26)

4,5,10,13,

19,22,27,28

133.03 - 7.51, 8.78 (6/26)

15,17 134.16 - 3.46 & 4.94 (16)

1,3,29,31 134.54 - 4.73 & 4.98

(2/30)

35,37 134.67 - 2.90 & 4.28

(36)

6.07 (33/39)

41,42 156.33 - 2.90 & 4.28 (36), 3.86

(45/48), 4.73 & 4.98 (2/30)

43,44 158.95 - 3.46 & 4.94 (16), 4.06

(51/54), 4.73 & 4.98 (2/30)


1.28.3 proximal cone-Calix[4]diphenanthrene (81c)

4

3 44

15

14

5

16

1743

29

28

19

18

302

OO

1

54

55

56

38

37 41

40

39

O45

46

47

35

32

3142

34

33

O48

49

50

36

51

52

53

13

87

6

27

2221

20

12

11

10

9

26

25

24

23

C atom δ

[ppm]

HMQC cross peaks


CH2CH3 (a) 10.26 0.94 1.90, 3.92

CH2CH3 (b) 10.50 1.00 2.03, 3.80, 3.98, 4.12

CH2CH3 (c) 10.75 1.06

CH2CH3 (d) 10.78 1.11

1.97, 1.99, 3.76-3.86, 3.97-

4.13

CH2CH3 (a) 23.04 0.94, 3.92

CH2CH3 (b) 23.33 1.00,

CH2CH3

(c+d) 23.54

1.87-2.03 1.06, 1.11,

3.80

3.97-4.13

30.04 4.66, 5.31 -

30.67 4.52, 4.94 -

31.42 3.04, 4.38 6.52 2,26,30,36

31.53 3.41, 4.73 -

OCH2 (a) 76.24 3.92 0.94, 1.86-1.95

OCH2 (c) 76.95 3.78, 3.85 1.06, 1.86-1.95

OCH2 (d) 77.37 3.97-4.13 1.11, 1.87-2.03

OCH2 (b) 77.81 3.97-4.13, 4.24 1.00, 1.87-2.03

p-ArCH 120.85 6.18 -

n.d. 122.51 6.39 -

n.d. 123.94 -

n.d. 124.03 7.19 7.61

n.d. 124.75 - 7.73

PhenCH 125.07 7.41, 7.49 n.d.

376 Appendix

C atom δ

[ppm]

HMQC cross peaks


n.d. 125.35 - 7.19

n.d. 125.62 - 8.73

n.d. 127.45 - -

n.d. 127.61 -

PhenCH 127.75 7.49

n.d. 127.84 6.88, 7.61

12,26 128.07 8.73

n.d. 128.20 -

n.d. 128.29 7.73

7.38-7.44

n.d. 128.54 6.52

n.d. 128.65 -

n.d. 128.76 -

n.d. 128.83 -

6.18, 6.52

7.18

n.d. 129.24 - 6.88, 7.49

n.d. 129.65* 4.52, 4.94

n.d. 129.82 - n.d.

n.d. 130.39 - 7.19

n.d. 130.50 -

5.31, 7.41,

7.61, 7.73

PhenC 130.60 - 8.73

n.d. 131.40 * 4.66, 5.31

n.d. 132.77 - 6.88, 7.20, 7.38

PhenCH 133.19 - 7.49, 8.73

133.82 - 3.41, 4.73, 4.66, 5.31

134.45 - 4.52, 4.94

134.89* - 3.04, 4.38

6.18 ArCCH2Ar

136.20* 3.41, 4.73

156.42 - 3.04 & 4.38, 3.41 & 4.73

41,42 157.04 -

3.04 & 4.38, 3.92, 4.52 & 4.94,

6.18, 6.51

43,44 157.86 - 3.41 & 4.73, 3.97-4.13 & 4.24

(51/54), 4.52 & 4.94, 4.66 & 5.31


1.29 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-


3 28 7

65

4

8

O

13

10

9 27

12

11

O35

36

37

14

38

39

40

4142

43

44

45

46

47

48

49

2

E/Z

C atom δ

1

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

37 10.68 1.03 1.93-2.08 (left) (36), 3.94

(35)

40 10.84 1.05 1.93-2.08 (right) (39),

3.78*,3.87 (38)

49 17.55 1.90, 2.12* 6.53 (41)

36 23.84 1.93-2.08 (left) 3.94 (35)

39 23.98 1.93-2.08 (right)

0.95*, 0.99*,

1.03, 1.05,

3.78* 3.87 (38)

8,14 31.57 2.88, 3.19, 4.32, 4.50

6.24*, 6.41*, 6.53*,

6.64 (11), 6.69 (4/6), 6.76

(10/12), 6.84*

35 77.42 3.78*, 3.94 1.93-2.08

(left) (36)

38 77.69 3.87

0.95*, 0.99*,

1.03, 1.05 1.93-2.08

(right) (39)

11 122.64 6.46*, 6.64, 6.76* 6.24*, 6.41*, 6.46*, 6.84*

1 Minor isomers are marked with an asterisk.

378 Appendix

C atom δ

1

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

44,48 126.27 7.28 7.17

n.d. 126.43 * 7.49* 7.49*

46 127.13 6.24*, 7.23*, 7.17 1.93-2.08* (right), 6.41*, 7.28

41 128.12 6.53 1.90 (49), 2.12*, 6.69 (4/6)

n.d. 128.29* n.d. 6.24*, 6.84*

45,47 128.67 7.17 7.17

n.d. 128.72* 6.24*

10/12 128.78 6.76, 7.11*, 7.33*

PhCH 129.03* 7.28*

6.64 (11), 6.76 (10/12)

m-ArH 129.68 * 6.41* 2.88*, 4.32*, 6.24*, 6.41*

4,6 129.81 6.69 3.19 (8/14), 4.50 (8/14), 6.53

(41), 6.69 (4/6)

4,6* 129.99* 6.84* 3.14* ,4.45*, 6.84*

5 132.42 - 1.90 (49), 6.53 (41)

n.d. 133.02* - n.d.

134.97 - 3,7

135.02* - 6.46*, 6.69 (4/6)

ArCH2Ar 135.91* - 2.88*, 4.32*, 4.45*

135.97 -

42, 9,13 136.00 -

1.90 (49), 2.12*, 3.19 (8/14),

4.50 (8/14), 6.53 (41), 6.64

(11), 6.69 (4/6), 6.76 (10/12),

7.28 (44/48), 7.49*

n.d. 137.22* - 1.93-2.08 (right)

n.d. 143.37* - 1.93-2.08 (right)

43 144.69 - 1.90 (49), 2.12*, 6.53 (41),

7.17, 7.28

n.d. 145.11* - 7.33*

28 155.78 - 3.19 (8/14), 3.87 (35), 4.50

(8/14), 6.69 (4/6)

27/28 156.79* -

2.88*, 3.15*, 3.78*, 4.32*,

4.45*, 6.24*, 6.41*, 6.46*,

6.53*, 6.84*


C atom δ

1

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

27 157.24 - 3.19 (8/14), 3.94 (38), 4.50

(8/14), 6.64 (11), 6.76 (10/12)

380 Appendix

1.30 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-

phenanthrene (86a and 86b)

4

3 44

15

14

5

16

17 43 21

20

19

18

OO54

55

56

51

52

53

13

87

6

12

11

10

9

22

57

4

3 44

15

14

5

16

1743

21

20

19

18

222

OO

1

54

55

56

38

37 41

40

39

O45

46

47

35

24

2342

34

33

O48

49

50

36

51

52

53

13

87

6

12

11

10

9

57

2

32

3130

25

29

28

27

26

58a

b

C atom δ

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

50,56a+b 10.11 0.94, 0.95 2.05 (49/55),

4.21& 4.38 (48/54)

47b 11.04 1.16 1.93 (46), 3.74 (45)

53a 11.17 1.24 2.00 (52), 3.77 & 3.82 (51)

53b 11.33 1.32 2.07 (52), 3.86 (51)

57 19.83 2.73, 2.74 7.55 (6)

23.32 49,55a+b

23.36 2.05 (2.05, 2.12)

0.94 & 0.95 (50/56),

4.21 & 4.38 (48/54)

46b 23.76 2.05 (1.93) 1.16 (47), 3.74 (45)

52a 23.90 2.05 (2.00) 1.24 (53), 3.77 & 3.82 (51)

52b 24.02 2.05 (2.07) 1.32 (53), 3.86 (51)

16,22 30.21 4.66, 4.72, 4.87 5.12 (18/20), 5.32 (18)

16,22 31.22 3.35, 3.39, 4.60, 4.62 6.03 (20), 6.27 (38/40),

7.54 & 7.61 (4/34)


C atom δ

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

51b 76.50 3.86 1.32 (53), 2.07 (52)

51a 76.73 3.77, 3.82 1.24 (52), 2.00 (53)

45b 77.00 3.74 1.16 (47), 1.93 (46)

77.77 48/54a+b

77.96 4.21, 4.38

0.94 & 0.95 (50/56),

2.05 & 2.12 (49/55)

39b 122.67 6.27 -

19a 122.82 5.94 -

19b 122.90 5.64 -

124.33 9

124.37 8.05 7.57

11 124.51 7.57 8.05

10 125.77 7.57 8.57, 8.60

18,20b 126.32 5.12 4.66, 4.87, 5.12 (18/20),

5.64 (19)

20a 126.84 6.03 3.35, 4.60, 5.33 (18)

18a 127.05 5.33 4.72, 4.87, 5.94 (19), 6.03

(20)

4 127.23 7.57 3.39, 7.57

n.d. 127.43 7.57 n.d.

38,40b 127.57 6.27 4.65, 6.27 (38/40)

n.d. 127.65 - 3.35, 4.60

PhenC 128.42 - -

12 128.50 8.57 7.57

12 128.60 8.60 7.57

7 130.28 - 2.74 (57), 8.05 (9)

PhenC 130.61 - 4.72

130.99 - 7.60, 8.60 PhenC (14)

131.08 - 4.65, 4.87

7.55, 8.57

21a 132.20 - 3.35, 4.65, 5.94 (19)

1,37b 132.67 - 3.39, 4.65, 6.27 (39)

133.27 -

PhenC (8) 133.33 -

4.66, 4.87, 7.55, 7.60

2.74 (57,58), 8.05, 7.57,

8.57 & 8.60 (12/26)

382 Appendix

C atom δ

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

17,21b 134.63 - 5.64 (19)

17a 134.94 - 4.65, 4.87

5.94 (19)

136.91 - 3,15

136.96 - 3.35, 3.39, 4.60, 4.87

43b 154.57 -

3.86 (51),

5.12 (18/20),

5.64 (19)

43a 154.88 -

3.77 & 3.82

(51), 5.33

(18), 5.94

(19), 6.03 (20)

41b

155.32

-

3.35, 3.39,

4.60, 4.62,

4.66, 4.87

3.74 (45),

6.27 (38/40)

159.55 - 3.39, 7.61

(4/34) 44a+b

159.69 -

4.21, 4.38,

4.60, 4.62,

4.66, 4.72,

4.87

3.35, 7.54

(4/34)


1.31 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-

25,26,27,28-tetra-n-propoxycalix[4]arene (88)

3 28 7

65

4

8

O38

39

40

4142

43

44

45

46

47

48

49

4

E/Z

C atom δ

1

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

10.35*

10.52 40

10.64*

0.96*, 1.00* 1.02* 1.05 1.88-2.08 (39), 3.94 (38)

3.79* (38), 3.88-4.00* (38)

17.15* 1.83*

17.29 1.88*, 1.96, 2.00* 49

17.68 2.16*

6.53 (41)

6.59 (41)

23.47 39

23.50*

1.88-2.08 0.96* (40), 1.05 (40), 3.79*

(38), 3.94 (38), 3.88-4.00* (38)

31.22* 2.90*, 3.19*,4.34*, 4.49* 8

31.30 3.22, 4.53 6.40, 6.47, 6.79, 6.90

76.96*

38 77.37

3.79*, 3.88-4.00*

3.94

0.96* (40), 1.00* (40),1.05

(40), 1.88-2.08 (39)

125.93

125.98 7.27-7.34, 7.43-7.48

44-48,

4,6

126.07* 6.22, (7.12-7.24)

6.79, 7.12-7.24, 7.43-7.48

1 Minor isomers are marked with an asterisk.

384 Appendix

C atom δ

1

[ppm]

HMQC cross peaks

[ppm]

HMBC cross peaks

[ppm]

126.69*

126.75

6.47, 7.27-7.34

127.80 4,6, 50

127.90* 6.22-6.90, 6.53, 6.59

1.83 (49), 1.87 (49), 1.96 (49),

2.00 (49), 6.79

128.21*

128.27

128.33*

2.04 (49), 2.16 (49)

6.90, 7.12-7.24 44-48

128.60*

7.12-7.24, 7.27-7.34

6.67, 7.27-7.34

129.19*

4,6

129.47

6.40, 6.47, 6.64, 6.67, 6.79,

6.90

2.90* (2,8),3.22 (2,8), 4.34*

(2,8), 4.53 (2,8), 6.22, 6.47

(4,6), 6.53 (41), 6.59 (41),

6.67(4,6), 6.79 (4,6), 6.90 (4,6)

132.12* - 5

132.36 - 1.96 (49), 6.53 (41), 6.59 (41)

3,7 134.63 - 2.90* (2,8),3.22 (2,8), 4.34*

(2,8), 4.53 (2,8), 6.79 (4,6)

135.57* -

43

135.71 -

1.83 (49), 1.87 (49), 1.96 (49),

2.00 (49), 2.04 (49), 2.16 (49),

6.59 (41), 7.27-7.34 (45-47),

7.43-7.48 (44-48)

42 144.18 -

1.83 (49), 1.87 (49), 1.96 (49),

2.00 (49), 2.04 (49), 2.16 (49),

6.53 (41), 6.59 (41), 6.67, 7.25,

7.27-7.34 (45-47)

154.78* -

2.90* (2,8),3.19* (2,8), 3.79*

(38), 4.34* (2,8), 4.49* (2,8),

6.40 28

155.22 - 3.22 (2,8), 3.94 (38), 4.53

(2,8), 6.47, 6.79, 6.90


1.32 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxy-

calix[4]arene (133)

22

21 25 1

24

23

2

3 28 7

65

4

820

OO

41

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

O 42

43

44

45

46

47

48

Br

38

39

40


[ppm]

HMBC cross peaks

[ppm]

10.4 0.98

10.5 1.04 31,34,37,40

10.6 1.02

1.86-1.97 (30/33/36/39),

3.81 & 3.84-3.92

(29/32/35/,38)

23.3 1.86-1.97

23.46 1.86-1.97 30,33,36,39

23.53 1.86-1.97

0.98 &1.02 &1.04

(31/34/37/40), 3.81 & 3.84-

3.92 (29/32/35/38)

31.1 3.16, 3.21, 4.45, 4.48

2,8,14,20

31.2 3.16, 3.21, 4.45, 4.48

6.47(16/18),

6.71-6.74 (10/12/22/24),

7.21 (4/6)

42 45.3 4.14 7.18 (48)

29,32,35,38 77.0 3.81, 3.84-3.92

0.98 & 1.02 & 1.04

(31/34/37/40),

1.86-1.97 (30/33/36/39)

17 122.0 6.39-6.43 -

11,23 122.4 6.65 -

44 125.3 - 4.14 (42),

7.11 (46), 7.18 (48)

47 127.5 7.25 7.57 (45)

16,18 128.1 6.47 6.47(16/18)

386 Appendix


[ppm]

HMBC cross peaks

[ppm]

46 128.49 7.11 7.18 (48)

10,12,22,24 128.55 6.71-6.74

3.16 & 3.21 (2/8/14/20),

6.65 (11/23),

6.71-6.74 (10/12/22/24)

128.86 4,6

128.92

7.21

4.45 & 4.48 (2/8),

7.21 (4/6)

5 130.8 - -

48 131.7 7.18 4.14 (42),

7.09-7.14 (46)

45 132.9 7.57 7.25 (47)

134.9 - 1,9,13,21

15,19 135.0 -

4.45 & 4.48 (2/8/14/20),

6.39-6.43 (17),

6.65 (11/23)

3,7 135.5 - 3.21 (2/8), 7.21 (4/6)

43 135.6 - 4.14 (42),

7.25 (47), 7.57 (45)

1,9,13,21

135.8 -

4.45, 4.48 (2,8,14,20), 6.65

(11,23)

26 156.5 -

3.16 & 4.45 (14/20),

3.81 (32),

6.46-6.48 (16/18)

25,27 156.9 -

3.21 (2/8/14/20),

3.84-3.92 (29/35),

4.48 (2/8/14/20),

6.65 (11/23),

6.71-6.74 (10/12/22/24)

28 161.2 -

3.21 (2/8),

3.84-3.92 (38),

4.48 (2/8), 7.21 (4/6)

41 195.6 - 4.14 (42), 7.21 (4/6)


1.33 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-

propoxycalixarene (136)

3 28 7

65

4

8

O

41O 42

43

44

45

46

47

48

Br

38

39

40

4


[ppm]

HMBC cross peaks

[ppm]

40 10.4 1.02 1.93 (39), 3.94 (38)

39 23.5 1.93 1.02 (40), 3.94 (38)

2,8 31.3 3.33, 4.50 7.38 (4/6)

42 45.4 4.10 7.21 (48)

38 77.2 3.94 1.02 (40), 1.93 (39)

44 125.0 -

4.10 (42), 7.02 (46),

7.11 (47), 7.21 (48),

7.50 (45)

47 127.6 7.11 7.50 (45)

46 128.5 7.02 7.21 (48)

4,6 129.2 7.38 3.33 (2/8), 4.50 (2/8),

7.38 (4/6)

5 131.2 - -

48 132.4 7.21 4.10 (42), 7.02 (46)

45 132.6 7.50 7.11 (47)

3,7 135.1 - 3.33 (2/8), 4.50 (2/8),

7.38 (4/6)

43 135.7 - 4.10 (42), 7.11 (47),

388 Appendix


[ppm]

HMBC cross peaks

[ppm]

7.50 (45)

28 161.1 - 3.33 (2/8), 3.94 (38),

4.50 (2/8), 7.38 (4/6)

41 195.5 - 4.10 (42), 7.38 (4/6)


1.34 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)

22

21 25 1

24

23

2

3 28 7

65

4

820

OO

I

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

38

39

40


[ppm]

HMBC cross peaks

[ppm]

31,37 10.3 0.95

10.58 34,40

10.64 1.02, 1.03

1.90 (30/36), 3.78 (32),

3.80 (38), 3.88 (29/35)

30,36 23.3 0.95

(31/37)

23.4

33,39 23.5

1.90 1.02 and

1.03

(34/40)

3.78 (32),

3.80 (38),

3.88 (29/35)

2,8 30.9 3.08, 4.37 6.72 (10/24), 6.73 (4/6)

14,20 31.2 3.16, 4.45 6.46 (16/18), 6.77

(12/22)

29,32,35,3

8 77.0 3.78, 3.80, 3.88

0.95 (31/37), 1.02 and

1.03 (34/40), 1.90 (30/36)

5 86.0 - 3.08 (2/8), 4.37 (2/8),

6.73 (4/6)

11,23 122.2

17 122.5 6.69 6.46 (16/18)

16,18 128.0 6.46

3.16 (14/20),

4.45 (14/20),

6.46 (16/18), 6.68 (17)

10,24 128.4 6.72 3.08 (2/8), 4.37 (2/8),

6.68 (11/23),

390 Appendix


[ppm]

HMBC cross peaks

[ppm]

6.77 (12/22)

12,22 128.9 6.77

3.16 (14/20), 4.45

(14/20), 6.68 (11/23),

6.72 (10/24)

134.7 -

1,9,13,21 135.0 -

3.08 (2/8), 3.16 (14/20),

4.37 (2/8), 4.45 (14/20),

6.68 (11/23)

15,19 136.0 - 3.16 (14/20), 4.45

(14/20), 6.69 (17)

4,6 136.8 6.73 6.73 (4/6)

3,7 137.6 - 3.08 (2/8), 4.37 (2/8)

26 156.3 - 3.80 (38),

6.46 (16/18)

28 156.5 - 3.78 (32),

6.73 (4/6)

25,27 157.1 -

3.08

(2/8), 4.37

(2/8), 3.16

(14/20),

4.45

(14/20)

3.88

(29/35), 6.72

and 6.77

(10/12/22/24)


1.35 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]-

arene (141a)

22

21 25 1

24

23

2

3 28 7

65

4

820

OO

41

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

38

39

40

42

43

44

45

46

47

48

Br


[ppm]

HMBC cross peaks

[ppm]

10.45 31,34,

37,40 10.53 1.00

1.91 (30,33,36,39),

3.86 (39,32,35,38)

23.40 30,33,

36,39 23.44 1.91

1.00 (31,34,37,40),

3.86 (39,32,35,38)

31.03 2,8,14,20

31.19 3.16, 4.45

6.58 (10/12/16/18/22/24),

6.88 (4/6)

76.7 39,32,

35,38 76.9 3.82-3.87

1.00 (31,34,37,40),

1.91 (30,33,36,39)

42 86.5 - 7.50 (48)

41 95.3 - 6.88 (4/6)

5 116.2 - -

11,23 122.2 (2) 6.58 -

17 122.3 6.70 -

44 125.7 - 7.50 (48)

43 126.2 - 7.26 (47)

47 127.1 7.26 7.59 (45)

10,12,16, 128.3 6.58 3.16 and 4.45 (2/8/14/20),

392 Appendix


[ppm]

HMBC cross peaks

[ppm]

128.4 18,22,24

128.5

6.58 (10/12/16/18/22/24)

46 128.9 7.13 7.50 (48)

4,6 131.9 6.88 3.16 and 4.45 (2/8/14/20),

6.88 (4/6)

45 132.5 7.59 7.26 (47)

48 133.1 7.50 7.13 (46)

134.5 - 6.57

(11/23)

135.3 - 6.70 (17)

135.4 - 6.88 (4/6)

1,3,7,9,

13,15,19,

21

136.0 - -

3.16 and

4.45

(2/8/14/20)

25,27 156.6 (2) - 6.58 (10/12/22/24)

26 156.8 - 6.58 (16/18)

28 157.9 - 6.88 (4/6)


1.36 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-

propoxycalix[4]arene (141b)

3 28 7

65

4

8

O

41

13

10

9 27

12

11

O

35

36

37

14

38

39

40

42

43

44

45

46

47

48Br

2


[ppm]

HMBC cross peaks

[ppm]

40 10.1 0.92 1.95 (39), 4.04 (38)

37 10.9 1.09 1.89 (36), 3.71 (35)

39 23.2 1.95 0.92 (40), 4.04 (38)

36 23.6 1.89 1.09 (37), 3.71 (35)

8,14 31.0 3.18, 4.44 6.27 (10/12), 7.31 (4/6)

38 76.8 4.04 0.92 (40), 1.95 (39)

35 77.2 3.71 1.09 (37), 1.89 (36)

42 87.0 - 7.53 (48)

41 95.0 - 7.31 (4/6)

5 116.1 - -

11 122.5 6.33 3.18 (8/14), 4.44 (8/14)

44 125.7 - 7.14 (46), 7.53 (48)

45 126.1 - 7.24 (47), 7.60 (45)

47 127.1 7.24 7.60 (45)

10,12 128.0 6.27 3.18 (8/14), 4.44 (8/14),

6.27 (10/12), 6.33 (11)

46 129.0 7.14 7.53 (46)

394 Appendix


[ppm]

HMBC cross peaks

[ppm]

4,6 132.4 7.31 3.18 (8/14), 4.44 (8/14),

7.31 (4/6)

45 132.5 7.60 7.24 (47)

9,13 133.0 - 3.18 (8/14), 4.44 (8/14),

6.33 (11)

48 133.2 7.53 7.14 (46)

3,7 137.2 - 3.18 (8/14), 4.44 (8/14),

7.31 (4/6)

27 155.5 -

3.18 (8/14), 3.71 (35), 4.44

(8/14), 6.27 (10/12), 6.33

(11)

28 158.9 - 3.18 (8/14), 4.04 (38), 4.44

(8/14), 7.31 (4/6)


1.37 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene

(137a)

22

21 25 1

24

23

2

3 28 7

65

4

820

OO

41

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

42

43

44

45

46

47

48

Br

38

39

40


[ppm]

HMBC cross peaks

[ppm]

10.4

10.47 31,34,

37,40 10.52

0.97-1.02 1.93 (30/33/36/39),

3.85 (29/32/35/38)

23.39 30,33,

36,39 23.42 1.89-1.96

1.00 (31/34/37/40),

3.85 (29/32/35/38)

2,8,24,20 31.2 3.10, 3.15, 4.43, 4.46 6.49 (4/6), 6.53 & 6.57

(10/12/22/24), 6.67 (16/18)

41 35.5 2.60 2.79 (42), 6.49 (4/6)

42 38.6 2.79 2.60 (41), 7.12 (48)

76.83 29,32,

35,38 76.85 3.83-3.87

1.00 (31/34/37/40),

1.93 (30/33/36/39)

17 121.96 -

11,23 122.02 6.55

-

44 124.6 - 2.79 (42), 7.04 (46), 7.12

(48), 7.19 (47), 7.53 (45)

47 127.4 7.19 7.04 (46), 7.53 (45)

46 127.6 7.04 7.12 (48), 7.19 (47)

396 Appendix


[ppm]

HMBC cross peaks

[ppm]

128.2 4,6,

10,12,22,24,

16,18 128.3

6.49, 6.52-6.55, 6.56-

6.59, 6.67

2.60 (41), 3.10 (2/8),

3.15 (14/20), 4.43 (2/8),

4.46 (14/20), 6.49 (4/6),

6.53 & 6.57 (10/12/22/24),

6.67 (16/18)

48 130.7 7.12 2.79 (42), 7.04 (46)

45 132.9 7.53 7.19 (47)

5 134.6 - 2.60 (41), 2.79 (42)

3,7 135.07 - 6.49 (4/6)

135.12 - 1,21,9,13

135.2 -

3.10 (2/8),

4.43 (2/8),

6.52-6.55 -

15,19 135.5 -

3.15

(14/20), 4.46

(14/20)

6.56-6.59,

6.67 (16/18)

43 141.6 - 2.60 (41), 2.79 (42),

7.19 (47), 7.53 (45)

28 155.1 - 3.10 (2/8), 3.84 (38),

4.43 (2/8), 6.49 (4/6)

25,27 156.6 -

3.10 (2/8), 3.15 (14/20),

3.85 (29/32/35/38),

4.43 (2/8), 4.46 (14/20),

6.53 & 6.57 (10/12/22/24)

26 156.9 -

3.15 (14/20),

3.85 (29/32/35/38),

4.46 (14/20), 6.67 (16/18)


1.38 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]-

arene (137b)

3 28 7

65

4

8

O

41

13

10

9 27

12

11

O35

36

37

14

42

43

44

45

46

47

48

Br

38

39

40

2


[ppm]

HMBC cross peaks

[ppm]

40 10.2 0.94 1.94 (39), 3.90 (38)

37 10.7 1.05 1.91 (36), 3.76 (35)

39 23.2 0.94 (40), 3.90 (38)

36 23.5 1.92

1.05 (37), 3.76 (35)

8,14 31.1 3.09, 4.42 6.31 (10/12), 6.70 (4/6)

41 35.5 2.71 2.93 (42), 6.70 (4/6)

42 38.7 2.93 2.71 (41), 7.06 (42)

38 76.7 3.90 0.94 (40), 1.94 (39)

35 76.9 3.76 1.05 (37), 1.91 (36)

11 122.1 6.41 3.09 (8/14), 4.42 (8/14)

44 124.7 - 2.93 (42), 7.03 (46), 7.06

(48), 7.14 (47), 7.52 (45)

47 127.3 7.14 7.52 (45)

46 127.6 7.03 7.06 (38)

10,12 127.9 6.31 3.09 (8/14), 4.42 (8/14),

6.31 (10/12)

4,6 128.7 6.70 2.71 (41), 3.09 (8/14),

4.42 (8/14), 6.70 (4/6)

398 Appendix


[ppm]

HMBC cross peaks

[ppm]

48 130.7 7.06 2.93 (42), 7.03 (46)

45 132.9 7.52 7.14 (47)

9,13 134.3 -

3.09 (8/14), 4.42 (8/14),

6.31 (10/12), 6.41 (11),

6.70 (4/6)

5 134.5 - 2.71 (41), 2.93 (42)

3,7 135.9 - 3.09 (8/14), 4.42 (8/14),

6.70 (4/6)

43 141.3 - 2.71 (41), 2.93 (42),

7.14 (47), 7.52 (45)

28 155.7 - 3.09 (8/14), 3.90 (38),

4.42 (8/14), 6.70 (4/6)

27 156.0 -

3.09 (8/14), 3.76 (35), 4.42

(8/14),6.31 (10/12),

6.41 (11)


1.39 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and

5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)

22

21 25 1

24

23

2

3 28 7

6

5

4

820

OO

41

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

O 42

43

44

45

46

47

38

39

40

Cl48


[ppm]

HMBC cross peaks

[ppm]

10.6 0.99

10.78 1.03 31,34,

37,40 10.84 1.04

1.89-2.00 (30/33/36/39),

3.82, 3.86-3.96

(29/32/35/38)

23.8

23.95 30,33,

36,39 24.01

1.89-2.00

0.99-1.04 (31/34/37/40),

3.82, 3.86-3.96

(29/32/35/38)

31.4

2,8,14,20 31.5

3.17, 3.18, 4.46, 4.47

6.58-6.67 (2 x)

(10/12/22/24), 6.76

(16/18), 7.01 (4/6)

77.4

77.6 29,32,

35,38 77.7

3.82, 3.86-3.96 0.99-1.04 (31/34/37/40),

1.89-2.00 (30/33/36/39)

17 122.4 6.48 -

11,23 122.7 6.62 -

46 126.7 7.26 7.41

6.48 (17), 6.59 (16/18) 16,18 128.6 6.59

10,12, 128.8 6.65 (2d)

3.17, 3.18, 4.46, 4.47

(2/8/14/20)

400 Appendix


[ppm]

HMBC cross peaks

[ppm]

6.76 (10/12/22/24) 22,24

129.2 6.76

3.17, 3.18, 4.46, 4.47

(2/8/14/20);

6.65 (10/12/22/24)

47 130.0 6.92 -

44 130.5 7.42 7.26

5 130.8 - -

45 131.1 7.41 6.92 (47), 7.42

4,6 131.3 7.01 3.17, 3.18, 4.46,

4.47(2/8); 7.01 (4/6)

43 131.7 - -

135.4 - 3.17, 3.18, 4.46, 4.47

(14/20); 6.48 (17)

136.0 - -

1,3,7,9,13,

15,19,21

136.3 - -

(3.83), 6.59 (16/18) 26 156.9 -

3.17, 3.18, 4.46, 4.47

(2/8/14/20);

3.83, 3.86-3.96

(29/32/35/38) 25,27 157.3 -

6.66, 6.75 (10/12/20/24)

28 162.2 -

3.17, 3.18, 4.46, 4.47

(2/8);

3.86-3.96 (38),

7.01 (4/6)

41 194.2 - 6.92 (47), 7.01 (4/6)


3 28 7

6

5

4

8

O

41

13

10

927

12

11

O35

36

37

14

O 42

43

44

45

46

47

38

39

40

2

Cl


[ppm]

HMBC cross peaks

[ppm]

3.97 (38) 40 10.3 0.99

1.88-1.98 (36/39)

37 10.5 1.02 3.82 (35)

36 23.4 1.02 (37), 3.82 (35)

39 23.5 1.88-1.98

0.99 (40), 3.97 (38)

8,14 31.1 3.19, 4.46 6.49 (10/12), 7.30 (4/6)

1.02 (37) 35 77.0 3.82

1.88-1.98 (36/39)

38 77.3 3.97 0.99 (40)

11 122.8 6.49 -

46 126.6 29 7.39 (44)

10,12 128.4 6.49 3.19, 4.46 (8/14),

6.49 (10/12)

47 129.5 6.99 7.37 (45)

44 130.0 7.39 7.29 (46)

45 130.5 7.37 6.99 (47)

5 130.8 - -

4/6 131.3 7.30 (s) 3.19, 4.46 (8/14),

7.30 (4/6)

43 131.4 - 7.39 (44)

402 Appendix


[ppm]

HMBC cross peaks

[ppm]

9,13 134.1 - 3.19, 4.46 (8/14),

6.49 (10/12)

3,7 136.0 - 3.19, 4.46 (8/14),

7.30 (4/6)

42 138.7 - 7.29 (46), 7.39 (44)

27 156.1 - 3.19, 4.46 (8/14),

3.82 (35), 6.49 (10/12)

28 162.2 - 3.19, 4.46 (8/14),

3.97 (38), 7.30 (4/6)

41 194.3 - 6.99 (47), 7.30 (4/6)


1.40 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171)

and 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-

arene (172)

3 28 7

65

4

8

OH36

37

13

10

9 27

12

11

O33

34

35

14

O 38

39

40

41

42

43

2

Br44


[ppm]

HMBC cross peaks

[ppm]

35 11.1 1.32 2.06 (34), 3.99 (33)

34 23.6 2.06 1.32 (35), 3.99 (33)

8,14 31.5 3.43, 4.27 6.92 (10/12), 7.59 (4/6)

33 78.7 3.99 1.32 (35), 2.06 (34)

39 119.7 - 7.29 (43), 7.34 (41),

7.41 (42), 7.66 (40)

11 125.8 6.81 -

42 127.2 7.41 7.66 (40)

5 127.6 - -

3,7 128.3 - 3.43(8/14), 4.27(8/14),

9.25 (36)

43 129.0 7.29 7.34 (41)

10,12 129.6 6.92 3.43(8/14), 4.27(8/14),

6.81 (11), 6.92 (10/12)

41 130.8 7.34 7.29 (43)

4,6 131.8 7.59 3.43(8/14), 4.27(8/14),

7.59 (4/6)

404 Appendix


[ppm]

HMBC cross peaks

[ppm]

9,13 132.6 - 3.43(8/14), 4.27(8/14),

6.81 (11), 6.92 (10/12)

40 133.2 7.66 7.41 (42)

38 141.7 - 7.41 (42), 7.66 (40)

27 151.9 -

3.43 (8/14), 3.99 (33),

4.27(8/14), 6.81 (11),

6.92 (10/12)

28 159.4 - 3.43(8/14), 4.27(8/14),

7.59 (4/6), 9.25 (36)

37 194.6 - 7.29 (43), 7.59 (4/6)


22

2125 1

24

23

2

3 28 7

65

4

820

OH36

O

37

19

29

30

31

16

1526

18

17

14

OH32

13

10

927

12

11

O33

34

35

O 38

39

40

41

42

43

51

O52

44

45

53

54

55

5657

O46

47

48

49

50

Br Br Br


[ppm]

HMBC cross peaks

[ppm]

10.9 31,35

11.0 1.30

2.06 (30/34), 4.01

(29/33)

30,34 23.6 2.06 1.30 (31/35), 4.01

(29/33)

8,14 31.2 3.42, 4.30

2,20 31.4 3.46, 4.27

6.93 (22/24), 7.30

(10/12), 7.48 and 7.67

(4/6/16/18)

78.7 29,33

78.9 4.01

1.30 (31/35), 2.06

(30/34)

39,53 119.7 - 7.28 (57), 7.34 (41/55),

7.40 (42/56), 7.65 (54)

46 120.1 - 7.11 (50), 7.34 (48/49),

7.53 (47)

23 125.7 6.81 -

42, 49, 56 127.3 7.34, 7.40 7.53 (47), 7.65 (54)

127.7 - 7,9,13,15,

5,17 127.8 -

3.42 (8/14), 4.30 (8/14)

3,7 128.4 - 8.77 (36)

43, 57 129.1 7.28 7.34 (55)

22,24 129.6 6.93 6.93 (22/24)

50 129.7 7.11 7.34 (48)

41,55 130.9 7.34 7.28 (43/57)

48 131.5 7.34 7.11 (50)

406 Appendix


[ppm]

HMBC cross peaks

[ppm]

4,6,16,18 131.8 7.67 7.48

10,12 131.96 7.30 3.42 (8/14), 4.30 (8/14)

7.30 (10/12)

4,6,16,18 132.00 7.48 3.42 (8/14), 4.30(8/14)

7.67

1,21 132.5 - 6.81 (23)

40,54 133.4 7.65 7.40 (56)

47 133.5 7.53 7.34 (49)

45 140.0 - 7.34 (49), 7.53 (47)

38,52 141.4 - 7.40 (42/56), 7.65

(40/54)

25 151.9 -

3.46 (2/20), 4.00 (29),

4.27 (2/20), 6.81 (23), 6.93

(22/24)

27 156.7 - 3.42 (8/14), 4.03 (33),

4.30 (8/14), 7.30 (10/12)

26,28 159.1 -

3.42 (8/14), 3.46 (2/20),

4.27 (2/20), 4.30 (8/14),

7.48 and 7.67 (4/6/16/18),

8.77 (32/36)

37,51 194.4 - 7.11 (50), 7.30 (10/12),

7.48 and 7.67 (4/6/16/18)


1.41 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)

22

21 25 1

24

23

2

3 28 7

65

4

820

OH36

O

37

19

29

30

31

16

15 26

18

17

14

OH32

13

10

9 27

12

11

O33

34

35

O 38

39

40

41

42

43

Br


[ppm]

HMBC cross peaks

[ppm]

31,35 11.0 1.32 2.07 (30/34), 3.98

(29/33)

30,34 23.6 2.07 1.32 (31/35), 3.98

(29/33)

31.5 2,8,14,20

31.6 3.39, 3.41, 4.29, 4.31

6.89 and 6.95

(10/12/22/24), 7.06

(16/18), 7.58 (4/6)

29,33 78.6 3.98 1.32 (31/35), 2.07

(30/34)

17 119.2 6.65 -

39 119.7 - 7.29 (43), 7.32 (41),

7.65 (40)

11,23 125.6 6.77 -

42 127.2 7.40 7.65 (40)

5 127.5 - -

15,19 128.1 -

3.39 (14/20), 4.31

(14/20), 6.65 (17), 8.26

(32)

3,7 128.5 - 9.28 (36)

16,18 128.6 7.06 3.39 (14/20), 4.31

408 Appendix


[ppm]

HMBC cross peaks

[ppm]

(14/20), 7.06 (16/18)

43 129.1 7.29 7.32 (41)

129.2 6.89 6.95

10,12,22,2

4 129.5 6.95

3.39 (14/20), 3.41 (2/8),

4.29 (2/8), 4.31 (14/20),

6.89

41 130.8 7.32 7.29 (43)

4,6 131.8 7.58 3.41 (2/8), 4.29 (2/8),

7.58 (4/6)

1,9,13,21 132.6 -

3.39 (14/20), 3.41 (2/8),

4.29 (2/8), 4.31 (14/20),

6.77 (11/23)

40 133.2 7.65 7.40 (42)

1,9,13,21 133.7 -

3.39 (14/20), 3.41 (2/8),

4.29 (2/8), 4.31 (14/20),

6.77 (11/23)

38 141.7 - 7.40 (42), 7.65 (40)

25,27 152.0 -

3.39 (14/20), 3.41 (2/8),

3.98 (29), 4.29 (2/8), 4.31

(14/20), 6.77 (11/23), 6.89

and 6.95 (10/12/22/24)

26 153.5 -

3.39 (14/20), 4.31

(14/20), 6.65 (17), 7.06

(16/18),

8.26 (32)

28 159.6 - 3.41 (2/8), 4.29 (2/8),

7.58 (4/6), 9.28 (36)

37 194.6 - 7.29 (43), 7.58 (4/6)


1.42 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),

5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179)

and paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)

22

21 25 1

24

23

2

3 28 7

6

5

4

820

OO

41

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

O 42

43

44

45

46

47

38

39

40

Br48


[ppm]

HMBC cross peaks

[ppm]

31,37 10.4

10.47 34,40

10.51

0.99 1.93, 3.83, 3.91

29,35 23.37

23.44 33,39

23.5

1.93 0.99, 3.83, 3.91

31.08 2,8,14,20

31.13 3.16, 3.17, 4.45 6.55, 6.65, 7.11 (4/6)

29,32,35,38 77.0 3.83, 3.91 0.99, 1.93

43 120.1 - 6.95 (47), 7.29 (46),

7.61 (44)

17 122.1 6.55 -

11,23 122.5 6.55 -

46 126.7 7.29 7.61 (44)

128.3

128.4 6.55

3.16 (2/8/14/20), 4.45

(2/8/14/20), 6.65 10,12,16,

18,22,24 128.7

6.65

- 6.55

410 Appendix


[ppm]

HMBC cross peaks

[ppm]

47 129.7 6.95 7.29 (45)

5 130.1 - -

45 130.8 7.29 6.95 (47)

4,6 131.2 7.11 3.16 (2/8/14/20), 4.45

(2/8/14/20), 7.11 (4/6)

44 133.2 7.61 7.29 (46)

134.6 - 6.55

-

135.1 - 6.55

135.5 -

1,3,7,9,

13,15,19,21

135.6 -

3.16 (2/8/14/20),

4.45 (2/8/14/20)

42 140.8 - 7.29 (46), 7.61 (44)

25,27 156.58 -

26 156.64 -

3.16 (2/8/14/20), 3.83

(29/35), 3.91 (32), 4.45

(2/8/14/20), 6.55, 6.65

28 161.9 - 3.16 (2/8), 3.91 (38),

4.45 (2/8), 7.11 (4/6)

41 194.8 - 6.95 (47), 7.11 (4/6)


22

21 25 1

24

23

2

3 28 7

65

4

820

OH38

O

39

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

O 40

41

42

43

44

45

Br


[ppm]

HMBC cross peaks

[ppm]

34 9.7 0.94 2.25 (33), 3.84 (32)

31,37 10.9 1.11 1.90 (30/36), 3.74

(29/35)

33 22.6 2.25 0.94 (34), 3.84 (32)

30,36 23.6 1.90 1.11 (31/37), 3.74

(29/35)

2,8 30.8 3.35, 4.34

14,20 30.9 3.22, 4.40

6.40 (10/12/22/24), 7.18

(16/18), 7.60 (4/6)

32 76.6 3.84 0.94 (34), 2.25 (33)

29,35 77.8 3.74 1.11 (31/37), 1.90

(30/36)

41 119.8 - 7.34 (43), 7.43 (45),

7.66 (42)

17 123.2 6.97 7.18 (16/18)

11,23 123.4 6.40 -

44 127.3 7.43 7.66 (42)

5 127.5 - 3.35 (2/8), 4.34 (2/8)

127.8 4.40, (14/20), 6.40

(10/12/22/24) 10,12,22,24

128.5

6.40

-

45 129.2 7.43 7.34 (43)

412 Appendix


[ppm]

HMBC cross peaks

[ppm]

16,18 129.3 7.18

3.22 (4/20), 4.40

(14/20), 6.97 (17), 7.18

(16/18)

3,7 130.3 - 5.99 (OH)

43 130.8 7.34 -

4,6 131.6 7.60 3.35 (2/8), 4.34 (2/8),

7.60 (4/6)

1,9 131.7 - -

42 133.3 7.66 6.40, 7.43 (44)

13,21 133.7 - 3.22 (14/20),

4.40 (14/20)

15,19 137.1 -

3.22 (14/20), 4.40

(14/20), 6.97 (17),

7.18 (16/18)

40 141.8 - 7.43 (44), 7.66 (44)

25,27 154.4 -

3.22 (14/20), 3.35 (2/8),

3.74 (29/35), 4.34 (2/8),

4.40 (14/20),

6.40 (10/12/22/24)

26 157.0 - 3.22 (14/20), 3.84 (32),

4.40 (14/20), 7.18 (16/18)

28 159.3 - 3.35 (2/8), 4.34 (2/8),

5.99 (OH), 7.60 (4/6)

39 195.1 - 7.43, (45), 7.60 (4/6)


22

21 251

24

23

2

3 7

820

O

19

29

30

31

16

1526

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

28

6

5

4

O

41

O42

38

39

40

47

46

45

44

43

Br


[ppm]

HMBC cross peaks

[ppm]

34 10.1 0.76 1.41 (33), 3.35 (32)

40 10.7 1.06 1.94 (39), 3.82 (38)

31,37 11.0 1.02 1.78 (30/36), 3.52

(29/35), 3.68 (29/35)

33 22.0 1.41 0.76 (34), 3.35 (32)

30,36 23.9 1.78 1.02 (31/37), 3.52

(29/35), 3.68 (29,35)

39 24.2 1.94 1.06 (40), 3.82 (38)

14,20 30.7 3.06, 4.07 6.32 (12/22),

7.09 (16/18)

2,8 36.2 3.68 6.91 (10/24), 7.75 (4/6)

38 74.8 3.82 1.06 (40), 1.94 (39)

32 75.5 3.35 0.76 (34), 1.41 (33)

29,35 76.5 3.52, 3.68 1.02 (31/37),

1.78 (30/36)

43 120.0 - 7.36 (45), 7.44 (46),

7.50 (47), 7.68 (44)

11,23 121.7 6.45 -

17 122.5 6.91 7.09 (16/18)

46 126.9 7.44 7.68 (44)

12,22 128.9 6.32 6.91 (10/24)

47 129.0 7.50 7.36 (45)

16,18 129.1 7.09 3.06 (14/20),

414 Appendix


[ppm]

HMBC cross peaks

[ppm]

4.07 (14/20), 7.09 (16/18)

10,24 129.4 6.92 6.32 (12/22), 6.45

(11/23)

5 129.9 - -

45 130.7 7.36 7.50 (47)

1,9 131.4 - 3.68 (2/8), 6.45

4,6 133.1 7.75 7.75 (4/6)

44 133.4 7.68 7.44 (46)

13,21 133.7 - 3.06 (14/20), 3.68 (2/8),

4.07 (14/20), 6.45 (11/23)

3,7 134.6 - n.d.

15,19 137.1 - 3.06 (14/20), 4.07

(14/20), 6.91 (10/24)

42 141.9 - 7.44 (46), 7.50 (47),

7.68 (44)

25,27 155.7 -

3.06 (14/20), 3.52

(29/35), 3.68 (29/35), 4.07

(14/20), 6.32 (12/22), 6.45

(11/23), 6.91 (10/24)

26 156.9 -

3.06 (14/20),

4.07 (14/20),

3.35 (32), 7.09 (16/18)

28 163.1 - 3.68 (2/8), 3.82 (38),

7.75 (4/6)

41 195.1 - 7.50 (47), 7.75 (4/6)


1.43 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene

(165), paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-

arene (175) and 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-


3 28 7

6

5

4

8

O

41

13

10

927

12

11

O35

36

37

14

O 42

43

44

45

46

47

38

39

40

2

Br


[ppm]

HMBC cross peaks

[ppm]

10.3 0.99 3.97 37,40

10.6 1.02 1.93

3.82

23.4 36,39

23.5 1.93

0.99, 1.03, 3.82 (35),

3.97 (38)

8,13 31.1 3.19, 4.45 6.49 (10/12), 7.30 (4/6)

35 77.0 3.82

38 77.3 3.97 0.99, 1.93

43 119.7 - 6.97 (47), 7.29 (45), 7.59

(44)

11 122.8 6.49 -

46 127.2 7.35 7.59 (44)

10,12 128.4 6.49 3.19 (8/14), 4.45 (8/14),

6.49 (10/12)

47 129.4 6.97 n.d.

5 130.2 - -

45 130.9 7.29 6.97

416 Appendix


[ppm]

HMBC cross peaks

[ppm]

4,6 131.4 7.30 3.19 (8/14), 4.45 (8/14),

7.30 (4/6)

44 133.1 7.59 7.35 (46)

9,13 134.1 - 3.19 (8/14), 4.45 (8/14),

6.49 (11)

3,7 136.1 - 3.19 (8/14), 4.45 (8/14)

42 140.8 - 7.35, 7.59

27 156.1 - 3.19 (8/14), 3.82 (35),

4.45 (8/14), 6.49 (10/12)

28 162.3 - 3.19 (8/14), 3.97 (38),

4.45 (8/14), 7.30 (4/6)

41 195.0 - 7.30 (4/6)


22

21 251

24

23

2

3 7

820

O

19

29

30

31

16

1526

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

28

6

5

4

O

41

O42

38

39

40

47

46

45

44

43

Br

48

49O50

51

52

53

54

Br


[ppm]

HMBC cross peaks

[ppm]

34 10.1 0.77 1.43 (33), 3.43 (32)

40 10.7 1.08 1.95 (39), 3.84 (38)

31,37 10.9 (2) 1.01 1.78 (30/36), 3.50

(29/35), 3.68 (29/35)

33 22.1 1.43 0.77 (34), 3.43 (32)

30,36 23.9 (2) 1.78 1.01 (31/37), 3.50

(29/35), 3.68 (29/35)

39 24.2 1.95 1.08 (40), 3.84 (38)

14,20 30.7 3.10, 4.09 6.28 (12/22),

7.57 (16/18)

2,8 36.0 3.67 6.94 (10/24), 7.75 (4/6)

38 75.0 3.84 1.08 (40), 1.95 (39)

32 75.6 3.43 0.77 (34), 1.43 (33)

29,35 76.5 (2) 3.50, 3.68 1.01 (31/37),

1.78 (30/36)

119.8 - 43,50

120.0 -

7.35 (46/52), 7.43

(47/54), 7.67 (44/51)

11,23 121.9 6.47 6.28 (12/22)

126.9 45,53

127.3 7.43 7.66 (44/51)

12,22 128.9 6.28 6.94 (10/24)

47,54 129.0 7.47 7.35 (46/52)

418 Appendix


[ppm]

HMBC cross peaks

[ppm]

129.2 7.42

10,24 129.7 6.94 6.28 (12/22)

130.0 - n.d. 5,7

130.6 - n.d.

46,52 130.8 n.d.

131.0 7.36

n.d.

16,18 131.5 7.57 7.57 (16/18)

1,9,13,21

132.8 - n.d.

4,6 133.0 7.76 7.75 (4/6)

133.3 44,51

133.4 7.67 7.46 (46/53)

3,7 134.5 - 3.67 (2/8)

15,19 137.6 - 3.10 (14/20), 4.09

(14/20), 7.57 (16/18)

141.5 - 42, 49

141.8 -

7.42 (47/54), 7.47

(46/53), 7.67 (44/51)

25,27 155.7 -

3.10 (14/20), 3.50

(29/35), 3.67 (2/8), 4.09

(14/20), 6.28 (12/22), 6.47

(11/23), 6.94 (10/24)

26 162.3 - 3.10 (14/20), 3.43 (32),

4.09 (14/20), 7.57 (16/18)

28 163.0 - 3.67 (2/8), 3.84 (38),

7.75 (4/6)

41 195.1 - 7.47 (47), 7.75 (4/6)

48 195.5 - 7.42 (54), 7.57 (16/18)


22

21 25 1

24

23

2

3 28 7

65

4

820

OH38

O

39

19

29

30

31

16

15 26

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

O 40

41

42

43

44

45

46

47O

48

49

50

51

52

Br Br


[ppm]

HMBC cross peaks

[ppm]

34 9.7 0.95 2.23 (33), 3.93 (32)

31,37 10.9 1.10 1.89 (30/36),

3.74 (29/35)

33 22.7 2.23 0.95 (34), 3.93 (32)

30,36 23.6 1.89 1.10 (31/37),

3.74 (29/35)

2,8 30.8 3.36, 4.32 6.38, 7.60

14,20 30.9 3.26, 4.41 7.65

32 76.7 3.93 0.95 (34), 2.23 (33)

29,35 77.9 3.74 1.10 (31/37),

1.89 (30/36)

41,48 119.8 - 7.38, 7.68

11,23 123.6 6.42 -

127.3 44,51

127.4 7.43 7.67 (42/49)

5 127.6 - -

128.2 6.42 - 10,12,22,24

128.5 6.38 6.43, 7.36

4.41

(14/20)

129.15 45,52

129.23 7.43 n.d.

3,7 130.0 - 3.36 (2/8), 4.32 (2/8),

6.07 (38)

420 Appendix


[ppm]

HMBC cross peaks

[ppm]

130.8 43,50

131.2 7.37 7.43

17 131.3 - -

4,6 131.6 7.60 7.60

16,18 131.7 7.65 7.65

131.9 - 1,9,13,21

132.8 -

3.26 (14/20),

4.41 (14/20), 6.43

133.3 7.68 42,49

133.4 7.66 7.43

15,19 137.7 - 3.26 (14/20), 4.41

(14/20), 7.65 (16/18)

141.3 - 40,47

141.7 -

7.43, 7.68

25,27 154.4 -

3.26 (14/20), 3.36 (2/8),

3.74 (29/35), 4.32 (2/8),

4.41 (14/20), 6.38

(10/12), 6.43 (11)

28 159.2 - 3.36 (2/8), 4.32 (2/8),

6.07 (38), 7.60 (4/6)

26 162.3 - 3.26 (14/20), 3.93 (32),

4.41 (14/20), 7.65 (16/18)

39 195.1 - 7.60 (4/6)

46 195.4 - 7.65

(16/18)

7.43


1.44 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and

5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174)

22

21 25 1

24

23

2

3 28 7

65

4

820

OH36

O

37

19

29

30

31

16

15 26

18

17

14

OH32

13

10

9 27

12

11

O33

34

35

O 38

39

40

41

42

43

Cl


[ppm]

HMBC cross peaks

[ppm]

31,35 11.1 1.32 2.07 (30/34),

3.96 and 4.01 (29/33)

30,34 23.6 2.07 1.32 (31/35),

3.96 and 4.01 (29/33)

31.5 2,8,14,20

31.6 3.39, 3.41, 4.29, 4.31

6.88 (12/22)6.95 (10/24),

7.06 (16/18), 7.59 (4/6)

29,33 78.6 3.99 1.32 (31/35),

2.07 (30/34)

17 119.2 6.65 -

11,23 125.6 6.78 -

42 126.7 7.35 7.47 (40)

5 127.8 - -

15,19 128.1 -

3.40 (2/8/24/20), 4.30

(2/8/24/20), 6.65 (17),

8.26 (32)

3,7 128.5 - 3.41 (2/8), 4.29 (2/8),

9.27 (36)

16,18 128.6 7.06 3.40 (2/8/24/20), 4.30

(2/8/24/20), 7.06 (16/18)

422 Appendix


[ppm]

HMBC cross peaks

[ppm]

12,22 129.1 6.88 3.41 (2/8), 4.29 (2/8),

6.95 (10/24)

43 129.2 7.32 7.41 (41), 7.47 (40)

10,24 129.5 6.95

3.39 (14/20), 4.31

(14/20), 6.88 (12/22),

6.78 (11/23)

40 130.1 7.47 7.35 (42)

41 130.7 7.41 n.d.

39 131.4 - 7.32 (43), 7.41 (41),

7.47 (40)

4/6 131.7 7.59 7.59 (4/6)

1,9 132.6 - 3.41 (2/8), 4.29 (2/8),

6.78 (11/23), 6.95 (10/24)

13,21 133.7 -

3.39 (14/20), 4.31

(14/20), 6.88 (12/22), 6.78

(11/23), 7.06 (16/18)

38 139.6 - 7.35 (42), 7.47 (40)

25,27 152.0 -

3.39 (14/20), 3.41 (2/8),

3.96 and 4.01 (29/33), 4.29

(2/8), 4.31 (14/20), 6.78

(11/23), 6.88 (12/22),

6.95 (10/24)

26 153.5 -

3.39 (14/20), 4.31

(14/20), 6.65 (17), 7.06

(16/18), 8.26 (32)

28 159.5 - 3.41 (2/8), 4.29 (2/8),

7.59 (4/6), 9.27 (36)

37 194.0 - 7.32 (43), 7.59 (4/6)


3 28 7

65

4

8

OH36

37

13

10

9 27

12

11

O33

34

35

14

O 38

39

40

41

42

43

2

Cl44


[ppm]

HMBC cross peaks

[ppm]

35 11.1 1.32 2.08 (34), 3.99 (33)

34 23.6 2.08 1.32 (35), 3.99 (33)

8,14 31.5 3.43, 4.28 6.92 (10/12), 7.59 (4/6)

33 78.7 3.99 1.32 (35), 2.08 (34)

11 125.8 6.81 -

42 126.7 7.35 7.48 (40)

5 128.0 - -

3,7 128.3 - 3.43 (8/14), 4.28 (8/14),

9.23 (36)

43 129.1 7.32 7.42 (41)

10,12 129.6 6.92 3.43 (8/14), 4.28 (8/14),

6.92 (10/12)

40 130.1 7.48 7.35 (42)

41 130.7 7.42 n.d.

39 131.3 - 7.32 (43), 7.42 (41),

7.48 (40)

4,6 131.7 7.59 7.59 (4/6)

9,13 132.7 - 3.43 (8/14), 4.28 (8/14),

6.81 (11)

38 139.6 - 7.35 (42), 7.48 (40)

27 151.9 -

3.43 (8/14), 3.99 (33),

4.28 (8/14), 6.81 (11),

6.92 (10/12)

424 Appendix


[ppm]

HMBC cross peaks

[ppm]

28 159.4 - 3.43 (8/14), 4.28 (8/14),

7.59 (4/6), 9.23 (36)

37 193.9 - 7.32 (43), 7.59 (4/6)


1.45 paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)

22

21 251

24

23

2

3 7

820

O

19

29

30

31

16

1526

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

28

6

5

4

O

41

O42

38

39

40

47

46

45

44

43

Cl


[ppm]

HMBC cross peaks

[ppm]

34 10.1 0.75 1.40 (33), 3.35 (32)

40 10.7 1.06 1.94 (39), 3.82 (38)

31,37 11.0 1.02 1.77 (30/36), 3.52

(29/35), 3.68 (29/35)

33 22.0 1.40 0.75 (34), 3.35 (32)

30,36 23.9 1.77 1.02 (31/37), 3.52

(29/35), 3.68 (29/35)

39 24.2 1.94 1.06 (40), 3.82 (38)

14,20 30.7 3.05, 4.07 6.32 (12/22),

7.09 (16/18)

2,8 36.2 3.68 6.91 (10/24), 7.76 (4/6)

38 74.8 3.82 1.06 (40), 1.94 (39)

32 75.5 3.35 0.75 (34), 1.40 (33)

29,35 76.5 3.52, 3.68 1.02 (31/37),

1.77 (30/36)

11,13 121.7 6.45 -

17 122.5 6.91 7.09 (16/18)

46 126.4 7.38 7.50 (44)

12/22 128.9 6.32 3.05 (14/20), 4.07

(14/20), 6.91

426 Appendix


[ppm]

HMBC cross peaks

[ppm]

16/18 129.07 7.09 7.09

47 129.11 7.50

10/24 129.4 6.91 6.32

44 130.2

n.d. 130.3 7.50 7.38, 7.50

45 130.6 7.44 -

1,9 131.4 - 6.45 (11/13)

n.d. 131.6 - 3.68 (2/8)

4,6 133.1 7.76 7.76

13,21 133.7 - 3.05 (14/20), 4.07

(14/20), 6.45 (11/13)

3,7 134.5 - -

15,19 137.2 -

3.05 (14/20), 4.07 3.05

(14/20), 6.91 (17),

7.09 (16/18)

42 139.9 - 7.38 (46), 7.50 (47)

25,27 155.8 -

3.52 (29/35), 3.68

(29/35), 4.07 (14/20), 6.32

(12/22), 6.45 (11/13),

6.91 (10/24)

26 156.9 - 3.05 (14/20), 3.35 (32),

7.09 (16/18)

28 163.1 - 3.68 (2/8), 3.82 (38),

7.76 (4/6)

41 194.5 - 7.50 (47), 7.76 (4/6)


1.46 paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177)

22

21 251

24

23

2

3 7

820

O

19

29

30

31

16

1526

18

17

14

O32

33

34

13

10

9 27

12

11

O35

36

37

28

6

5

4

O

41

O42

38

39

40

47

46

45

44

43

Cl

48

49O50

51

52

53

54

Cl


[ppm]

HMBC cross peaks

[ppm]

34 10.1 0.76 1.42 (33), 3.42 (32)

40 10.7 1.08 1.96 (39), 3.84 (38)

31,37 11.0 1.01 1.76 (30/36),

3.50 and 3.67 (29/35)

33 22.1 1.42 0.76 (34), 3.42 (32)

30,36 23.8 1.76 1.01 (31/37),

3.50 and 3.67 (29/35)

39 24.3 1.96 1.08 (40), 3.84 (38)

14,20 30.8 3.10, 4.08 6.27 (12/22),

7.57 (16/18)

2,8 36.0 3.67 6.94 (10/24), 7.75 (4/6)

38 75.0 3.84 1.08 (40), 1.96 (39)

32 75.6 3.42 0.76 (34), 1.42 (33)

29,35 76.5 3.50, 3.67 1.01 (31/37),

1.76 (30/36)

11,23 122.0 3.47 6.27 (12/22),

6.94 (10/24)

44-47,

51-54 126.4 7.38 7.43

428 Appendix


[ppm]

HMBC cross peaks

[ppm]

n.d. 126.8 - 7.43

12,22 128.9 6.27 3.10 (14/20), 4.08

(14/20), 6.94 (10/24)

n.d. 129.1 - n.d.

44-47,

51-54 129.3 7.48 n.d.

10,24 129.7 6.94 3.67 (2/8), 6.27 (12/22)

130.21 n.d. 44-47,

51-54 130.24 7.48

n.d.

n.d. 130.3 - n.d.

44-47,

51-54 130.7 7.44 n.d.

n.d. 130.9 - n.d.

n.d. 131.0 - n.d.

16,18 131.4 7.57 3.10 (14/20), 4.08

(14/20), 7.57 (16/18)

n.d. 131.5 - n.d.

1,9 131.57 - 3.67 (2/8), 6.47 (11/23)

n.d. 131.64 - n.d.

13,21 132.8 - 3.10 (14/20), 4.08

(14/20), 6.47 (11/23)

4,6 133.0 7.75 3.10 (14/20), 4.08

(14/20), 7.75 (4/6)

3,7 134.5 - 3.67 (2/8)

15,19 137.6 - 3.10 (14/20), 4.08

(14/20), 7.57 (16/18)

n.d. 139.4 - 7.43

n.d. 139.8 - 7.43

25,27 155.7 -

3.10 (14/20), 3.50

(29/35), 3.67 (29/35/2/8),

4.08 (14/20), 6.27 (12/22),



[ppm]

HMBC cross peaks

[ppm]

6.47 (11/23), 6.94 (10/24)

26 162.3 - 3.10 (14/20), 3.42 (32),

4.08 (14/20), 7.57 (16/18)

28 163.0 - 3.67 (2/8), 3.84 (38),

7.75 (4/6)

41 194.5 - 7.43, 7.75 (4/6)

48 194.9 - 7.43, 7.57 (16/18)

H atom δ [ppm] H-H-Cosy

[ppm] H atom δ [ppm]

H-H-Cosy

[ppm]

34 0.76 3.42 2,8 3.67 -

31,37 1.01 3.50, 3.67 29,35 3.64-3.72 1.01, 1.76,

3.50

40 1.08 3.84 38 3.84 1.08, 1.96

33 1.37-1.47 3.42 14,20 4.08 3.10

30,36 1.72-1.81 3.50, 3.67 12,22 6.27 6.47, 6.94

39 1.91-2.01 3.84 11,23 6.47 6.27, 6.94

14,20 3.10 4.08 10,24 6.94 6.27, 6.47

32 3.42 0.76, 1.42

22/51,

45/52,

36/53,

47/54

7.36-7.50 7.36-7.50

3.49 16,18 7.57 - 29,35

3.51

1.06, 1.76,

3.67 4,6 7.75 -

430 Appendix

1.47 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184)

36

35 39 1

38

37

2

3 42 14

13

5

4

1534

OO

33

43

44

45

23

22 40

32

31

21

O46

47

48

20

17

1641

19

18

O49

50

51

52

53

54

12

76

11

10

98

O

3 35 14

13

5

4

15

O

20

17

16 34

19

18

O42

43

44

21

45

46

47

12

76

11

10

98

O 3029

24

2827

26

25

O

2

a b



48,54 10.0 a+b 0.95 2.06 (47/53),

4.03 and 4.25 (46/52)

45,51 11.0 a+b 1.15 1.92 (44/50),

3.67 and 3.80 (43/49)

47,53 23.4 a+b 2.06 0.95 (48/54),

4.03 and 4.25 (46/52)

23.71 b

23.74 a 44,50

23.8 b

1.92 1.15 (45/51),

3.67 and 3.80 (43/49)

15,34 25.5 a

15,21 25.6 b 4.03, 4.49 6.22 (17/19/36)

2,34 31.2 b

2,21 31.3 a 3.24, 4.43

6.18 (37), 6.22 (19/36/38),

7.56 (4/23/32)

77.2 b 43,46,49,

52 77.3 a 3.67, 3.80, 4.01, 4.25

0.95 (48/54), 1.15 (45/51),

1.92 (44/50), 2.06 (47/53)

11,25 122.6 b

11,30 122.7 a 7.85 7.27 (9/27/28)

18 o. 37 122.8 b -

18,37 122.9 a 6.22

18 o. 37 123.0 b -

-




8,27 124.2 a

8,28 124.3 b 7.70 7.42 (10/26/29)

4,23 125.6 a

4,32 125.7 b 7.56 3.24 and 4.43 (2/21/34)

17,38 127.3 a -

17,19 127.5 b -

36,38 127.8 b 6.17

19,38 128.0 a -

6.22

3.24 and

4.43

(2/21/34),

4.03 and 4.49

(15/21/34),

6.22

(17/19,36/38)

6.18

(36/38)

9,27,28 128.5 7.27 7.83 (11/30), 7.85 (11/25)

5,31 129.27 b -

5,24 129.29 a - -

16,35 131.8 a -

16,20 131.9 b - 4.03 and 4.49 (15/21/34)

1,35 132.3 b -

1,20 132.5 a -

3.24 and 4.43 (2/21/34),

6.22 (18/37)

14,33 134.27 a -

14,22 134.30 b -

4.03 and 4.49 (15/21/34),

7.56 (4/23/32)

10,26 134.56 b

10,29 134.58 a 7.42 7.70 (8/27/28)

7,26 135.95 a -

7,29 135.99 b -

7.27 (9/27/28), 7.83

(11/30), 7.85 (11/25)

3,22,33 137.3 a+b - 3.24 and 4.43 (2/21/34)

13,23 142.2 b -

13,32 142.3 a -

4.03 and 4.49 (15/21/34),

7.56 (4/23/32), 7.83 (11/30),

7.85 (11/25)

12,31 145.31 a -

12,24 145.33 b -

7.27 (9/27/28), 7.42

(10/26/29), 7.70 (8/27/28)

432 Appendix



155.0 b - 3.67 (43),

6.18 (36/38)

155.3 a -

39,41

155.6 b - 3.80 (49)

3.24 and

4.43

(2/21/34),

4.03 and 4.49

(15/21/34),

6.22

(17/19,36/38)

40,42 165.1 a+b -

3.24 and 4.43 (2/21/34),

4.03 and 4.49 (15/21/34),

7.56 (4/23/32)

6,25,30 193.6 a+b - 7.56 (4/23/32), 7.70

(8/27/28)


3 35 14

13

5

4

15

O

20

17

16 34

19

18

O42

43

44

21

45

46

47

12

76

11

10

98

O

2


[ppm]

HMBC cross peaks

[ppm]

48,54 10.0 0.95 2.04 (47/53),

4.01 and 4.27 (46/52)

45,51 11.0 1.15 1.90 (44/50),

3.69 and 3.77 (43/49)

47,53 23.4 2.04 0.95 (48/54),

4.01 and 4.27 (46/52),

44,50 23.7 1.90 1.15 (45/51),

3.69 and 3.77 (43/49)

15,34 25.5 4.00, 4.49 6.20 (17/36)

2,21 31.3 3.26, 4.43 6.20 (19/38), 7.56 (4/23)

43,46,49,

52 77.3 3.73, 4.01, 4.27

0.95 (48/54), 1.15 (45/51),

1.90 (44/50), 2.04 (47/53)

11,30 122.7 7.83 7.26 (9/28)

18,37 122.9 6.20 -

8,27 124.2 7.69 7.42 (10/29)

4,23 125.6 7.56 3.26 (2/21), 4.43 (2/21)

17,36 127.3 4.00, 4.49

(15/34)

19,38 128.0

6.20 6.20

(17/19/36/38) 3.26, 4.43

(2/21)

9,28 128.5 7.26 7.83 (11/30)

5,24 129.3 - -

16,35 131.8 - 4.00 (15/34), 4.49 15/34)

1,20 132.5 - 3.26 (2/21), 4.43 (2/21),

434 Appendix


[ppm]

HMBC cross peaks

[ppm]

6.20 (18/37)

14,33 134.3 - 4.00 (15/34), 4.49 (15/34),

7.56 (4/23)

10,29 134.6 7.42 7.69 (8/27)

7,26 135.9 - 7.26 (9/28), 7.83 (11/30)

3,22 137.3 - 3.26 (2/21), 4.43 (2/21)

13,32 142.3 - 4.00 (15/34), 4.49 (15/34),

7.56 (4/23), 7.83 (11/30)

12,31 145.3 - 7.26 (9/28), 7.42 (10/29),

7.69 (8/27), 7.82 (11/30)

39,41 155.3 -

3.26 (2/21), 3.69 (43/49),

3.77 (43/49), 4.43 (2/21),

4.49 (15/34), 6.20

(17/19/36/38)

40,42 165.1 -

3.26 (2/21), 4.01

(46/52,15/34), 4.27 (46/52),

4.43 (2/21), 4.49 (15/34),

7.56 (4/23)

6,25 193.6 - 7.26 (9/28), 7.56 (4/23),

7.69 (8/27), 7.83 (11/30)


1.48 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-

dibenzyloxycalix[4]arene (212)

22

21 25 1

24

23

2

3 28 7

6

5

4

8

OHO

36

2

37

38

39

41

42 42

47

46

45

44

43

29

30

35

34 33

32

31


[ppm]

HMBC cross peaks

[ppm]

2,20 31.4 3.16, 4.23 6.50 (22/24), 6.87 (4/6)

29 78.4 5.00 7.62 (31/35)

23 125.3 6.68 6.50 (22/24)

biphenyl 126.2 7.25 7.18

biphenyl 127.0 7.39 7.44

31,35 127.4 7.62 7.36 (32/33/34)

biphenyl 127.5 7.39 7.38

3,7 127.7 - 6.87 (4/6), 7.56 (OH)

33 128.1 7.36 7.62 (31/35)

biphenyl 128.2 7.22

7.18, 7.22

32,34 128.9 7.36 7.36 (32/34)

22,24 129.2 6.50 6.50 (22/24)

biphenyl 130.0 7.18 7.18, 7.25

4,6 130.3 6.87 6.87 (4/6)

biphenyl 130.6 7.42 7.38

biphenyl 130.8 7.42 7.38

5 132.1 - -

436 Appendix


[ppm]

HMBC cross peaks

[ppm]

1,21 133.0 -

3.16 (2/20), 4.23 (2/20),

6.50 (22/24), 6.68 (23),

6.87 (4/6)

30 137.0 - 5.00 (29), 7.36 (32/34)

37 140.6 - 7.18, 7.42

36 140.7 - 6.87 (4/6), 7.37, 7.41

42 142.3 - 7.18, 7.22, 7.42

25 151.9 - 3.16 (2/20), 4.23 (2/20),

5.00 (29), 6.50 (22/24)

28 152.4 - 3.16 (2/20), 4.23 (2/20),

6.87 (4/6), 7.56 (OH)


1.49 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-

propoycalix[4]arene (214)

22

21 25 1

24

23

2

3 28 7

6

5

4

8

OHO

35

29

30

31

2

36

37

38

39

40 41

46

45

44

43

42


[ppm]

HMBC cross peaks

[ppm]

31 11.00 1.27 1.97-2.06 (30), 3.91 (29)

30 23.61 1.97-2.06 1.27 (31), 3.91 (29)

2,20 31.49 3.18, 4.21 6.54 (22/24), 6.87(4/6)

29 78.30 3.91 1.27 (31), 1.97-2.06 (30)

23 125.19 6.66 -

biphenyl 126.17 7.25 7.18

biphenyl 126.88 7.16-7.25, 7.36-7.45

biphenyl 127.53

7.16-7.25,

7.36-7.45 6.87, 7.36-7.45

3,7 127.79 - 3.18 (2/8), 4.21 (2/8),

8.04 (OH)

biphenyl 128.19 7.22 7.16-7.25

22,24 129.10 6.54 6.54 (22/24)

biphenyl 129.99 7.18 7.18

4,6 130.25 6.87 3.18 (2/8), 4.21 (2/8),

6.87 (4/6)

bipheny 130.67 7.43 7.36-7.45

biphenyl 130.86 7.40 7.36-7.45

438 Appendix


[ppm]

HMBC cross peaks

[ppm]

5 132.00 - 7.36-7.45

1,21 133.16 -

3.18 (2/8), 4.21 (2/8),

6.54 (22/24), 6.66 (23),

6.87 (4/6)

36 140.56 - 7.16-7.25, 7.36-7.45

35 140.69 - 6.87 (4/6), 7.36-7.45

41 142.32 - 7.16-7.25

25 151.99 -

3.18 (2/8), 4.21 (2/8),

3.91 (29), 6.54 (22/24),

6.66 (23)

28 152.52 - 3.18 (2/8), 4.21 (2/8),

6.87 (4/6), 8.04 (OH)


1.50 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-


2

3 28 7

6

5

4

8

O

13

10

9 27

12

11

O35

36

37

14

38

39

40

41

42

43

44

45

4647

48

49

51

52

53

Br


[ppm]

HMBC cross peaks

[ppm]

40 10.2 0.86 1.89 (39), 3.96 (38)

37 11.2 1.07 1.81 (36), 3.57 (35)

39 23.7 1.89 0.86 (40), 3.96 (38)

36 24.1 1.81 1.07 (37), 3.57 (35)

8,14 31.4 2.97, 4.31 5.53 (10/12),

6.88 and 6.97 (4/6)

38 77.0 3.96 0.86 (40), 1.89 (39)

35 77.4 3.57, 3.67 1.07 (37), 1.81 (36)

11 122.3 6.12 -

48 124.5 - 7.22, 7.32, 7.66 (49)

n.d. 127.0 7.42 7.45

n.d. 127.5 7.32 7.66

127.9

128.0 5.53, 5.65

128.2 10/12

128.3 5.53, 5.65

2.97 (8/14), 4.31 (8/14),

5.53 (10/12)

n.d. 128.5 7.47 7.32

n.d. 129.0 7.22 7.32

n.d. 130.6 7.45 2.97 (8/14), 4.31 (8/14),

440 Appendix


[ppm]

HMBC cross peaks

[ppm]

n.d. 130.7

n.d. 130.8

6.88

6.97

6.88, 6.97, 7.42

n.d. 131.1 7.34 7.47

n.d. 133.1

n.d. 133.15 7.32, 7.65 7.22, 7.32

n.d. 133.24 - n.d.

n.d. 133.3 - n.d.

6.12

n.d. 133.4 - 2.97 (8/14), 4.31 (8/14)

n.d. 135.0 - -

n.d. 135.7 - -

n.d. 136.97 - -

n.d. 137.00 - -

137.3 - n.d.

137.4 - 2.97 (8/14), 4.31 (8/14)

n.d. 140.6 - 7.31, 7.42, 7.45

n.d. 142.3 - 6.88 and 6.97 (4/6),

7.47 (43)

n.d. 143.7 - 7.22, 7.31, 7.66 (48)

27 155.5 -

2.97 (8/14), 3.57 (35),

4.31 (8/14), 5.53 (10/12),

6.12 (11)

28 157.7 -

2.97 (8/14), 3.96 (38),

4.31 (8/14), 6.88 and 6.97

(4/6)


1.51 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes

(217a and 217b)

2

4

3 52

19

18

5

20

2151

25

24

23

22

OOH56

57

58

17

1211

6

16

15

14

13

10

9

8

7

26

a

4

3 52

19

18

5

20

2151

25

24

23

22

262

OOH

1

46

45 49

48

47

O53

54

55

43

28

27

50

42

41

OH

44

56

57

58

17

1211

6

16

15

14

13

40

3534

29

33

32

31

30

10

9

8

7 39

38

37

36

b


[ppm]

HMBC cross peaks

[ppm]

55,58 10.9

58 10.96a

55,58 11.03

1.28 2.10, 4.06

54,57 23.6

57 23.7a

54,57 23.8

2.10 1.28, 4.06

29.0 5.87

29.2 4.82

5.69

31.6

2,20,

26,44

31.7 3.65, 4.47 6.63, 6.91, 8.32, 8.38

53,56 77.8

56 78.1 a+b

53,56 78.5

4.06 1.28, 2.10

122.4 8.38 - - 4,42

122.5 8.32 - -

n.d. 122.9 n.d.

3.66,

4.47 -

tripheny-

lene 123.2 8.58 - -

n.d. 123.6 n.d. - -

7.58

442 Appendix


[ppm]

HMBC cross peaks

[ppm]

n.d. 123.66

n.d. 123.68 n.d. - -

23b 123.74 5.87 - -

tripheny-

lene 124.3 8.24 - - -

47b 124.9 6.66

n.d. 125.3 n.d.

n.d. 125.36

n.d. 125.38

n.d. 125.40

n.d.

4.82 8.60

tripheny-

lene 126.0 7.59

6.67,

6.78

-

n.d. 126.6 n.d. - - 8.32

tripheny-

lene 127.4

tripheny-

lene 127.5

7.59 - -

22,24b 127.8 5.69 -

24a 128.0 6.63 - 5.87

22a 128.8 5.87

n.d. 128.9 -

46,48b 129.0 6.91

n.d. 129.1 -

n.d. 129.3 -

tripheny-

lene 129.5

tripheny-

lene 129.6

8.34

6.63,

6.68,

6.78,

6.91

8.56

n.d. 129.98 -

n.d. 130.01 - - 7.58

n.d. 130.78 -

3.66,

4.47,

4.82

- 8.35



[ppm]

HMBC cross peaks

[ppm]

n.d. 130.79

n.d. 130.9 -

-

n.d. 131.3 - -

n.d. 131.45 - -

n.d. 131.48 - -

6.24

n.d. 132.4 - 6.63 -

n.d. 133.8 -

3.66,

4.47 5.88 -

n.d. 134.7 - 4.83 6.24 -

152.8 -

153.2 - 49,51

153.6 -

4.07, 5.69,

5.88, 6.63,

6.91

50,52 154.90 -

4.47, 4.83 3.65, 6.78,

6.68, 8.32,

8.38

444 Appendix

1.52 29,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and

221b)

2

4

3 52

19

18

5

20

2151

25

24

23

22

OO59

60

61

17

1211

6

16

15

14

13

10

9

8

7

62

63

64

26

a

4

3 52

19

18

5

20

2151

25

24

23

22

262

OO

1

46

45 49

48

47

O53

54

55

43

28

27

50

42

41

O

44

59

60

61

17

1211

6

16

15

14

13

40

3534

29

33

32

31

30

10

9

8

7 39

38

37

36

62

63

64

56

57

58

b


[ppm]

HMBC cross peaks

[ppm]

10.1 „4.26“, „4.43“

10.2 1.00

1.87-

2.24

11.0 1.18

11.2 1.26

55,58,

61,64

11.3 1.33

„3.80“

23.4 1.00,

„4.26“, „4.43“

23.5

1.87-2.24

(2.17)

23.8 1.18

23.9 1.26

54,57,

60,63

24.0

1.87-2.24

(2.04) 1.33

„3.80“

30.9 5.04, 5.28, 6.06, 8.36

31.0 4.53, 4.85, 4.87

31.4

2,20,

26,44

31.5

3.41, 3.47, 4.61, 4.64,

4.68 6.38, 8.42

76.5 3.74-3.84 („3.80“) 1.33, 1.87-2.24 53,56,

59,62 77.7

4.19-4.31 („4.26“),

4.41-4.53 („4.43“) 1.18, 1.25, 1.87-2.24



[ppm]

HMBC cross peaks

[ppm]

78.0 4.51 1.00, 1.87-2.24

47b 122.8 6.27

„3.44

“,

„4.64

“

-

23a 122.88 5.91 -

triphenyle

ne 122.91 8.42 -

23b 123.0 5.57

-

tripheny-

lene 123.2 8.36

„3.44

“,

„4.64

“,

7.51-

7.70

-

n.d. 123.3 n.d. 8.42

n.d. 123.36 n.d. -

n.d. 123.38 n.d. -

n.d. 123.5 n.d. -

n.d. 123.6 n.d.

-

tripheny-

lene 125.49

8.58-

8.69 -

tripheny-

lene 125.52

7.51-7.70 (7.54)

-

22/24b 126.3 5.04 -

tripheny-

lene 126.4 7.51-7.70 (7.61)

4.53,

„4.86“,

8.67

5.04,

5.57

tripheny-

lene 126.54 8.58-8.69 (8.61, 8.67)

3.47, 8.32

446 Appendix


[ppm]

HMBC cross peaks

[ppm]

tripheny-

lene 126.56

24a 126.9 6.06 5.28

22a 127.2 5.28

6.06

tripheny-

lene 127.5 7.51-7.70 (7.67) -

46/48a 127.7 6.38

„4.64“,

„4.86“

6.38

n.d. 129.7 - 7.61, 8.67

tripheny-

lene 129.8 8.30-8.36 (8.32)

n.d. 129.9 - -

n.d. 130.1 - 7.54

n.d. 130.8 - 7.67, 8.33

n.d. 131.09 - -

n.d. 131.11 - -

n.d. 131.90 - „3.44“, 4.53, „4.64“,

„4.86“, 5.91, 8.36, 8.42

n.d. 131.93 -

n.d. 132.0 -

n.d. 132.5 - „3.44“, „4.64“, „4.86“,

6.27

n.d. 134.0 - -

n.d. 134.2 - -

n.d. 134.6 - 4.53, „4.86“, 5.57

n.d. 134.9 - 5.91

n.d. 136.7 - „3.44“, „4.64“

n.d. 136.8 -

154.3 - - 4.53,

„4.86“ 49,51a+b

154.7 - 5.28,

6.06

5.04 4.67,

6.38



[ppm]

HMBC cross peaks

[ppm]

155.4 - „3.44“, 6.38

160.8 - „4.86

“, 8.42 50,52a+b

160.9 -

„3.44“, 3.49,

4.21, 4.53, „4.64“ 8.36

448 Appendix

1.53 Structure (157)

C-Atom δ

[ppm]

HMQC-Kreuzsignale

[ppm]

HMBC-Kreuzsignale

[ppm]

16.6 2.27 7.10

126.3 7.10 -

128.9 7.10 7.10

129.7 8.06 7.66

130.0 7.89 2.27

130.7 - 7.10

131.4 - -

131.9

132.0 7.66 7.66, 8.06, 7.89

148.3 - 2.27, 7.10

164.9 - 7.89, 8.06

172.5 - 7.89, 8.06

449

2 Crystal Structure Data

2.1 Transannular cyclization-product (cone) (60)

Table 1. Crystal data and structure refinement for C56H60O4.

Empirical formula C56H60O4 Formula weight 797.04 Temperature 110(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, P2(1)/c

Unit cell dimensions a = 20.5290(7) Å α = 90° b = 17.7566(6) Å β = 92.535(3)° c = 24.2824(8) Å γ = 90°

Volume 8842.9(5) Å 3

Z, Calculated density 8, 1.197 Mg/m3 Absorption coefficient 0.073 mm-1 F(000) 3424 Crystal size 0.420 x 0.217 x 0.165 mm θ range for data collection 2.47 to 25.00 deg. Limiting indices -24<=h<=24, -21<=k<=21, -28<=l<=28 Reflections collected / unique 61209 / 15535 [R(int) = 0.0963] Completeness to θ = 25.00 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.998 and 0.966 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 15535 / 0 / 1089 Goodness-of-fit on F2 0.813 Final R indices [I>2σ(I)] R1 = 0.0438, wR2 = 0.0831 [6248 refs] R indices (all data) R1 = 0.1387, wR2 = 0.1085 Largest diff. peak and hole 0.580 and -0.370 e.Å-3

450 Appendix

Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C56H60O4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(11) 5005(1) 1782(1) 1098(1) 29(1) O(12) 5407(1) 3652(1) 1426(1) 35(1) O(13) 4829(1) 2370(1) 3230(1) 35(1) O(14) 3790(1) 624(1) 1686(1) 31(1) C(101) 5358(1) 647(2) 683(1) 27(1) C(102) 4840(1) 224(2) 985(1) 31(1) C(103) 4935(1) 361(1) 1603(1) 25(1) C(104) 5557(1) 350(1) 1852(1) 23(1) C(105) 5684(1) 577(1) 2390(1) 22(1) C(106) 5159(1) 832(1) 2686(1) 25(1) C(107) 4526(1) 841(1) 2461(1) 23(1) C(108) 3990(1) 1227(2) 2766(1) 30(1) C(109) 3962(1) 2042(2) 2580(1) 29(1) C(110) 3524(1) 2279(2) 2159(1) 34(1) C(111) 3575(2) 2988(2) 1926(1) 33(1) C(112) 4095(2) 3438(2) 2072(1) 35(1) C(113) 4551(2) 3229(2) 2488(1) 30(1) C(114) 5199(1) 3636(2) 2573(1) 33(1) C(115) 5716(1) 3146(2) 2312(1) 27(1) C(116) 6053(1) 2610(2) 2625(1) 26(1) C(117) 6420(1) 2053(2) 2388(1) 26(1) C(118) 6469(1) 2066(2) 1815(1) 27(1) C(119) 6156(1) 2609(2) 1487(1) 28(1) C(120) 6171(2) 2567(2) 862(1) 34(1) C(121) 6013(2) 1789(2) 639(1) 32(1) C(122) 6441(2) 1406(2) 307(1) 35(1) C(123) 6324(2) 671(2) 150(1) 38(1) C(124) 5796(2) 285(2) 352(1) 35(1) C(125) 5451(1) 1415(2) 788(1) 27(1) C(126) 5781(1) 3145(2) 1746(1) 28(1) C(127) 4431(1) 2555(2) 2760(1) 28(1) C(128) 4420(1) 591(1) 1922(1) 25(1) C(129) 6698(1) 1398(1) 2717(1) 24(1) C(130) 6571(1) 1311(1) 3335(1) 24(1) C(131) 6477(1) 440(1) 3249(1) 24(1) C(132) 6377(1) 592(1) 2619(1) 24(1) C(133) 7045(1) 1598(2) 3778(1) 29(1) C(134) 7526(1) 2121(2) 3669(1) 38(1) C(135) 7945(2) 2388(2) 4091(1) 44(1) C(136) 7894(2) 2133(2) 4620(1) 50(1) C(137) 7421(2) 1617(2) 4737(1) 45(1) C(138) 6996(2) 1359(2) 4323(1) 38(1) C(139) 7037(1) -64(1) 3420(1) 23(1) C(140) 7018(1) -454(2) 3914(1) 27(1) C(141) 7507(1) -948(2) 4082(1) 32(1) C(142) 8029(1) -1061(2) 3754(1) 32(1) C(143) 8061(1) -676(2) 3263(1) 29(1) C(144) 7569(1) -178(2) 3101(1) 26(1)

Crystal Structure Data 451

C(145) 4576(1) 2289(2) 792(1) 34(1) C(146) 3994(2) 1901(2) 526(1) 45(1) C(147) 3539(2) 2469(2) 236(1) 61(1) C(148) 5749(2) 4314(2) 1266(1) 39(1) C(149) 5247(2) 4822(2) 973(2) 73(1) C(150) 4800(2) 4482(2) 576(2) 77(1) C(151) 4635(2) 2783(2) 3712(1) 46(1) C(152) 5176(2) 2699(2) 4169(1) 58(1) C(153) 5217(2) 1910(2) 4365(1) 65(1) C(154) 3471(1) -95(2) 1654(1) 40(1) C(155) 2790(2) 17(2) 1421(2) 55(1) C(156) 2436(2) -727(2) 1346(2) 81(1) O(21) 9854(1) 1620(1) 1044(1) 31(1) O(22) 10098(1) -251(1) 1346(1) 31(1) O(23) 9602(1) 1004(1) 3182(1) 37(1) O(24) 8744(1) 2989(1) 1717(1) 37(1) C(201) 10302(1) 2775(2) 698(1) 29(1) C(202) 9826(2) 3238(2) 1017(1) 33(1) C(203) 9905(1) 3048(1) 1628(1) 26(1) C(204) 10523(1) 2958(1) 1870(1) 26(1) C(205) 10635(1) 2702(1) 2406(1) 24(1) C(206) 10089(1) 2508(1) 2697(1) 25(1) C(207) 9458(1) 2590(2) 2473(1) 27(1) C(208) 8879(1) 2262(2) 2760(1) 35(1) C(209) 8779(1) 1468(2) 2539(1) 35(1) C(210) 8329(1) 1312(2) 2104(1) 40(1) C(211) 8321(2) 616(2) 1845(1) 41(1) C(212) 8801(2) 94(2) 1984(1) 40(1) C(213) 9262(2) 236(2) 2410(1) 35(1) C(214) 9870(2) -249(2) 2496(1) 36(1) C(215) 10433(1) 180(2) 2248(1) 28(1) C(216) 10818(1) 661(2) 2575(1) 28(1) C(217) 11244(1) 1169(2) 2350(1) 24(1) C(218) 11292(1) 1175(2) 1779(1) 28(1) C(219) 10927(1) 693(2) 1437(1) 26(1) C(220) 10945(2) 768(2) 814(1) 34(1) C(221) 10873(2) 1573(2) 627(1) 29(1) C(222) 11351(2) 1937(2) 336(1) 36(1) C(223) 11293(2) 2687(2) 200(1) 38(1) C(224) 10785(2) 3104(2) 393(1) 33(1) C(225) 10331(1) 1993(2) 770(1) 28(1) C(226) 10499(1) 200(2) 1684(1) 26(1) C(227) 9204(1) 896(2) 2707(1) 32(1) C(228) 9376(1) 2887(2) 1942(1) 28(1) C(229) 11587(1) 1771(1) 2693(1) 26(1) C(230) 11493(1) 1820(1) 3319(1) 26(1) C(231) 11446(1) 2705(1) 3264(1) 24(1) C(232) 11323(1) 2607(1) 2627(1) 25(1) C(233) 11961(1) 1424(2) 3715(1) 27(1) C(234) 12635(2) 1520(2) 3706(1) 33(1) C(235) 13049(2) 1129(2) 4071(1) 40(1) C(236) 12802(2) 638(2) 4448(1) 46(1) C(237) 12140(2) 536(2) 4466(1) 45(1) C(238) 11720(2) 929(2) 4103(1) 38(1) C(239) 12031(1) 3175(1) 3450(1) 24(1) C(240) 12050(1) 3457(2) 3985(1) 35(1) C(241) 12565(2) 3902(2) 4177(1) 46(1) C(242) 13071(2) 4068(2) 3842(1) 42(1) C(243) 13059(1) 3787(2) 3316(1) 34(1) C(244) 12543(1) 3347(2) 3120(1) 30(1) C(245) 9208(1) 1605(2) 774(1) 38(1)

452 Appendix

C(246) 9070(2) 853(2) 515(1) 43(1) C(247) 8379(2) 825(2) 256(1) 47(1) C(248) 10395(1) -951(2) 1205(1) 32(1) C(249) 9930(1) -1366(2) 821(1) 29(1) C(250) 10179(2) -2146(2) 693(1) 44(1) C(251) 9260(2) 773(2) 3673(1) 65(1) C(252) 9686(2) 733(2) 4151(2) 70(1) C(253) 9312(2) 562(2) 4657(1) 58(1) C(254) 8503(2) 3738(2) 1834(2) 60(1) C(255) 7787(2) 3763(2) 1762(2) 78(1) C(256) 7511(2) 4507(2) 1933(2) 82(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C56H60O4. _____________________________________________________________ O(11)-C(125) 1.377(3) O(11)-C(145) 1.441(3) O(12)-C(126) 1.398(3) O(12)-C(148) 1.432(3) O(13)-C(127) 1.412(3) O(13)-C(151) 1.451(3) O(14)-C(128) 1.393(3) O(14)-C(154) 1.434(3) C(101)-C(124) 1.390(4) C(101)-C(125) 1.399(4) C(101)-C(102) 1.517(4) C(102)-C(103) 1.523(3) C(103)-C(104) 1.390(3) C(103)-C(128) 1.398(4) C(104)-C(105) 1.381(3) C(105)-C(106) 1.397(4) C(105)-C(132) 1.503(3) C(106)-C(107) 1.387(3) C(107)-C(128) 1.389(3) C(107)-C(108) 1.517(4) C(108)-C(109) 1.517(4) C(109)-C(127) 1.383(4) C(109)-C(110) 1.396(4) C(110)-C(111) 1.386(4) C(111)-C(112) 1.367(4) C(112)-C(113) 1.396(4) C(113)-C(127) 1.394(4) C(113)-C(114) 1.521(4) C(114)-C(115) 1.531(4) C(115)-C(116) 1.384(3) C(115)-C(126) 1.386(4) C(116)-C(117) 1.385(4) C(117)-C(118) 1.400(3) C(117)-C(129) 1.508(3) C(118)-C(119) 1.390(3) C(119)-C(126) 1.392(4) C(119)-C(120) 1.521(4) C(120)-C(121) 1.513(4) C(121)-C(125) 1.394(4)


C(121)-C(122) 1.396(4) C(122)-C(123) 1.377(4) C(123)-C(124) 1.391(4) C(129)-C(130) 1.543(3) C(129)-C(132) 1.590(3) C(130)-C(133) 1.506(4) C(130)-C(131) 1.571(3) C(131)-C(139) 1.501(3) C(131)-C(132) 1.558(3) C(133)-C(134) 1.389(4) C(133)-C(138) 1.398(4) C(134)-C(135) 1.391(4) C(135)-C(136) 1.370(4) C(136)-C(137) 1.374(4) C(137)-C(138) 1.381(4) C(139)-C(144) 1.381(4) C(139)-C(140) 1.388(3) C(140)-C(141) 1.381(3) C(141)-C(142) 1.378(4) C(142)-C(143) 1.379(4) C(143)-C(144) 1.386(3) C(145)-C(146) 1.502(4) C(146)-C(147) 1.525(4) C(148)-C(149) 1.523(4) C(149)-C(150) 1.434(4) C(151)-C(152) 1.543(4) C(152)-C(153) 1.482(4) C(154)-C(155) 1.498(4) C(155)-C(156) 1.515(4) O(21)-C(225) 1.378(3) O(21)-C(245) 1.453(3) O(22)-C(226) 1.390(3) O(22)-C(248) 1.433(3) O(23)-C(227) 1.397(3) O(23)-C(251) 1.469(4) O(24)-C(228) 1.399(3) O(24)-C(254) 1.451(3) C(201)-C(224) 1.392(4) C(201)-C(225) 1.401(4) C(201)-C(202) 1.515(4) C(202)-C(203) 1.525(3) C(203)-C(204) 1.382(4) C(203)-C(228) 1.384(4) C(204)-C(205) 1.389(3) C(205)-C(206) 1.394(4) C(205)-C(232) 1.498(4) C(206)-C(207) 1.392(4) C(207)-C(228) 1.394(4) C(207)-C(208) 1.519(4) C(208)-C(209) 1.519(4) C(209)-C(227) 1.390(4) C(209)-C(210) 1.399(4) C(210)-C(211) 1.387(4) C(211)-C(212) 1.383(4) C(212)-C(213) 1.394(4) C(213)-C(227) 1.382(4) C(213)-C(214) 1.525(4) C(214)-C(215) 1.530(4) C(215)-C(226) 1.382(4) C(215)-C(216) 1.388(4) C(216)-C(217) 1.386(4)

454 Appendix

C(217)-C(218) 1.393(3) C(217)-C(229) 1.510(3) C(218)-C(219) 1.388(3) C(219)-C(226) 1.395(4) C(219)-C(220) 1.521(3) C(220)-C(221) 1.506(4) C(221)-C(222) 1.393(4) C(221)-C(225) 1.395(4) C(222)-C(223) 1.376(4) C(223)-C(224) 1.378(4) C(229)-C(230) 1.543(3) C(229)-C(232) 1.586(3) C(230)-C(233) 1.503(4) C(230)-C(231) 1.579(3) C(231)-C(239) 1.515(3) C(231)-C(232) 1.566(3) C(233)-C(234) 1.395(4) C(233)-C(238) 1.395(4) C(234)-C(235) 1.386(4) C(235)-C(236) 1.377(4) C(236)-C(237) 1.374(4) C(237)-C(238) 1.392(4) C(239)-C(244) 1.384(4) C(239)-C(240) 1.392(3) C(240)-C(241) 1.385(4) C(241)-C(242) 1.379(4) C(242)-C(243) 1.370(4) C(243)-C(244) 1.383(4) C(245)-C(246) 1.497(4) C(246)-C(247) 1.528(4) C(248)-C(249) 1.497(3) C(249)-C(250) 1.513(4) C(251)-C(252) 1.424(4) C(252)-C(253) 1.508(4) C(254)-C(255) 1.473(4) C(255)-C(256) 1.503(5) C(125)-O(11)-C(145) 114.8(2) C(126)-O(12)-C(148) 114.5(2) C(127)-O(13)-C(151) 111.4(2) C(128)-O(14)-C(154) 113.5(2) C(124)-C(101)-C(125) 118.0(3) C(124)-C(101)-C(102) 122.5(3) C(125)-C(101)-C(102) 119.1(3) C(101)-C(102)-C(103) 109.6(2) C(104)-C(103)-C(128) 117.7(2) C(104)-C(103)-C(102) 120.1(3) C(128)-C(103)-C(102) 121.7(3) C(105)-C(104)-C(103) 122.6(3) C(104)-C(105)-C(106) 117.6(2) C(104)-C(105)-C(132) 119.4(2) C(106)-C(105)-C(132) 122.9(2) C(107)-C(106)-C(105) 122.1(3) C(106)-C(107)-C(128) 118.2(3) C(106)-C(107)-C(108) 120.0(2) C(128)-C(107)-C(108) 121.2(2) C(109)-C(108)-C(107) 107.6(2) C(127)-C(109)-C(110) 116.7(3) C(127)-C(109)-C(108) 121.2(2) C(110)-C(109)-C(108) 121.4(3) C(111)-C(110)-C(109) 121.0(3)


C(112)-C(111)-C(110) 119.8(3) C(111)-C(112)-C(113) 121.5(3) C(127)-C(113)-C(112) 116.4(3) C(127)-C(113)-C(114) 121.1(3) C(112)-C(113)-C(114) 121.7(3) C(113)-C(114)-C(115) 107.0(2) C(116)-C(115)-C(126) 118.4(3) C(116)-C(115)-C(114) 120.2(3) C(126)-C(115)-C(114) 120.6(3) C(115)-C(116)-C(117) 122.1(3) C(116)-C(117)-C(118) 117.8(3) C(116)-C(117)-C(129) 122.1(2) C(118)-C(117)-C(129) 119.8(2) C(119)-C(118)-C(117) 122.0(3) C(118)-C(119)-C(126) 117.7(3) C(118)-C(119)-C(120) 120.6(3) C(126)-C(119)-C(120) 121.4(3) C(121)-C(120)-C(119) 112.8(2) C(125)-C(121)-C(122) 117.8(3) C(125)-C(121)-C(120) 120.6(3) C(122)-C(121)-C(120) 121.5(3) C(123)-C(122)-C(121) 121.0(3) C(122)-C(123)-C(124) 119.9(3) C(101)-C(124)-C(123) 120.7(3) O(11)-C(125)-C(121) 119.6(3) O(11)-C(125)-C(101) 118.2(3) C(121)-C(125)-C(101) 121.8(3) C(115)-C(126)-C(119) 122.0(3) C(115)-C(126)-O(12) 118.4(3) C(119)-C(126)-O(12) 119.3(2) C(109)-C(127)-C(113) 123.4(3) C(109)-C(127)-O(13) 118.2(2) C(113)-C(127)-O(13) 118.4(3) C(107)-C(128)-O(14) 118.6(2) C(107)-C(128)-C(103) 121.6(3) O(14)-C(128)-C(103) 119.6(2) C(117)-C(129)-C(130) 121.1(2) C(117)-C(129)-C(132) 118.1(2) C(130)-C(129)-C(132) 88.22(19) C(133)-C(130)-C(129) 121.9(2) C(133)-C(130)-C(131) 120.1(2) C(129)-C(130)-C(131) 89.62(19) C(139)-C(131)-C(132) 116.3(2) C(139)-C(131)-C(130) 117.5(2) C(132)-C(131)-C(130) 88.37(19) C(105)-C(132)-C(131) 116.2(2) C(105)-C(132)-C(129) 116.8(2) C(131)-C(132)-C(129) 88.41(18) C(134)-C(133)-C(138) 117.7(3) C(134)-C(133)-C(130) 122.2(3) C(138)-C(133)-C(130) 120.1(3) C(133)-C(134)-C(135) 120.6(3) C(136)-C(135)-C(134) 120.6(3) C(135)-C(136)-C(137) 119.9(3) C(136)-C(137)-C(138) 120.0(3) C(137)-C(138)-C(133) 121.4(3) C(144)-C(139)-C(140) 117.7(2) C(144)-C(139)-C(131) 123.1(2) C(140)-C(139)-C(131) 119.2(2) C(141)-C(140)-C(139) 121.7(3) C(142)-C(141)-C(140) 119.7(3)

456 Appendix

C(141)-C(142)-C(143) 119.6(3) C(142)-C(143)-C(144) 120.1(3) C(139)-C(144)-C(143) 121.2(3) O(11)-C(145)-C(146) 113.0(2) C(145)-C(146)-C(147) 110.8(3) O(12)-C(148)-C(149) 106.4(2) C(150)-C(149)-C(148) 117.7(3) O(13)-C(151)-C(152) 108.5(2) C(153)-C(152)-C(151) 110.5(3) O(14)-C(154)-C(155) 108.6(2) C(154)-C(155)-C(156) 111.4(3) C(225)-O(21)-C(245) 116.4(2) C(226)-O(22)-C(248) 113.2(2) C(227)-O(23)-C(251) 110.4(2) C(228)-O(24)-C(254) 111.1(2) C(224)-C(201)-C(225) 117.0(3) C(224)-C(201)-C(202) 122.3(3) C(225)-C(201)-C(202) 119.9(3) C(201)-C(202)-C(203) 109.5(2) C(204)-C(203)-C(228) 118.0(3) C(204)-C(203)-C(202) 119.7(3) C(228)-C(203)-C(202) 122.0(3) C(203)-C(204)-C(205) 123.1(3) C(204)-C(205)-C(206) 116.9(3) C(204)-C(205)-C(232) 119.2(3) C(206)-C(205)-C(232) 123.8(2) C(207)-C(206)-C(205) 122.1(3) C(206)-C(207)-C(228) 118.2(3) C(206)-C(207)-C(208) 120.9(2) C(228)-C(207)-C(208) 120.3(3) C(209)-C(208)-C(207) 106.9(2) C(227)-C(209)-C(210) 117.5(3) C(227)-C(209)-C(208) 120.1(3) C(210)-C(209)-C(208) 121.7(3) C(211)-C(210)-C(209) 120.9(3) C(212)-C(211)-C(210) 119.4(3) C(211)-C(212)-C(213) 120.9(3) C(227)-C(213)-C(212) 118.0(3) C(227)-C(213)-C(214) 119.7(3) C(212)-C(213)-C(214) 121.6(3) C(213)-C(214)-C(215) 107.1(2) C(226)-C(215)-C(216) 118.3(3) C(226)-C(215)-C(214) 120.7(3) C(216)-C(215)-C(214) 120.1(3) C(217)-C(216)-C(215) 121.8(3) C(216)-C(217)-C(218) 118.1(3) C(216)-C(217)-C(229) 122.0(2) C(218)-C(217)-C(229) 119.4(2) C(219)-C(218)-C(217) 122.0(3) C(218)-C(219)-C(226) 117.7(3) C(218)-C(219)-C(220) 120.3(3) C(226)-C(219)-C(220) 121.7(2) C(221)-C(220)-C(219) 112.1(2) C(222)-C(221)-C(225) 117.8(3) C(222)-C(221)-C(220) 122.0(3) C(225)-C(221)-C(220) 120.1(3) C(223)-C(222)-C(221) 121.0(3) C(222)-C(223)-C(224) 119.8(3) C(223)-C(224)-C(201) 121.5(3) O(21)-C(225)-C(221) 117.0(3)


O(21)-C(225)-C(201) 120.6(3) C(221)-C(225)-C(201) 121.9(3) C(215)-C(226)-O(22) 119.2(2) C(215)-C(226)-C(219) 122.1(3) O(22)-C(226)-C(219) 118.5(2) C(213)-C(227)-C(209) 122.2(3) C(213)-C(227)-O(23) 119.1(3) C(209)-C(227)-O(23) 118.6(3) C(203)-C(228)-C(207) 121.4(3) C(203)-C(228)-O(24) 119.7(2) C(207)-C(228)-O(24) 118.8(3) C(217)-C(229)-C(230) 120.6(2) C(217)-C(229)-C(232) 117.3(2) C(230)-C(229)-C(232) 89.35(19) C(233)-C(230)-C(229) 120.0(2) C(233)-C(230)-C(231) 123.6(2) C(229)-C(230)-C(231) 89.07(19) C(239)-C(231)-C(232) 116.5(2) C(239)-C(231)-C(230) 118.6(2) C(232)-C(231)-C(230) 88.79(18) C(205)-C(232)-C(231) 116.8(2) C(205)-C(232)-C(229) 117.0(2) C(231)-C(232)-C(229) 88.02(18) C(234)-C(233)-C(238) 118.0(3) C(234)-C(233)-C(230) 122.6(3) C(238)-C(233)-C(230) 119.4(3) C(235)-C(234)-C(233) 120.5(3) C(236)-C(235)-C(234) 120.7(3) C(237)-C(236)-C(235) 119.8(3) C(236)-C(237)-C(238) 120.0(3) C(237)-C(238)-C(233) 121.0(3) C(244)-C(239)-C(240) 118.2(3) C(244)-C(239)-C(231) 124.2(2) C(240)-C(239)-C(231) 117.6(3) C(241)-C(240)-C(239) 120.5(3) C(242)-C(241)-C(240) 120.5(3) C(243)-C(242)-C(241) 119.2(3) C(242)-C(243)-C(244) 120.7(3) C(243)-C(244)-C(239) 120.9(3) O(21)-C(245)-C(246) 111.0(2) C(245)-C(246)-C(247) 110.9(3) O(22)-C(248)-C(249) 108.1(2) C(248)-C(249)-C(250) 111.6(2) C(252)-C(251)-O(23) 112.2(3) C(251)-C(252)-C(253) 110.9(3) O(24)-C(254)-C(255) 110.6(3) C(254)-C(255)-C(256) 112.3(3) _____________________________________________________________

458 Appendix

Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C56H60O4. The anisotropic displacement factor exponent takes the form: -2 pi2 [h2 a*2 U11 + ... + 2 h k a

* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(11) 32(1) 29(1) 26(1) 1(1) 4(1) 7(1) O(12) 41(1) 28(1) 34(1) 12(1) -5(1) -3(1) O(13) 40(1) 38(1) 27(1) 0(1) 1(1) 9(1) O(14) 23(1) 31(1) 37(1) 0(1) -5(1) -1(1) C(101) 26(2) 35(2) 19(2) 0(1) -8(1) 1(2) C(102) 36(2) 28(2) 29(2) -2(1) -5(1) 5(2) C(103) 28(2) 19(2) 27(2) -1(1) -1(1) 0(1) C(104) 24(2) 20(2) 25(2) -1(1) 5(1) 1(1) C(105) 21(2) 21(2) 23(2) 2(1) -2(1) 1(1) C(106) 30(2) 24(2) 21(2) 3(1) 0(1) -4(1) C(107) 22(2) 25(2) 24(2) 3(1) 2(1) 0(1) C(108) 24(2) 35(2) 30(2) 6(1) 2(1) -3(1) C(109) 26(2) 32(2) 29(2) -1(1) 5(1) 5(2) C(110) 31(2) 39(2) 34(2) -4(2) 4(2) 4(2) C(111) 35(2) 38(2) 26(2) 2(2) -2(1) 12(2) C(112) 41(2) 31(2) 33(2) 3(2) 3(2) 11(2) C(113) 39(2) 28(2) 25(2) -2(1) 8(2) 8(2) C(114) 43(2) 23(2) 32(2) 0(1) -4(2) 3(2) C(115) 30(2) 20(2) 30(2) -1(1) -2(1) -1(1) C(116) 29(2) 23(2) 24(2) -2(1) -1(1) 0(1) C(117) 22(2) 27(2) 28(2) 1(1) -3(1) -2(1) C(118) 20(2) 31(2) 31(2) -1(1) 8(1) -2(1) C(119) 31(2) 28(2) 24(2) 4(1) 0(1) -7(2) C(120) 35(2) 33(2) 33(2) 6(2) 6(2) -6(2) C(121) 38(2) 38(2) 19(2) 2(1) 4(1) -1(2) C(122) 35(2) 45(2) 24(2) 2(2) 2(1) -2(2) C(123) 32(2) 53(2) 29(2) -6(2) 4(2) 10(2) C(124) 39(2) 38(2) 26(2) -8(2) -5(2) 9(2) C(125) 32(2) 32(2) 16(2) -1(1) 1(1) 9(2) C(126) 33(2) 20(2) 30(2) 7(1) -5(2) -4(2) C(127) 29(2) 34(2) 20(2) 0(1) 0(1) 11(2) C(128) 25(2) 18(2) 33(2) 4(1) -7(1) 0(1) C(129) 22(2) 28(2) 23(2) 1(1) 3(1) -1(1) C(130) 23(2) 28(2) 23(2) -1(1) 2(1) 5(1) C(131) 21(2) 24(2) 27(2) 0(1) 2(1) 0(1) C(132) 25(2) 23(2) 23(2) -2(1) 2(1) 4(1) C(133) 29(2) 28(2) 30(2) -7(1) -1(1) 8(2) C(134) 31(2) 48(2) 34(2) -3(2) -2(2) -2(2) C(135) 32(2) 50(2) 49(2) -11(2) -2(2) -6(2) C(136) 51(2) 55(2) 42(2) -20(2) -13(2) 10(2) C(137) 61(3) 45(2) 29(2) -9(2) -7(2) 8(2) C(138) 48(2) 38(2) 29(2) -4(2) 0(2) -2(2) C(139) 24(2) 23(2) 22(2) 1(1) -1(1) 0(1) C(140) 22(2) 32(2) 28(2) -1(1) 4(1) 5(1) C(141) 36(2) 32(2) 27(2) 3(1) -4(2) 2(2) C(142) 28(2) 34(2) 33(2) 3(2) -4(2) 7(2) C(143) 23(2) 33(2) 30(2) -1(1) 3(1) 2(2)


C(144) 29(2) 25(2) 23(2) 4(1) 2(1) 0(1) C(145) 38(2) 34(2) 30(2) -1(1) 4(2) 8(2) C(146) 45(2) 42(2) 48(2) 2(2) -5(2) 4(2) C(147) 50(2) 63(3) 66(3) 3(2) -15(2) 15(2) C(148) 48(2) 25(2) 44(2) 12(2) -1(2) -7(2) C(149) 95(3) 48(3) 73(3) 33(2) -26(3) -19(2) C(150) 66(3) 90(3) 73(3) 46(2) -5(2) -1(2) C(151) 54(2) 63(2) 21(2) -2(2) 4(2) 20(2) C(152) 93(3) 51(2) 32(2) -2(2) 6(2) 13(2) C(153) 73(3) 80(3) 43(2) -8(2) 10(2) 3(2) C(154) 30(2) 33(2) 56(2) -1(2) -6(2) -7(2) C(155) 30(2) 50(2) 85(3) -2(2) -14(2) -7(2) C(156) 44(2) 73(3) 125(4) -3(3) -24(2) -23(2) O(21) 30(1) 35(1) 30(1) 6(1) -1(1) -7(1) O(22) 35(1) 24(1) 34(1) -6(1) -6(1) -1(1) O(23) 42(1) 41(1) 28(1) 2(1) 1(1) -11(1) O(24) 28(1) 41(1) 41(1) -2(1) -3(1) 5(1) C(201) 39(2) 28(2) 21(2) 1(1) -5(1) -9(2) C(202) 41(2) 26(2) 31(2) 5(1) -4(2) -4(2) C(203) 32(2) 16(2) 28(2) 0(1) -4(2) -1(1) C(204) 33(2) 23(2) 23(2) -1(1) 5(1) -3(1) C(205) 27(2) 16(2) 30(2) -4(1) 2(1) -1(1) C(206) 29(2) 25(2) 21(2) -2(1) 3(1) 0(1) C(207) 26(2) 24(2) 30(2) -2(1) 4(1) -2(1) C(208) 29(2) 44(2) 32(2) -3(2) 4(2) 2(2) C(209) 27(2) 49(2) 28(2) -1(2) 9(2) -13(2) C(210) 28(2) 59(2) 34(2) 6(2) 10(2) -9(2) C(211) 38(2) 60(2) 27(2) -6(2) 4(2) -21(2) C(212) 43(2) 47(2) 30(2) -6(2) 10(2) -18(2) C(213) 40(2) 38(2) 28(2) 2(2) 7(2) -12(2) C(214) 52(2) 27(2) 29(2) -1(1) 0(2) -13(2) C(215) 36(2) 20(2) 28(2) 1(1) 0(1) 3(2) C(216) 37(2) 24(2) 22(2) 0(1) -1(1) 3(2) C(217) 20(2) 19(2) 33(2) -1(1) 0(1) 4(1) C(218) 28(2) 28(2) 29(2) -1(1) 5(1) 5(1) C(219) 31(2) 25(2) 22(2) -7(1) -2(1) 4(2) C(220) 41(2) 37(2) 24(2) -6(1) 0(1) -1(2) C(221) 37(2) 29(2) 22(2) -3(1) -1(1) -9(2) C(222) 40(2) 43(2) 25(2) -4(2) 3(2) -7(2) C(223) 42(2) 51(2) 22(2) 0(2) 1(2) -19(2) C(224) 41(2) 33(2) 24(2) 4(1) -8(2) -16(2) C(225) 28(2) 32(2) 25(2) -1(1) -1(1) -6(2) C(226) 29(2) 20(2) 28(2) -4(1) -4(1) 0(1) C(227) 30(2) 39(2) 26(2) 2(2) -1(1) -12(2) C(228) 25(2) 24(2) 33(2) -3(1) -4(2) 3(1) C(229) 24(2) 26(2) 27(2) -3(1) 3(1) -1(1) C(230) 27(2) 25(2) 26(2) -3(1) 3(1) -4(1) C(231) 20(2) 28(2) 24(2) -4(1) 4(1) 0(1) C(232) 28(2) 25(2) 22(2) -2(1) 2(1) -4(1) C(233) 33(2) 27(2) 21(2) -8(1) 2(1) 3(2) C(234) 38(2) 35(2) 26(2) 1(1) 0(2) 1(2) C(235) 37(2) 48(2) 35(2) 0(2) -2(2) 5(2) C(236) 48(2) 59(2) 29(2) 3(2) -7(2) 13(2) C(237) 55(3) 48(2) 32(2) 12(2) 3(2) 0(2) C(238) 42(2) 47(2) 26(2) 1(2) 6(2) -3(2) C(239) 26(2) 21(2) 24(2) 2(1) -2(1) 1(1) C(240) 30(2) 49(2) 25(2) -5(2) 3(1) -7(2) C(241) 44(2) 60(2) 32(2) -15(2) 0(2) -15(2) C(242) 33(2) 52(2) 40(2) -12(2) -2(2) -18(2) C(243) 22(2) 40(2) 41(2) 4(2) 4(2) -7(2) C(244) 27(2) 33(2) 28(2) -6(1) 3(1) -2(2)

460 Appendix

C(245) 36(2) 39(2) 38(2) 3(2) 4(2) -4(2) C(246) 48(2) 42(2) 39(2) -3(2) 3(2) -5(2) C(247) 42(2) 50(2) 47(2) -6(2) -5(2) -7(2) C(248) 36(2) 28(2) 31(2) -3(1) -2(2) 1(2) C(249) 32(2) 30(2) 25(2) -1(1) 1(1) -7(2) C(250) 64(2) 33(2) 35(2) -9(2) -8(2) -5(2) C(251) 75(3) 84(3) 36(2) 12(2) -10(2) -46(2) C(252) 90(3) 53(3) 65(3) 10(2) -3(2) -5(2) C(253) 100(3) 47(2) 28(2) 10(2) 12(2) 2(2) C(254) 44(2) 46(2) 89(3) -2(2) -9(2) 15(2) C(255) 50(3) 56(3) 127(4) -11(2) -15(3) 18(2) C(256) 59(3) 86(3) 100(3) 9(3) -2(2) 22(2) ______________________________________________________________________ Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (A2 x 103) for C56H60O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(10A) 4871 -321 907 38 H(10B) 4401 399 856 38 H(104) 5910 179 1644 28 H(106) 5238 1005 3053 30 H(10C) 3567 976 2681 36 H(10D) 4085 1199 3169 36 H(110) 3186 1949 2030 41 H(111) 3250 3161 1666 39 H(112) 4147 3904 1887 42 H(11A) 5306 3707 2971 39 H(11B) 5178 4137 2394 39 H(116) 6030 2624 3015 31 H(118) 6723 1691 1645 33 H(12A) 5852 2931 699 40 H(12B) 6609 2717 747 40 H(122) 6819 1655 188 42 H(123) 6603 429 -97 46 H(124) 5735 -232 263 41 H(129) 7177 1363 2663 29 H(130) 6135 1534 3401 29 H(131) 6064 263 3409 29 H(132) 6662 259 2401 29 H(134) 7571 2297 3303 45 H(135) 8268 2750 4012 53 H(136) 8186 2312 4905 59 H(137) 7386 1438 5103 54 H(138) 6664 1012 4410 46 H(140) 6660 -379 4143 33 H(141) 7484 -1208 4423 38 H(142) 8366 -1403 3866 38 H(143) 8419 -752 3036 35 H(144) 7598 90 2764 31 H(14A) 4824 2540 503 40


H(14B) 4425 2684 1044 40 H(14C) 3755 1628 810 54 H(14D) 4140 1528 255 54 H(14E) 3403 2846 502 91 H(14F) 3154 2208 78 91 H(14G) 3768 2719 -59 91 H(14H) 6099 4181 1016 47 H(14I) 5948 4571 1594 47 H(14J) 4989 5067 1257 87 H(14K) 5485 5225 784 87 H(15A) 5044 4251 282 115 H(15B) 4506 4869 418 115 H(15C) 4544 4096 757 115 H(15D) 4219 2580 3840 55 H(15E) 4570 3321 3618 55 H(15F) 5600 2852 4024 70 H(15G) 5082 3035 4481 70 H(15H) 4799 1761 4512 98 H(15I) 5562 1867 4655 98 H(15J) 5317 1579 4056 98 H(15K) 3461 -322 2025 48 H(15L) 3711 -438 1414 48 H(15M) 2804 276 1060 66 H(15N) 2547 343 1672 66 H(15O) 2676 -1051 1100 122 H(15P) 1996 -636 1186 122 H(15Q) 2405 -974 1705 122 H(20A) 9374 3127 881 39 H(20B) 9910 3781 960 39 H(204) 10888 3078 1659 31 H(206) 10150 2313 3060 30 H(20C) 8969 2251 3163 42 H(20D) 8484 2571 2680 42 H(210) 8026 1688 1984 48 H(211) 7988 498 1574 50 H(212) 8817 -366 1786 47 H(21A) 9807 -741 2310 44 H(21B) 9964 -338 2894 44 H(216) 10789 640 2964 33 H(218) 11584 1519 1619 34 H(22A) 11364 566 691 41 H(22B) 10589 463 639 41 H(222) 11723 1663 230 43 H(223) 11602 2916 -27 46 H(224) 10765 3628 316 39 H(229) 12063 1762 2624 31 H(230) 11046 1628 3388 31 H(231) 11044 2895 3436 28 H(232) 11629 2925 2419 30 H(234) 12812 1857 3447 40 H(235) 13506 1201 4061 48 H(236) 13089 370 4695 55 H(237) 11969 198 4726 54 H(238) 11263 859 4120 46 H(240) 11706 3343 4221 42 H(241) 12570 4095 4542 55 H(242) 13424 4374 3974 50 H(243) 13407 3895 3084 41 H(244) 12540 3161 2753 35 H(24A) 9177 2000 487 45 H(24B) 8877 1714 1047 45

462 Appendix

H(24C) 9122 454 799 51 H(24D) 9388 755 229 51 H(24E) 8065 940 537 70 H(24F) 8292 320 107 70 H(24G) 8337 1196 -42 70 H(24H) 10490 -1254 1541 38 H(24I) 10810 -857 1023 38 H(24J) 9868 -1077 474 35 H(24K) 9502 -1407 990 35 H(25A) 10599 -2106 519 66 H(25B) 9864 -2401 441 66 H(25C) 10233 -2436 1035 66 H(25D) 8908 1138 3739 78 H(25E) 9057 274 3606 78 H(25F) 9919 1218 4202 84 H(25G) 10016 335 4100 84 H(25H) 9061 1006 4758 87 H(25I) 9618 428 4963 87 H(25J) 9015 140 4580 87 H(25K) 8697 4106 1582 72 H(25L) 8636 3879 2217 72 H(25M) 7598 3357 1985 94 H(25N) 7659 3669 1370 94 H(25O) 7653 4615 2316 123 H(25P) 7034 4487 1903 123 H(25Q) 7667 4906 1693 123 ______________________________________________________________________


2.2 proximal cone-Calix[4]diphenanthrenes (81a)

Table 1. Crystal data and structure refinement for C56H56O4. Empirical formula C56H56O4 Formula weight 793.01 Temperature 113(2) K Wavelength 0.71073 A Crystal system, space group Orthorhombic, P2(1)2(1)2(1) Unit cell dimensions a = 11.0221(6) Å α = 90° b = 13.3367(8) Å β = 90° c = 29.6439(15) Å γ = 90° Volume 4357.6(4) A3 Z, Calculated density 4, 1.209 Mg/m3 Absorption coefficient 0.074 mm-1 F(000) 1696 Crystal size 0.22 x 0.20 x 0.10 mm θ range for data collection 3.14 to 26.00 deg. Limiting indices -12<=h<=13, -16<=k<=16, -36<=l<=36 Reflections collected / unique 28159 / 4774 [R(int) = 0.0450] Completeness to θ = 26.00 99.6 % Absorption correction None Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4774 / 0 / 545 Goodness-of-fit on F2 1.009 Final R indices [I>2σ(I)] R1 = 0.0367, wR2 = 0.0552 [6093 refs] R indices (all data) R1 = 0.0525, wR2 = 0.0567 Absolute structure parameter 0(10) Largest diff. peak and hole 0.198 and -0.156 e.Å-3

464 Appendix

Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C56H56O4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(1) -315(1) 3790(1) 9462(1) 24(1) O(2) -375(1) 3654(1) 8405(1) 21(1) O(3) 1568(1) 1666(1) 7842(1) 20(1) O(4) 1052(1) 1792(1) 8920(1) 20(1) C(11) -1179(2) 3040(2) 9399(1) 21(1) C(12) -941(2) 2080(2) 9569(1) 21(1) C(13) -1807(2) 1336(2) 9495(1) 25(1) C(14) -2861(2) 1543(2) 9261(1) 26(1) C(15) -3049(2) 2493(2) 9084(1) 25(1) C(16) -2214(2) 3257(2) 9151(1) 21(1) C(17) -2392(2) 4276(2) 8923(1) 26(1) C(18) -491(2) 4363(2) 9865(1) 25(1) C(19) 550(2) 5079(2) 9915(1) 26(1) C(21) -1468(2) 3756(2) 8184(1) 19(1) C(22) -2474(2) 4132(2) 8417(1) 23(1) C(23) -3565(2) 4224(2) 8186(1) 27(1) C(24) -3661(2) 3906(2) 7740(1) 29(1) C(25) -2685(2) 3457(2) 7531(1) 26(1) C(26) -1569(2) 3360(2) 7748(1) 21(1) C(27) -574(2) 2704(2) 7570(1) 22(1) C(28) 319(2) 4571(2) 8447(1) 25(1) C(29) 1188(2) 4719(2) 8063(1) 26(1) C(31) 471(2) 1215(2) 7957(1) 17(1) C(32) -591(2) 1702(2) 7820(1) 18(1) C(33) -1663(2) 1279(2) 7951(1) 20(1) C(34) -1719(2) 373(2) 8191(1) 18(1) C(35) -645(2) -124(2) 8330(1) 17(1) C(36) 485(2) 361(2) 8231(1) 16(1) C(37) 1705(2) 59(2) 8427(1) 19(1) C(38) 1970(2) 1384(2) 7394(1) 25(1) C(39) 3148(2) 1912(2) 7302(1) 31(1) C(41) 1251(2) 923(2) 9160(1) 18(1) C(42) 1732(2) 80(2) 8948(1) 18(1) C(43) 2084(2) -749(2) 9224(1) 19(1) C(44) 1659(2) -778(2) 9675(1) 22(1) C(45) 1037(2) 56(2) 9853(1) 23(1) C(46) 867(2) 923(2) 9613(1) 19(1) C(47) 234(2) 1835(2) 9806(1) 24(1) C(48) 2129(2) 2350(2) 8807(1) 23(1) C(49) 2576(2) 3017(2) 9184(1) 25(1) C(110) 368(2) 5750(2) 10325(1) 36(1) C(210) 2023(2) 5608(2) 8156(1) 35(1) C(310) 4150(2) 1640(2) 7628(1) 38(1) C(311) -2891(2) 7(2) 8314(1) 22(1) C(312) -3022(2) -818(2) 8570(1) 24(1) C(313) -1986(2) -1398(2) 8696(1) 19(1) C(314) -2153(2) -2293(2) 8941(1) 25(1) C(315) -1212(2) -2914(2) 9043(1) 26(1)


C(316) -56(2) -2662(2) 8889(1) 25(1) C(317) 126(2) -1783(2) 8653(1) 21(1) C(318) -804(2) -1091(2) 8566(1) 17(1) C(410) 3613(2) 3671(2) 9023(1) 36(1) C(411) 2864(2) -1577(2) 9076(1) 21(1) C(412) 3597(2) -1542(2) 8683(1) 23(1) C(413) 4312(2) -2341(2) 8557(1) 28(1) C(414) 4364(2) -3208(2) 8817(1) 34(1) C(415) 3717(2) -3252(2) 9212(1) 34(1) C(416) 2980(2) -2444(2) 9353(1) 26(1) C(417) 2425(2) -2463(2) 9786(1) 32(1) C(418) 1830(2) -1658(2) 9942(1) 30(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C56H56O4. ______________________________________________________________________ O(1)-C(11) 1.394(2) O(1)-C(18) 1.432(2) O(2)-C(21) 1.379(2) O(2)-C(28) 1.448(2) O(3)-C(31) 1.393(2) O(3)-C(38) 1.449(2) O(4)-C(41) 1.378(2) O(4)-C(48) 1.441(2) C(11)-C(16) 1.388(3) C(11)-C(12) 1.399(3) C(12)-C(13) 1.394(3) C(12)-C(47) 1.511(3) C(13)-C(14) 1.381(3) C(13)-H(13) 0.9500 C(14)-C(15) 1.386(3) C(14)-H(14) 0.9500 C(15)-C(16) 1.387(3) C(15)-H(15) 0.9500 C(16)-C(17) 1.531(3) C(17)-C(22) 1.517(3) C(17)-H(17A) 0.9900 C(17)-H(17B) 0.9900 C(18)-C(19) 1.499(3) C(18)-H(18A) 0.9900 C(18)-H(18B) 0.9900 C(19)-C(110) 1.522(3) C(19)-H(19A) 0.9900 C(19)-H(19B) 0.9900 C(21)-C(22) 1.398(3) C(21)-C(26) 1.401(3) C(22)-C(23) 1.390(3) C(23)-C(24) 1.392(3) C(23)-H(23) 0.9500 C(24)-C(25) 1.379(3) C(24)-H(24) 0.9500 C(25)-C(26) 1.395(3) C(25)-H(25) 0.9500 C(26)-C(27) 1.498(3) C(27)-C(32) 1.527(3)

466 Appendix

C(27)-H(27A) 0.9900 C(27)-H(27B) 0.9900 C(28)-C(29) 1.500(3) C(28)-H(28A) 0.9900 C(28)-H(28B) 0.9900 C(29)-C(210) 1.526(3) C(29)-H(29A) 0.9900 C(29)-H(29B) 0.9900 C(31)-C(36) 1.398(3) C(31)-C(32) 1.399(3) C(32)-C(33) 1.366(3) C(33)-C(34) 1.405(3) C(33)-H(33) 0.9500 C(34)-C(35) 1.417(3) C(34)-C(311) 1.428(3) C(35)-C(36) 1.433(3) C(35)-C(318) 1.479(3) C(36)-C(37) 1.520(3) C(37)-C(42) 1.544(3) C(37)-H(37A) 0.9900 C(37)-H(37B) 0.9900 C(38)-C(39) 1.502(3) C(38)-H(38A) 0.9900 C(38)-H(38B) 0.9900 C(39)-C(310) 1.513(3) C(39)-H(39A) 0.9900 C(39)-H(39B) 0.9900 C(41)-C(42) 1.393(3) C(41)-C(46) 1.408(3) C(42)-C(43) 1.429(3) C(43)-C(44) 1.417(3) C(43)-C(411) 1.466(3) C(44)-C(45) 1.408(3) C(44)-C(418) 1.427(3) C(45)-C(46) 1.371(3) C(45)-H(45) 0.9500 C(46)-C(47) 1.514(3) C(47)-H(47A) 0.9900 C(47)-H(47B) 0.9900 C(48)-C(49) 1.511(3) C(48)-H(48A) 0.9900 C(48)-H(48B) 0.9900 C(49)-C(410) 1.515(3) C(49)-H(49A) 0.9900 C(49)-H(49B) 0.9900 C(110)-H(11A) 0.9800 C(110)-H(11B) 0.9800 C(110)-H(11C) 0.9800 C(210)-H(21A) 0.9800 C(210)-H(21B) 0.9800 C(210)-H(21C) 0.9800 C(310)-H(31A) 0.9800 C(310)-H(31B) 0.9800 C(310)-H(31C) 0.9800 C(311)-C(312) 1.344(3) C(311)-H(311) 0.9500 C(312)-C(313) 1.429(3) C(312)-H(312) 0.9500 C(313)-C(314) 1.409(3) C(313)-C(318) 1.419(3) C(314)-C(315) 1.362(3)


C(314)-H(314) 0.9500 C(315)-C(316) 1.395(3) C(315)-H(315) 0.9500 C(316)-C(317) 1.379(3) C(316)-H(316) 0.9500 C(317)-C(318) 1.404(3) C(317)-H(317) 0.9500 C(410)-H(41A) 0.9800 C(410)-H(41B) 0.9800 C(410)-H(41C) 0.9800 C(411)-C(412) 1.420(3) C(411)-C(416) 1.424(3) C(412)-C(413) 1.378(3) C(412)-H(412) 0.9500 C(413)-C(414) 1.391(3) C(413)-H(413) 0.9500 C(414)-C(415) 1.373(3) C(414)-H(414) 0.9500 C(415)-C(416) 1.413(3) C(415)-H(415) 0.9500 C(416)-C(417) 1.423(3) C(417)-C(418) 1.340(3) C(417)-H(417) 0.9500 C(418)-H(418) 0.9500 C(11)-O(1)-C(18) 113.70(16) C(21)-O(2)-C(28) 114.73(15) C(31)-O(3)-C(38) 112.29(15) C(41)-O(4)-C(48) 115.11(15) C(16)-C(11)-O(1) 118.88(19) C(16)-C(11)-C(12) 122.3(2) O(1)-C(11)-C(12) 118.7(2) C(13)-C(12)-C(11) 117.8(2) C(13)-C(12)-C(47) 120.4(2) C(11)-C(12)-C(47) 121.7(2) C(14)-C(13)-C(12) 120.8(2) C(14)-C(13)-H(13) 119.6 C(12)-C(13)-H(13) 119.6 C(13)-C(14)-C(15) 119.9(2) C(13)-C(14)-H(14) 120.1 C(15)-C(14)-H(14) 120.1 C(14)-C(15)-C(16) 121.2(2) C(14)-C(15)-H(15) 119.4 C(16)-C(15)-H(15) 119.4 C(15)-C(16)-C(11) 117.9(2) C(15)-C(16)-C(17) 120.3(2) C(11)-C(16)-C(17) 121.6(2) C(22)-C(17)-C(16) 109.38(18) C(22)-C(17)-H(17A) 109.8 C(16)-C(17)-H(17A) 109.8 C(22)-C(17)-H(17B) 109.8 C(16)-C(17)-H(17B) 109.8 H(17A)-C(17)-H(17B) 108.2 O(1)-C(18)-C(19) 108.53(17) O(1)-C(18)-H(18A) 110.0 C(19)-C(18)-H(18A) 110.0 O(1)-C(18)-H(18B) 110.0 C(19)-C(18)-H(18B) 110.0 H(18A)-C(18)-H(18B) 108.4 C(18)-C(19)-C(110) 110.60(18) C(18)-C(19)-H(19A) 109.5

468 Appendix

C(110)-C(19)-H(19A) 109.5 C(18)-C(19)-H(19B) 109.5 C(110)-C(19)-H(19B) 109.5 H(19A)-C(19)-H(19B) 108.1 O(2)-C(21)-C(22) 119.57(19) O(2)-C(21)-C(26) 118.07(19) C(22)-C(21)-C(26) 121.9(2) C(23)-C(22)-C(21) 118.3(2) C(23)-C(22)-C(17) 121.9(2) C(21)-C(22)-C(17) 119.1(2) C(22)-C(23)-C(24) 120.4(2) C(22)-C(23)-H(23) 119.8 C(24)-C(23)-H(23) 119.8 C(25)-C(24)-C(23) 120.0(2) C(25)-C(24)-H(24) 120.0 C(23)-C(24)-H(24) 120.0 C(24)-C(25)-C(26) 121.4(2) C(24)-C(25)-H(25) 119.3 C(26)-C(25)-H(25) 119.3 C(25)-C(26)-C(21) 117.4(2) C(25)-C(26)-C(27) 122.48(19) C(21)-C(26)-C(27) 119.2(2) C(26)-C(27)-C(32) 109.36(17) C(26)-C(27)-H(27A) 109.8 C(32)-C(27)-H(27A) 109.8 C(26)-C(27)-H(27B) 109.8 C(32)-C(27)-H(27B) 109.8 H(27A)-C(27)-H(27B) 108.3 O(2)-C(28)-C(29) 112.65(17) O(2)-C(28)-H(28A) 109.1 C(29)-C(28)-H(28A) 109.1 O(2)-C(28)-H(28B) 109.1 C(29)-C(28)-H(28B) 109.1 H(28A)-C(28)-H(28B) 107.8 C(28)-C(29)-C(210) 110.56(19) C(28)-C(29)-H(29A) 109.5 C(210)-C(29)-H(29A) 109.5 C(28)-C(29)-H(29B) 109.5 C(210)-C(29)-H(29B) 109.5 H(29A)-C(29)-H(29B) 108.1 O(3)-C(31)-C(36) 119.00(19) O(3)-C(31)-C(32) 116.99(18) C(36)-C(31)-C(32) 123.8(2) C(33)-C(32)-C(31) 116.71(19) C(33)-C(32)-C(27) 120.6(2) C(31)-C(32)-C(27) 122.48(19) C(32)-C(33)-C(34) 122.5(2) C(32)-C(33)-H(33) 118.7 C(34)-C(33)-H(33) 118.7 C(33)-C(34)-C(35) 120.8(2) C(33)-C(34)-C(311) 117.6(2) C(35)-C(34)-C(311) 121.50(19) C(34)-C(35)-C(36) 117.13(18) C(34)-C(35)-C(318) 116.46(18) C(36)-C(35)-C(318) 126.40(19) C(31)-C(36)-C(35) 118.5(2) C(31)-C(36)-C(37) 116.61(19) C(35)-C(36)-C(37) 124.79(18) C(36)-C(37)-C(42) 113.31(16) C(36)-C(37)-H(37A) 108.9 C(42)-C(37)-H(37A) 108.9


C(36)-C(37)-H(37B) 108.9 C(42)-C(37)-H(37B) 108.9 H(37A)-C(37)-H(37B) 107.7 O(3)-C(38)-C(39) 108.09(17) O(3)-C(38)-H(38A) 110.1 C(39)-C(38)-H(38A) 110.1 O(3)-C(38)-H(38B) 110.1 C(39)-C(38)-H(38B) 110.1 H(38A)-C(38)-H(38B) 108.4 C(38)-C(39)-C(310) 113.67(19) C(38)-C(39)-H(39A) 108.8 C(310)-C(39)-H(39A) 108.8 C(38)-C(39)-H(39B) 108.8 C(310)-C(39)-H(39B) 108.8 H(39A)-C(39)-H(39B) 107.7 O(4)-C(41)-C(42) 120.38(17) O(4)-C(41)-C(46) 116.41(19) C(42)-C(41)-C(46) 123.1(2) C(41)-C(42)-C(43) 117.94(18) C(41)-C(42)-C(37) 117.31(18) C(43)-C(42)-C(37) 124.32(19) C(44)-C(43)-C(42) 118.16(19) C(44)-C(43)-C(411) 117.08(19) C(42)-C(43)-C(411) 124.76(19) C(45)-C(44)-C(43) 119.5(2) C(45)-C(44)-C(418) 120.4(2) C(43)-C(44)-C(418) 120.1(2) C(46)-C(45)-C(44) 122.6(2) C(46)-C(45)-H(45) 118.7 C(44)-C(45)-H(45) 118.7 C(45)-C(46)-C(41) 117.0(2) C(45)-C(46)-C(47) 122.97(19) C(41)-C(46)-C(47) 120.0(2) C(12)-C(47)-C(46) 113.13(18) C(12)-C(47)-H(47A) 109.0 C(46)-C(47)-H(47A) 109.0 C(12)-C(47)-H(47B) 109.0 C(46)-C(47)-H(47B) 109.0 H(47A)-C(47)-H(47B) 107.8 O(4)-C(48)-C(49) 113.60(17) O(4)-C(48)-H(48A) 108.8 C(49)-C(48)-H(48A) 108.8 O(4)-C(48)-H(48B) 108.8 C(49)-C(48)-H(48B) 108.8 H(48A)-C(48)-H(48B) 107.7 C(48)-C(49)-C(410) 110.61(19) C(48)-C(49)-H(49A) 109.5 C(410)-C(49)-H(49A) 109.5 C(48)-C(49)-H(49B) 109.5 C(410)-C(49)-H(49B) 109.5 H(49A)-C(49)-H(49B) 108.1 C(19)-C(110)-H(11A) 109.5 C(19)-C(110)-H(11B) 109.5 H(11A)-C(110)-H(11B) 109.5 C(19)-C(110)-H(11C) 109.5 H(11A)-C(110)-H(11C) 109.5 H(11B)-C(110)-H(11C) 109.5 C(29)-C(210)-H(21A) 109.5 C(29)-C(210)-H(21B) 109.5 H(21A)-C(210)-H(21B) 109.5 C(29)-C(210)-H(21C) 109.5

470 Appendix

H(21A)-C(210)-H(21C) 109.5 H(21B)-C(210)-H(21C) 109.5 C(39)-C(310)-H(31A) 109.5 C(39)-C(310)-H(31B) 109.5 H(31A)-C(310)-H(31B) 109.5 C(39)-C(310)-H(31C) 109.5 H(31A)-C(310)-H(31C) 109.5 H(31B)-C(310)-H(31C) 109.5 C(312)-C(311)-C(34) 121.4(2) C(312)-C(311)-H(311) 119.3 C(34)-C(311)-H(311) 119.3 C(311)-C(312)-C(313) 120.3(2) C(311)-C(312)-H(312) 119.8 C(313)-C(312)-H(312) 119.8 C(314)-C(313)-C(318) 120.3(2) C(314)-C(313)-C(312) 119.2(2) C(318)-C(313)-C(312) 120.44(19) C(315)-C(314)-C(313) 122.1(2) C(315)-C(314)-H(314) 119.0 C(313)-C(314)-H(314) 119.0 C(314)-C(315)-C(316) 118.4(2) C(314)-C(315)-H(315) 120.8 C(316)-C(315)-H(315) 120.8 C(317)-C(316)-C(315) 120.2(2) C(317)-C(316)-H(316) 119.9 C(315)-C(316)-H(316) 119.9 C(316)-C(317)-C(318) 123.1(2) C(316)-C(317)-H(317) 118.4 C(318)-C(317)-H(317) 118.4 C(317)-C(318)-C(313) 115.50(19) C(317)-C(318)-C(35) 125.09(19) C(313)-C(318)-C(35) 119.30(19) C(49)-C(410)-H(41A) 109.5 C(49)-C(410)-H(41B) 109.5 H(41A)-C(410)-H(41B) 109.5 C(49)-C(410)-H(41C) 109.5 H(41A)-C(410)-H(41C) 109.5 H(41B)-C(410)-H(41C) 109.5 C(412)-C(411)-C(416) 116.7(2) C(412)-C(411)-C(43) 123.7(2) C(416)-C(411)-C(43) 119.5(2) C(413)-C(412)-C(411) 121.6(2) C(413)-C(412)-H(412) 119.2 C(411)-C(412)-H(412) 119.2 C(412)-C(413)-C(414) 121.1(2) C(412)-C(413)-H(413) 119.5 C(414)-C(413)-H(413) 119.5 C(415)-C(414)-C(413) 119.2(2) C(415)-C(414)-H(414) 120.4 C(413)-C(414)-H(414) 120.4 C(414)-C(415)-C(416) 121.2(2) C(414)-C(415)-H(415) 119.4 C(416)-C(415)-H(415) 119.4 C(415)-C(416)-C(417) 120.0(2) C(415)-C(416)-C(411) 120.1(2) C(417)-C(416)-C(411) 119.7(2) C(418)-C(417)-C(416) 120.4(2) C(418)-C(417)-H(417) 119.8 C(416)-C(417)-H(417) 119.8 C(417)-C(418)-C(44) 122.2(2)


C(417)-C(418)-H(418) 118.9 C(44)-C(418)-H(418) 118.9 ______________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C56H56O4. The anisotropic displacement factor exponent takes the form: -2 pi² [ h2 a*2 U11 + ... + 2 h k a* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(1) 27(1) 25(1) 22(1) -7(1) 5(1) -4(1) O(2) 19(1) 21(1) 23(1) 1(1) -2(1) 0(1) O(3) 23(1) 23(1) 15(1) -1(1) 4(1) -6(1) O(4) 21(1) 19(1) 19(1) 2(1) 0(1) -1(1) C(11) 17(1) 25(1) 20(1) -4(1) 8(1) -3(1) C(12) 22(1) 23(1) 17(1) -4(1) 6(1) 0(1) C(13) 30(2) 23(1) 23(1) 0(1) 8(1) 1(1) C(14) 22(1) 28(1) 29(1) -2(1) 4(1) -6(1) C(15) 19(1) 30(1) 27(1) 0(1) 2(1) 2(1) C(16) 17(1) 23(1) 24(1) -5(1) 7(1) 3(1) C(17) 25(1) 24(1) 29(1) -1(1) 4(1) 3(1) C(18) 27(1) 25(1) 23(1) -5(1) 4(1) 2(1) C(19) 30(1) 25(1) 23(1) -3(1) -1(1) -1(1) C(21) 19(1) 13(1) 26(1) 4(1) -1(1) 0(1) C(22) 23(1) 15(1) 30(1) 4(1) 3(1) 0(1) C(23) 22(1) 21(1) 38(1) 6(1) 3(1) 2(1) C(24) 26(2) 22(1) 39(2) 8(1) -8(1) 0(1) C(25) 33(2) 20(1) 24(1) 6(1) -5(1) -3(1) C(26) 26(1) 15(1) 21(1) 6(1) -1(1) -4(1) C(27) 27(1) 20(1) 17(1) 3(1) 0(1) -1(1) C(28) 26(1) 23(1) 25(1) -2(1) -2(1) -3(1) C(29) 28(1) 27(1) 23(1) 4(1) -3(1) -2(1) C(31) 16(1) 19(1) 15(1) -4(1) 2(1) -5(1) C(32) 24(1) 18(1) 13(1) -2(1) 0(1) -1(1) C(33) 22(1) 20(1) 18(1) -2(1) -3(1) 5(1) C(34) 21(1) 19(1) 15(1) -2(1) -1(1) -1(1) C(35) 21(1) 19(1) 12(1) -4(1) 2(1) -1(1) C(36) 20(1) 17(1) 12(1) -4(1) 1(1) 0(1) C(37) 22(1) 17(1) 17(1) -2(1) 4(1) -2(1) C(38) 28(1) 30(1) 17(1) -3(1) 3(1) -3(1) C(39) 30(2) 36(2) 29(1) 2(1) 11(1) -5(1) C(41) 17(1) 19(1) 18(1) 3(1) -3(1) -3(1)

472 Appendix

C(42) 14(1) 21(1) 18(1) 0(1) 2(1) -4(1) C(43) 15(1) 20(1) 21(1) 1(1) -2(1) -2(1) C(44) 21(1) 25(1) 20(1) 3(1) -5(1) -1(1) C(45) 24(1) 32(2) 14(1) 3(1) -1(1) -3(1) C(46) 16(1) 26(1) 16(1) -3(1) -1(1) -3(1) C(47) 30(2) 27(1) 14(1) -2(1) 3(1) 0(1) C(48) 26(1) 19(1) 23(1) 0(1) 4(1) 0(1) C(49) 23(1) 25(1) 26(1) -1(1) -3(1) 1(1) C(110) 38(2) 34(2) 35(1) -7(1) 5(1) -4(1) C(210) 35(2) 35(2) 35(1) 8(1) -6(1) -9(1) C(310) 27(2) 41(2) 46(2) -2(1) 5(1) -10(1) C(311) 18(1) 24(1) 25(1) 0(1) 0(1) 1(1) C(312) 18(1) 26(1) 27(1) -5(1) 5(1) -5(1) C(313) 19(1) 20(1) 17(1) -4(1) 2(1) -3(1) C(314) 27(1) 24(1) 22(1) 0(1) 8(1) -6(1) C(315) 36(2) 17(1) 26(1) 3(1) 3(1) -4(1) C(316) 29(1) 19(1) 26(1) -1(1) -4(1) 0(1) C(317) 24(1) 19(1) 20(1) -2(1) 0(1) -3(1) C(318) 18(1) 19(1) 14(1) -3(1) -1(1) -4(1) C(410) 25(1) 33(1) 49(2) 4(1) -8(1) -4(1) C(411) 17(1) 22(1) 24(1) -3(1) -5(1) -2(1) C(412) 16(1) 24(1) 28(1) -3(1) -5(1) 0(1) C(413) 19(1) 33(1) 33(1) -10(1) -4(1) 1(1) C(414) 25(1) 25(1) 51(2) -12(1) -10(1) 7(1) C(415) 32(2) 21(1) 48(2) 1(1) -10(1) 1(1) C(416) 24(1) 24(1) 31(1) 2(1) -8(1) -3(1) C(417) 34(2) 27(1) 36(2) 14(1) -4(1) -2(1) C(418) 33(2) 33(1) 23(1) 11(1) -2(1) 0(1) ______________________________________________________________________


Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103) for C56H56O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(13) -1670 678 9607 30 H(14) -3456 1035 9221 31 H(15) -3763 2623 8914 30 H(17A) -3145 4594 9036 31 H(17B) -1702 4722 8997 31 H(18A) -529 3911 10130 30 H(18B) -1264 4739 9847 30 H(19A) 616 5497 9640 31 H(19B) 1315 4697 9949 31 H(23) -4251 4507 8333 33 H(24) -4399 3999 7579 35 H(25) -2774 3207 7233 31 H(27A) 220 3036 7614 26 H(27B) -691 2590 7243 26 H(28A) 778 4556 8733 30 H(28B) -247 5147 8459 30 H(29A) 729 4839 7781 31 H(29B) 1680 4105 8022 31 H(33) -2400 1610 7876 24 H(37A) 2337 518 8311 22 H(37B) 1907 -627 8323 22 H(38A) 1355 1580 7167 30 H(38B) 2086 648 7377 30 H(39A) 3010 2644 7315 38 H(39B) 3415 1746 6992 38 H(45) 723 15 10151 28 H(47A) 65 1716 10130 28 H(47B) 785 2419 9785 28 H(48A) 1958 2770 8539 27 H(48B) 2781 1873 8724 27 H(49A) 2853 2597 9439 30 H(49B) 1903 3446 9292 30 H(11A) -258 6250 10259 54 H(11B) 1132 6090 10397 54 H(11C) 113 5341 10583 54 H(21A) 1542 6226 8168 52 H(21B) 2626 5661 7914 52 H(21C) 2437 5509 8445 52 H(31A) 3918 1846 7933 57 H(31B) 4899 1983 7540 57 H(31C) 4281 913 7622 57 H(311) -3593 354 8213 27 H(312) -3808 -1017 8667 28 H(314) -2947 -2468 9038 30 H(315) -1340 -3505 9216 31 H(316) 609 -3098 8946 29 H(317) 918 -1640 8545 25 H(41A) 4290 3247 8925 53 H(41B) 3881 4107 9270 53

474 Appendix

H(41C) 3339 4084 8769 53 H(412) 3594 -953 8502 27 H(413) 4776 -2300 8287 34 H(414) 4841 -3762 8722 40 H(415) 3765 -3837 9394 40 H(417) 2477 -3050 9967 39 H(418) 1510 -1673 10239 35 ______________________________________________________________________


2.3 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-

phenanthrene (86a)

Table 1. Crystal data and structure refinement for C58H60O4. Empirical formula C58H60O4 Formula weight 821.06 Temperature 113(2) K Wavelength 0.71073 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 11.1909(4) Å α = 93.885(4°

b = 14.9553(6) Å β = 90.615(3° c = 27.4641(13) Å γ = 93.971(3°

Volume 4574.4(3) Å3 Z, Calculated density 4, 1.192 Mg/m3 Absorption coefficient 0.073 mm-1 F(000) 1760 Crystal size 0.32 x 0.27 x 0.22 mm θ range for data collection 2.85 to 25.25 deg. Limiting indices -13<=h<=13, -17<=k<=17, -32<=l<=32 Reflections collected / unique 68021 / 16546 [R(int) = 0.1126] Completeness to θ = 25.25 99.7 % Absorption correction None Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 16546 / 0 / 1129 Goodness-of-fit on F2 0.829 Final R indices [I>2σ(I)] R1 = 0.0502, wR2 = 0.0892 R indices (all data) R1 = 0.1506, wR2 = 0.0997 Largest diff. peak and hole 0.450 and -0.376 e. Å-3

476 Appendix

Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C58H60O4. U(eq) is defined as one third of the trace of the Orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(1) 5382(2) -22(1) 3579(1) 25(1) O(2) 6913(2) 2134(1) 3859(1) 23(1) O(3) 9713(2) 2438(1) 3559(1) 22(1) O(4) 8316(2) 320(1) 3495(1) 24(1) C(11) 5953(3) -42(2) 4031(1) 21(1) C(12) 6765(3) -697(2) 4088(1) 22(1) C(13) 7327(3) -715(2) 4541(1) 24(1) C(14) 7096(3) -94(2) 4915(1) 27(1) C(15) 6316(3) 563(2) 4846(1) 28(1) C(16) 5739(3) 601(2) 4398(1) 19(1) C(17) 4932(3) 1354(2) 4318(1) 27(1) C(18) 4212(3) -471(2) 3565(1) 38(1) C(19) 3686(3) -429(3) 3055(1) 42(1) C(21) 6527(3) 2620(2) 4270(1) 21(1) C(22) 5497(3) 2258(2) 4498(1) 22(1) C(23) 5132(3) 2714(2) 4913(1) 25(1) C(24) 5678(3) 3550(2) 5079(1) 24(1) C(25) 6705(3) 3916(2) 4838(1) 20(1) C(26) 7199(3) 3373(2) 4459(1) 21(1) C(27) 8513(3) 3473(2) 4309(1) 22(1) C(28) 6801(3) 2578(2) 3415(1) 27(1) C(29) 5576(3) 2388(2) 3175(1) 34(1) C(31) 9687(3) 2133(2) 4023(1) 18(1) C(32) 9122(3) 2611(2) 4395(1) 19(1) C(33) 9103(3) 2293(2) 4856(1) 23(1) C(34) 9631(3) 1512(2) 4946(1) 24(1) C(35) 10149(3) 1017(2) 4569(1) 21(1) C(36) 10185(2) 1314(2) 4103(1) 18(1) C(37) 10733(3) 757(2) 3689(1) 22(1) C(38) 10812(3) 2964(2) 3485(1) 28(1) C(39) 10834(3) 3229(2) 2973(1) 46(1) C(41) 8995(3) -406(2) 3556(1) 19(1) C(42) 10225(3) -207(2) 3653(1) 21(1) C(43) 10891(3) -909(2) 3745(1) 21(1) C(44) 10415(3) -1806(2) 3707(1) 21(1) C(45) 9187(3) -1990(2) 3587(1) 20(1) C(46) 8439(3) -1258(2) 3572(1) 20(1) C(47) 7083(3) -1349(2) 3671(1) 24(1) C(48) 7788(3) 350(2) 3019(1) 26(1) C(49) 8631(3) 773(2) 2665(1) 32(1) C(110) 4397(3) -925(2) 2670(1) 43(1) C(210) 5501(3) 2879(3) 2708(1) 53(1) C(211) 5236(3) 4041(2) 5501(1) 28(1) C(212) 5715(3) 4852(2) 5674(1) 29(1) C(213) 5198(3) 5325(2) 6120(1) 39(1) C(214) 6665(3) 5290(2) 5406(1) 25(1) C(215) 7105(3) 6181(2) 5540(1) 31(1) C(216) 7910(3) 6641(2) 5262(1) 32(1)


C(217) 8267(3) 6228(2) 4827(1) 31(1) C(218) 7886(3) 5356(2) 4695(1) 25(1) C(219) 7123(3) 4842(2) 4982(1) 25(1) C(310) 12018(3) 3787(2) 2876(1) 60(1) C(410) 7992(3) 878(2) 2178(1) 44(1) C(411) 11139(3) -2520(2) 3814(1) 22(1) C(412) 10722(3) -3382(2) 3794(1) 25(1) C(413) 11482(3) -4105(2) 3959(1) 37(1) C(414) 9531(3) -3616(2) 3600(1) 25(1) C(415) 9101(3) -4527(2) 3503(1) 35(1) C(416) 8011(3) -4752(2) 3285(1) 39(1) C(417) 7299(3) -4086(2) 3141(1) 38(1) C(418) 7673(3) -3200(2) 3238(1) 29(1) C(419) 8766(3) -2930(2) 3490(1) 24(1) O(5) 508(2) 5331(1) 1455(1) 29(1) O(6) 3479(2) 5657(1) 1528(1) 25(1) O(7) 4973(2) 7750(1) 1462(1) 21(1) O(8) 2062(2) 7389(1) 1165(1) 23(1) C(51) 1024(3) 5188(2) 1000(1) 23(1) C(52) 791(3) 5742(2) 629(1) 21(1) C(53) 1310(3) 5574(2) 183(1) 25(1) C(54) 2067(3) 4890(2) 106(1) 28(1) C(55) 2324(3) 4365(2) 482(1) 24(1) C(56) 1820(3) 4514(2) 939(1) 20(1) C(57) 2172(3) 3972(2) 1356(1) 29(1) C(58) -600(3) 4834(3) 1501(1) 69(2) C(59) -843(4) 4744(4) 2035(2) 125(2) C(61) 4114(3) 4905(2) 1450(1) 20(1) C(62) 3531(3) 4047(2) 1441(1) 20(1) C(63) 4236(3) 3298(2) 1420(1) 18(1) C(64) 5454(3) 3422(2) 1289(1) 19(1) C(65) 5952(3) 4303(2) 1235(1) 21(1) C(66) 5333(3) 5043(2) 1338(1) 18(1) C(67) 5867(3) 5990(2) 1300(1) 23(1) C(68) 3045(3) 5808(2) 2013(1) 31(1) C(69) 3982(3) 6271(2) 2359(1) 34(1) C(71) 4843(3) 7336(2) 993(1) 17(1) C(72) 5302(3) 6486(2) 900(1) 18(1) C(73) 5192(3) 6083(2) 432(1) 22(1) C(74) 4642(3) 6499(2) 64(1) 25(1) C(75) 4157(3) 7314(2) 167(1) 21(1) C(76) 4235(3) 7734(2) 635(1) 18(1) C(77) 3633(3) 8611(2) 730(1) 22(1) C(78) 5921(3) 8467(2) 1500(1) 23(1) C(79) 7122(3) 8140(2) 1631(1) 27(1) C(81) 1642(3) 7781(2) 760(1) 19(1) C(82) 2305(3) 8485(2) 579(1) 20(1) C(83) 1782(3) 8953(2) 197(1) 21(1) C(84) 736(3) 8530(2) -43(1) 21(1) C(85) 196(3) 7736(2) 123(1) 24(1) C(86) 589(3) 7383(2) 537(1) 23(1) C(87) 4(3) 6529(2) 713(1) 25(1) C(88) 1996(3) 7937(2) 1618(1) 27(1) C(89) 788(3) 7830(2) 1852(1) 32(1) C(510) -1660(6) 3929(4) 2115(2) 183(3) C(610) 3488(3) 6454(2) 2873(1) 57(1) C(611) 6123(3) 2663(2) 1172(1) 25(1) C(612) 5682(3) 1805(2) 1222(1) 23(1) C(613) 6381(3) 1025(2) 1045(1) 35(1) C(614) 4528(3) 1664(2) 1439(1) 24(1)

478 Appendix

C(615) 4120(3) 810(2) 1580(1) 31(1) C(616) 3065(3) 670(2) 1826(1) 36(1) C(617) 2386(3) 1394(2) 1949(1) 35(1) C(618) 2754(3) 2237(2) 1809(1) 27(1) C(619) 3810(3) 2403(2) 1546(1) 22(1) C(710) 7190(3) 7817(2) 2142(1) 33(1) C(810) 782(3) 8394(3) 2338(1) 60(1) C(811) 261(3) 8923(2) -460(1) 27(1) C(812) 699(3) 9691(2) -625(1) 25(1) C(813) 150(3) 10066(2) -1068(1) 31(1) C(814) 1681(3) 10194(2) -356(1) 23(1) C(815) 2077(3) 11070(2) -481(1) 26(1) C(816) 2917(3) 11597(2) -202(1) 26(1) C(817) 3346(3) 11274(2) 224(1) 28(1) C(818) 2986(3) 10425(2) 353(1) 23(1) C(819) 2191(3) 9844(2) 59(1) 19(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C58H60O4. ______________________________________________________________________ O(1)-C(11) 1.393(3) O(1)-C(18) 1.428(3) O(2)-C(21) 1.390(3) O(2)-C(28) 1.436(3) O(3)-C(31) 1.382(3) O(3)-C(38) 1.437(3) O(4)-C(41) 1.387(3) O(4)-C(48) 1.432(3) C(11)-C(16) 1.381(4) C(11)-C(12) 1.396(4) C(12)-C(13) 1.392(4) C(12)-C(47) 1.514(4) C(13)-C(14) 1.377(4) C(14)-C(15) 1.380(4) C(15)-C(16) 1.389(4) C(16)-C(17) 1.517(4) C(17)-C(22) 1.502(4) C(18)-C(19) 1.519(4) C(19)-C(110) 1.516(4) C(21)-C(26) 1.377(4) C(21)-C(22) 1.411(4) C(22)-C(23) 1.369(4) C(23)-C(24) 1.398(4) C(24)-C(25) 1.428(4) C(24)-C(211) 1.440(4) C(25)-C(26) 1.416(4) C(25)-C(219) 1.458(4) C(26)-C(27) 1.531(4) C(27)-C(32) 1.530(4) C(28)-C(29) 1.515(4) C(29)-C(210) 1.525(4) C(31)-C(32) 1.390(4) C(31)-C(36) 1.409(4) C(32)-C(33) 1.384(4)


C(33)-C(34) 1.380(4) C(34)-C(35) 1.386(4) C(35)-C(36) 1.385(4) C(36)-C(37) 1.523(4) C(37)-C(42) 1.509(4) C(38)-C(39) 1.487(4) C(39)-C(310) 1.551(4) C(41)-C(46) 1.382(4) C(41)-C(42) 1.407(4) C(42)-C(43) 1.365(4) C(43)-C(44) 1.405(4) C(44)-C(45) 1.414(4) C(44)-C(411) 1.428(4) C(45)-C(46) 1.426(4) C(45)-C(419) 1.458(4) C(46)-C(47) 1.543(4) C(48)-C(49) 1.503(4) C(49)-C(410) 1.531(4) C(211)-C(212) 1.345(4) C(212)-C(214) 1.444(4) C(212)-C(213) 1.515(4) C(214)-C(215) 1.412(4) C(214)-C(219) 1.422(4) C(215)-C(216) 1.367(4) C(216)-C(217) 1.382(4) C(217)-C(218) 1.367(4) C(218)-C(219) 1.397(4) C(411)-C(412) 1.337(4) C(412)-C(414) 1.441(4) C(412)-C(413) 1.513(4) C(414)-C(415) 1.419(4) C(414)-C(419) 1.427(4) C(415)-C(416) 1.362(4) C(416)-C(417) 1.394(4) C(417)-C(418) 1.369(4) C(418)-C(419) 1.420(4) O(5)-C(51) 1.392(3) O(5)-C(58) 1.412(4) O(6)-C(61) 1.378(3) O(6)-C(68) 1.432(3) O(7)-C(71) 1.393(3) O(7)-C(78) 1.453(3) O(8)-C(81) 1.385(3) O(8)-C(88) 1.448(3) C(51)-C(52) 1.390(4) C(51)-C(56) 1.393(4) C(52)-C(53) 1.377(4) C(52)-C(87) 1.524(4) C(53)-C(54) 1.379(4) C(54)-C(55) 1.380(4) C(55)-C(56) 1.392(4) C(56)-C(57) 1.510(4) C(57)-C(62) 1.531(4) C(58)-C(59) 1.507(5) C(59)-C(510) 1.503(6) C(61)-C(62) 1.397(4) C(61)-C(66) 1.406(4) C(62)-C(63) 1.412(4) C(63)-C(64) 1.416(4) C(63)-C(619) 1.455(4) C(64)-C(65) 1.412(4)

480 Appendix

C(64)-C(611) 1.424(4) C(65)-C(66) 1.361(4) C(66)-C(67) 1.510(4) C(67)-C(72) 1.522(4) C(68)-C(69) 1.505(4) C(69)-C(610) 1.536(4) C(71)-C(76) 1.378(4) C(71)-C(72) 1.414(4) C(72)-C(73) 1.382(4) C(73)-C(74) 1.383(4) C(74)-C(75) 1.380(4) C(75)-C(76) 1.393(4) C(76)-C(77) 1.524(4) C(77)-C(82) 1.534(4) C(78)-C(79) 1.510(4) C(79)-C(710) 1.518(4) C(81)-C(82) 1.370(4) C(81)-C(86) 1.399(4) C(82)-C(83) 1.440(4) C(83)-C(84) 1.425(4) C(83)-C(819) 1.456(4) C(84)-C(85) 1.401(4) C(84)-C(811) 1.435(4) C(85)-C(86) 1.367(4) C(86)-C(87) 1.506(4) C(88)-C(89) 1.507(4) C(89)-C(810) 1.528(4) C(611)-C(612) 1.358(4) C(612)-C(614) 1.437(4) C(612)-C(613) 1.507(4) C(614)-C(615) 1.407(4) C(614)-C(619) 1.427(4) C(615)-C(616) 1.377(4) C(616)-C(617) 1.390(4) C(617)-C(618) 1.380(4) C(618)-C(619) 1.408(4) C(811)-C(812) 1.328(4) C(812)-C(814) 1.455(4) C(812)-C(813) 1.514(4) C(814)-C(819) 1.416(4) C(814)-C(815) 1.418(4) C(815)-C(816) 1.375(4) C(816)-C(817) 1.390(4) C(817)-C(818) 1.376(4) C(818)-C(819) 1.407(4) C(11)-O(1)-C(18) 112.6(2) C(21)-O(2)-C(28) 113.9(2) C(31)-O(3)-C(38) 110.8(2) C(41)-O(4)-C(48) 115.4(2) C(16)-C(11)-O(1) 119.4(3) C(16)-C(11)-C(12) 122.3(3) O(1)-C(11)-C(12) 118.2(3) C(13)-C(12)-C(11) 117.8(3) C(13)-C(12)-C(47) 119.8(3) C(11)-C(12)-C(47) 122.3(3) C(14)-C(13)-C(12) 120.4(3) C(13)-C(14)-C(15) 120.7(3) C(14)-C(15)-C(16) 120.4(3) C(11)-C(16)-C(15) 118.3(3)


C(11)-C(16)-C(17) 121.8(3) C(15)-C(16)-C(17) 119.9(3) C(22)-C(17)-C(16) 112.4(3) O(1)-C(18)-C(19) 108.2(3) C(110)-C(19)-C(18) 112.2(3) C(26)-C(21)-O(2) 119.9(3) C(26)-C(21)-C(22) 123.2(3) O(2)-C(21)-C(22) 116.7(3) C(23)-C(22)-C(21) 117.2(3) C(23)-C(22)-C(17) 122.4(3) C(21)-C(22)-C(17) 120.0(3) C(22)-C(23)-C(24) 121.7(3) C(23)-C(24)-C(25) 120.0(3) C(23)-C(24)-C(211) 120.8(3) C(25)-C(24)-C(211) 119.2(3) C(26)-C(25)-C(24) 117.8(3) C(26)-C(25)-C(219) 124.9(3) C(24)-C(25)-C(219) 117.1(3) C(21)-C(26)-C(25) 118.3(3) C(21)-C(26)-C(27) 117.0(3) C(25)-C(26)-C(27) 123.7(3) C(32)-C(27)-C(26) 110.0(2) O(2)-C(28)-C(29) 112.5(3) C(28)-C(29)-C(210) 110.4(3) O(3)-C(31)-C(32) 119.7(3) O(3)-C(31)-C(36) 119.0(3) C(32)-C(31)-C(36) 121.2(3) C(33)-C(32)-C(31) 118.9(3) C(33)-C(32)-C(27) 119.0(3) C(31)-C(32)-C(27) 122.1(3) C(34)-C(33)-C(32) 120.6(3) C(33)-C(34)-C(35) 120.3(3) C(34)-C(35)-C(36) 120.7(3) C(35)-C(36)-C(31) 118.2(3) C(35)-C(36)-C(37) 120.3(3) C(31)-C(36)-C(37) 121.5(3) C(42)-C(37)-C(36) 112.3(2) O(3)-C(38)-C(39) 108.9(2) C(38)-C(39)-C(310) 110.5(3) C(46)-C(41)-O(4) 120.0(3) C(46)-C(41)-C(42) 123.3(3) O(4)-C(41)-C(42) 116.3(3) C(43)-C(42)-C(41) 117.0(3) C(43)-C(42)-C(37) 122.8(3) C(41)-C(42)-C(37) 120.0(3) C(42)-C(43)-C(44) 122.6(3) C(43)-C(44)-C(45) 119.0(3) C(43)-C(44)-C(411) 120.8(3) C(45)-C(44)-C(411) 120.1(3) C(44)-C(45)-C(46) 118.8(3) C(44)-C(45)-C(419) 117.1(3) C(46)-C(45)-C(419) 124.1(3) C(41)-C(46)-C(45) 117.5(3) C(41)-C(46)-C(47) 118.4(3) C(45)-C(46)-C(47) 123.0(3) C(12)-C(47)-C(46) 110.8(2) O(4)-C(48)-C(49) 112.8(2) C(48)-C(49)-C(410) 110.9(3) C(212)-C(211)-C(24) 123.4(3) C(211)-C(212)-C(214) 119.0(3) C(211)-C(212)-C(213) 120.1(3)

482 Appendix

C(214)-C(212)-C(213) 120.7(3) C(215)-C(214)-C(219) 118.8(3) C(215)-C(214)-C(212) 121.2(3) C(219)-C(214)-C(212) 119.9(3) C(216)-C(215)-C(214) 122.1(3) C(215)-C(216)-C(217) 118.6(3) C(218)-C(217)-C(216) 120.7(3) C(217)-C(218)-C(219) 122.6(3) C(218)-C(219)-C(214) 116.7(3) C(218)-C(219)-C(25) 122.6(3) C(214)-C(219)-C(25) 120.3(3) C(412)-C(411)-C(44) 123.1(3) C(411)-C(412)-C(414) 118.6(3) C(411)-C(412)-C(413) 121.4(3) C(414)-C(412)-C(413) 120.1(3) C(415)-C(414)-C(419) 118.4(3) C(415)-C(414)-C(412) 121.3(3) C(419)-C(414)-C(412) 120.3(3) C(416)-C(415)-C(414) 121.6(3) C(415)-C(416)-C(417) 120.3(3) C(418)-C(417)-C(416) 119.7(3) C(417)-C(418)-C(419) 122.1(3) C(418)-C(419)-C(414) 117.5(3) C(418)-C(419)-C(45) 122.6(3) C(414)-C(419)-C(45) 119.5(3) C(51)-O(5)-C(58) 113.5(2) C(61)-O(6)-C(68) 115.2(2) C(71)-O(7)-C(78) 112.8(2) C(81)-O(8)-C(88) 114.1(2) C(52)-C(51)-O(5) 119.9(3) C(52)-C(51)-C(56) 121.7(3) O(5)-C(51)-C(56) 118.2(3) C(53)-C(52)-C(51) 118.2(3) C(53)-C(52)-C(87) 120.4(3) C(51)-C(52)-C(87) 121.4(3) C(52)-C(53)-C(54) 121.4(3) C(55)-C(54)-C(53) 119.8(3) C(54)-C(55)-C(56) 120.7(3) C(55)-C(56)-C(51) 118.1(3) C(55)-C(56)-C(57) 120.0(3) C(51)-C(56)-C(57) 121.9(3) C(56)-C(57)-C(62) 111.4(3) O(5)-C(58)-C(59) 109.0(3) C(510)-C(59)-C(58) 111.8(4) O(6)-C(61)-C(62) 120.5(3) O(6)-C(61)-C(66) 117.2(3) C(62)-C(61)-C(66) 122.1(3) C(61)-C(62)-C(63) 118.4(3) C(61)-C(62)-C(57) 117.2(3) C(63)-C(62)-C(57) 123.4(3) C(64)-C(63)-C(62) 118.7(3) C(64)-C(63)-C(619) 116.9(3) C(62)-C(63)-C(619) 124.3(3) C(65)-C(64)-C(63) 118.9(3) C(65)-C(64)-C(611) 120.9(3) C(63)-C(64)-C(611) 120.0(3) C(66)-C(65)-C(64) 122.5(3) C(65)-C(66)-C(61) 117.6(3) C(65)-C(66)-C(67) 123.1(3) C(61)-C(66)-C(67) 119.1(3) C(66)-C(67)-C(72) 114.0(2)


O(6)-C(68)-C(69) 112.7(2) C(68)-C(69)-C(610) 111.9(3) C(76)-C(71)-O(7) 120.5(3) C(76)-C(71)-C(72) 121.1(3) O(7)-C(71)-C(72) 118.4(3) C(73)-C(72)-C(71) 118.3(3) C(73)-C(72)-C(67) 119.5(3) C(71)-C(72)-C(67) 122.2(3) C(74)-C(73)-C(72) 120.9(3) C(73)-C(74)-C(75) 119.8(3) C(74)-C(75)-C(76) 120.9(3) C(71)-C(76)-C(75) 118.8(3) C(71)-C(76)-C(77) 123.0(3) C(75)-C(76)-C(77) 118.2(3) C(76)-C(77)-C(82) 110.4(2) O(7)-C(78)-C(79) 112.7(2) C(78)-C(79)-C(710) 113.8(3) C(82)-C(81)-O(8) 119.4(3) C(82)-C(81)-C(86) 123.5(3) O(8)-C(81)-C(86) 116.9(3) C(81)-C(82)-C(83) 118.3(3) C(81)-C(82)-C(77) 117.1(3) C(83)-C(82)-C(77) 123.6(3) C(84)-C(83)-C(82) 117.1(3) C(84)-C(83)-C(819) 117.5(3) C(82)-C(83)-C(819) 125.2(3) C(85)-C(84)-C(83) 120.1(3) C(85)-C(84)-C(811) 120.9(3) C(83)-C(84)-C(811) 119.0(3) C(86)-C(85)-C(84) 121.8(3) C(85)-C(86)-C(81) 117.5(3) C(85)-C(86)-C(87) 121.4(3) C(81)-C(86)-C(87) 120.6(3) C(86)-C(87)-C(52) 111.8(3) O(8)-C(88)-C(89) 112.6(2) C(88)-C(89)-C(810) 110.5(3) C(612)-C(611)-C(64) 122.9(3) C(611)-C(612)-C(614) 118.4(3) C(611)-C(612)-C(613) 120.5(3) C(614)-C(612)-C(613) 121.1(3) C(615)-C(614)-C(619) 118.7(3) C(615)-C(614)-C(612) 120.9(3) C(619)-C(614)-C(612) 120.3(3) C(616)-C(615)-C(614) 122.1(3) C(615)-C(616)-C(617) 119.4(3) C(618)-C(617)-C(616) 119.8(3) C(617)-C(618)-C(619) 122.5(3) C(618)-C(619)-C(614) 117.4(3) C(618)-C(619)-C(63) 122.7(3) C(614)-C(619)-C(63) 119.7(3) C(812)-C(811)-C(84) 124.0(3) C(811)-C(812)-C(814) 118.5(3) C(811)-C(812)-C(813) 121.2(3) C(814)-C(812)-C(813) 120.2(3) C(819)-C(814)-C(815) 119.1(3) C(819)-C(814)-C(812) 120.2(3) C(815)-C(814)-C(812) 120.5(3) C(816)-C(815)-C(814) 121.8(3) C(815)-C(816)-C(817) 118.7(3) C(818)-C(817)-C(816) 120.8(3)

484 Appendix

C(817)-C(818)-C(819) 122.0(3) C(818)-C(819)-C(814) 117.4(3) C(818)-C(819)-C(83) 122.5(3) C(814)-C(819)-C(83) 119.8(3) ______________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C58H60O4. The anisotropic displacement factor exponent takes the form: -2 pi2 [h2 a*2 U11 + ... + 2 h k a* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(1) 17(1) 33(2) 23(1) -1(1) -1(1) 1(1) O(2) 25(1) 21(1) 22(1) -4(1) 3(1) 0(1) O(3) 24(1) 22(1) 20(1) 0(1) 1(1) -4(1) O(4) 27(1) 23(1) 22(1) -2(1) -3(1) 1(1) C(11) 15(2) 32(2) 16(2) 6(2) -3(2) -6(2) C(12) 20(2) 22(2) 23(2) 0(2) 1(2) -3(2) C(13) 22(2) 25(2) 25(2) 5(2) 1(2) 0(2) C(14) 26(2) 33(2) 21(2) 5(2) -3(2) -3(2) C(15) 27(2) 34(2) 21(2) -4(2) 2(2) 0(2) C(16) 18(2) 17(2) 22(2) -1(2) 3(2) -4(2) C(17) 17(2) 34(2) 29(2) -5(2) -1(2) 0(2) C(18) 23(2) 54(3) 32(2) -6(2) 0(2) -12(2) C(19) 23(2) 70(3) 31(2) -13(2) -4(2) -1(2) C(21) 19(2) 26(2) 20(2) -4(2) -1(2) 6(2) C(22) 10(2) 25(2) 31(2) -4(2) -5(2) 2(2) C(23) 15(2) 30(2) 29(2) 0(2) 2(2) -4(2) C(24) 20(2) 27(2) 27(2) -3(2) -1(2) 12(2) C(25) 14(2) 25(2) 20(2) -3(2) -3(2) 1(2) C(26) 16(2) 22(2) 24(2) -1(2) -2(2) -1(2) C(27) 25(2) 15(2) 26(2) -4(2) -5(2) -2(2) C(28) 31(2) 28(2) 23(2) -3(2) -2(2) 5(2) C(29) 29(2) 42(3) 29(2) -12(2) -7(2) 8(2) C(31) 15(2) 24(2) 14(2) 1(2) -3(2) -6(2) C(32) 17(2) 19(2) 20(2) -1(2) -1(2) -1(2) C(33) 25(2) 18(2) 23(2) -7(2) 2(2) -1(2) C(34) 27(2) 27(2) 18(2) 4(2) 0(2) -2(2) C(35) 20(2) 16(2) 26(2) -2(2) -5(2) 3(2)


C(36) 6(2) 20(2) 25(2) -6(2) -1(1) -2(2) C(37) 20(2) 24(2) 20(2) -3(2) 1(2) -1(2) C(38) 36(2) 24(2) 22(2) -3(2) 1(2) -2(2) C(39) 72(3) 35(3) 28(2) 2(2) 5(2) -9(2) C(41) 24(2) 16(2) 19(2) 1(2) -1(2) 9(2) C(42) 22(2) 24(2) 15(2) -4(2) 5(2) 1(2) C(43) 17(2) 24(2) 21(2) -3(2) 1(2) 2(2) C(44) 26(2) 22(2) 14(2) -4(2) 2(2) 4(2) C(45) 28(2) 19(2) 12(2) -1(2) 1(2) 1(2) C(46) 20(2) 22(2) 18(2) -2(2) -3(2) -5(2) C(47) 24(2) 20(2) 25(2) 1(2) -1(2) -4(2) C(48) 26(2) 25(2) 28(2) -1(2) -7(2) 4(2) C(49) 42(2) 29(2) 25(2) -4(2) 1(2) -1(2) C(110) 36(2) 55(3) 37(2) -9(2) -7(2) 4(2) C(210) 53(3) 73(3) 33(2) 2(2) -11(2) 22(2) C(211) 21(2) 41(3) 22(2) -3(2) 4(2) 10(2) C(212) 30(2) 33(2) 24(2) -10(2) -5(2) 17(2) C(213) 34(2) 53(3) 29(2) -12(2) 3(2) 10(2) C(214) 17(2) 30(2) 26(2) -5(2) -6(2) 9(2) C(215) 30(2) 35(2) 26(2) -15(2) -6(2) 11(2) C(216) 28(2) 33(2) 32(2) -12(2) -7(2) 7(2) C(217) 26(2) 32(2) 33(2) -7(2) -4(2) 2(2) C(218) 26(2) 26(2) 22(2) -11(2) -1(2) 5(2) C(219) 27(2) 25(2) 22(2) -9(2) -5(2) 5(2) C(310) 92(3) 43(3) 41(3) -6(2) 27(2) -30(2) C(410) 60(3) 41(3) 31(2) -2(2) -4(2) 10(2) C(411) 21(2) 27(2) 19(2) -2(2) 2(2) 7(2) C(412) 35(2) 20(2) 21(2) 2(2) 4(2) 10(2) C(413) 40(2) 32(2) 41(2) 3(2) -3(2) 13(2) C(414) 38(2) 19(2) 19(2) 2(2) 2(2) 7(2) C(415) 46(3) 25(2) 35(2) 7(2) 1(2) 10(2) C(416) 53(3) 13(2) 50(3) 0(2) -11(2) -3(2) C(417) 38(2) 33(3) 42(2) 3(2) -8(2) -9(2) C(418) 36(2) 22(2) 28(2) 2(2) -3(2) -4(2) C(419) 31(2) 22(2) 18(2) 4(2) -2(2) 0(2) O(5) 22(1) 31(2) 32(1) -4(1) 2(1) 1(1) O(6) 28(1) 20(1) 28(1) -1(1) 2(1) 3(1) O(7) 28(1) 17(1) 19(1) -3(1) -2(1) 1(1) O(8) 24(1) 22(1) 24(1) -1(1) -5(1) 3(1) C(51) 17(2) 27(2) 24(2) -6(2) 3(2) -4(2) C(52) 14(2) 24(2) 24(2) -2(2) -4(2) 0(2) C(53) 24(2) 24(2) 28(2) 0(2) -6(2) 3(2) C(54) 27(2) 29(2) 26(2) -8(2) -4(2) 1(2) C(55) 19(2) 21(2) 31(2) -4(2) -2(2) -2(2) C(56) 20(2) 8(2) 31(2) -1(2) -4(2) -4(2) C(57) 29(2) 20(2) 37(2) -3(2) 2(2) -1(2) C(58) 37(3) 115(4) 47(3) -13(3) 11(2) -39(3) C(59) 94(4) 168(6) 100(4) -16(4) 75(4) -64(4) C(61) 25(2) 16(2) 19(2) -1(2) -1(2) 5(2) C(62) 18(2) 22(2) 18(2) -1(2) 1(2) -6(2) C(63) 27(2) 12(2) 16(2) 0(2) -3(2) 0(2) C(64) 27(2) 14(2) 16(2) 1(2) -5(2) 4(2) C(65) 20(2) 20(2) 23(2) -2(2) -2(2) 2(2) C(66) 18(2) 12(2) 23(2) 1(2) -7(2) 0(2) C(67) 25(2) 24(2) 20(2) 3(2) -1(2) 4(2) C(68) 31(2) 18(2) 42(2) -3(2) 15(2) 5(2) C(69) 43(2) 25(2) 35(2) -1(2) 1(2) 1(2) C(71) 17(2) 21(2) 12(2) -2(2) 0(2) -5(2) C(72) 16(2) 16(2) 21(2) 0(2) 2(2) -1(2) C(73) 23(2) 12(2) 31(2) -3(2) -1(2) 4(2) C(74) 28(2) 29(2) 18(2) -4(2) 0(2) 3(2)

486 Appendix

C(75) 17(2) 19(2) 27(2) 1(2) -4(2) 1(2) C(76) 16(2) 15(2) 23(2) -1(2) 0(2) -2(2) C(77) 21(2) 20(2) 24(2) 2(2) -2(2) 4(2) C(78) 27(2) 16(2) 26(2) -4(2) 0(2) -1(2) C(79) 27(2) 27(2) 25(2) -2(2) 0(2) -5(2) C(81) 20(2) 15(2) 22(2) -1(2) 0(2) 9(2) C(82) 18(2) 21(2) 21(2) -4(2) -3(2) 5(2) C(83) 20(2) 24(2) 20(2) -5(2) 4(2) 6(2) C(84) 20(2) 23(2) 19(2) -7(2) -2(2) 7(2) C(85) 17(2) 20(2) 33(2) -5(2) -4(2) 0(2) C(86) 19(2) 24(2) 26(2) -1(2) -2(2) 3(2) C(87) 22(2) 20(2) 32(2) -2(2) -6(2) -1(2) C(88) 29(2) 29(2) 21(2) -1(2) -6(2) 1(2) C(89) 26(2) 34(2) 33(2) -2(2) -2(2) -5(2) C(510) 191(7) 222(8) 126(6) 33(6) -63(5) -60(6) C(610) 78(3) 54(3) 36(3) -3(2) 14(2) -3(2) C(611) 25(2) 28(2) 23(2) -5(2) -6(2) 8(2) C(612) 33(2) 16(2) 19(2) -5(2) -8(2) 6(2) C(613) 50(3) 21(2) 35(2) -7(2) -6(2) 11(2) C(614) 34(2) 19(2) 19(2) -5(2) -12(2) 1(2) C(615) 45(3) 17(2) 30(2) 0(2) -2(2) 6(2) C(616) 56(3) 17(2) 35(2) 1(2) -5(2) 2(2) C(617) 39(2) 32(3) 34(2) 8(2) 1(2) -7(2) C(618) 31(2) 22(2) 28(2) 1(2) -1(2) 4(2) C(619) 30(2) 24(2) 12(2) -4(2) -6(2) 1(2) C(710) 33(2) 39(2) 27(2) 1(2) -7(2) -2(2) C(810) 46(3) 86(4) 40(3) -28(2) 13(2) -14(2) C(811) 21(2) 33(2) 25(2) -5(2) -3(2) 2(2) C(812) 25(2) 33(2) 17(2) -1(2) 3(2) 11(2) C(813) 30(2) 38(2) 24(2) -1(2) -2(2) 9(2) C(814) 18(2) 26(2) 24(2) 1(2) 7(2) 9(2) C(815) 30(2) 33(2) 17(2) 9(2) 7(2) 11(2) C(816) 19(2) 31(2) 30(2) 8(2) 4(2) 4(2) C(817) 26(2) 31(2) 27(2) 2(2) 1(2) -1(2) C(818) 22(2) 22(2) 26(2) 6(2) -1(2) 5(2) C(819) 15(2) 23(2) 20(2) -1(2) 2(2) 2(2) ______________________________________________________________________ Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103) for C58H60O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(13) 7873 -1160 4593 29 H(14) 7478 -117 5224 32 H(15) 6173 993 5106 33 H(17A) 4743 1358 3966 32 H(17B) 4170 1239 4491 32 H(18A) 3698 -175 3809 45 H(18B) 4260 -1104 3642 45 H(19A) 2850 -694 3047 51 H(19B) 3669 207 2978 51


H(23) 4491 2456 5093 30 H(27A) 8559 3595 3959 27 H(27B) 8931 3986 4502 27 H(28A) 7418 2378 3184 33 H(28B) 6951 3234 3486 33 H(29A) 4953 2586 3404 41 H(29B) 5424 1733 3098 41 H(33) 8724 2616 5114 27 H(34) 9639 1313 5267 29 H(35) 10482 468 4632 25 H(37A) 10585 1028 3377 26 H(37B) 11611 772 3742 26 H(38A) 11504 2607 3548 33 H(38B) 10868 3506 3714 33 H(39A) 10144 3590 2913 55 H(39B) 10759 2684 2746 55 H(43) 11709 -787 3838 25 H(47A) 6632 -1228 3373 28 H(47B) 6848 -1970 3753 28 H(48A) 7065 696 3046 32 H(48B) 7532 -269 2891 32 H(49A) 9313 393 2608 39 H(49B) 8951 1370 2805 39 H(11A) 5183 -605 2638 65 H(11B) 3965 -957 2356 65 H(11C) 4502 -1535 2765 65 H(21A) 5611 3528 2788 79 H(21B) 4715 2732 2551 79 H(21C) 6130 2692 2486 79 H(211) 4571 3779 5666 33 H(21D) 4547 4938 6247 58 H(21E) 4886 5889 6031 58 H(21F) 5826 5453 6372 58 H(215) 6832 6471 5832 37 H(216) 8218 7232 5365 38 H(217) 8782 6553 4619 37 H(218) 8151 5090 4394 30 H(31A) 12087 4328 3099 91 H(31B) 12016 3959 2538 91 H(31C) 12698 3425 2929 91 H(41A) 7676 288 2039 66 H(41B) 8561 1147 1951 66 H(41C) 7331 1269 2232 66 H(411) 11955 -2375 3904 27 H(41D) 12277 -3837 4062 55 H(41E) 11565 -4559 3689 55 H(41F) 11098 -4389 4234 55 H(415) 9584 -4990 3591 42 H(416) 7736 -5367 3232 47 H(417) 6557 -4246 2975 46 H(418) 7185 -2751 3134 35 H(53) 1144 5937 -77 30 H(54) 2410 4781 -206 34 H(55) 2850 3897 429 29 H(57A) 1895 3334 1282 34 H(57B) 1774 4190 1657 34 H(58A) -575 4232 1330 83 H(58B) -1249 5146 1351 83 H(59A) -75 4702 2211 150 H(59B) -1212 5288 2171 150 H(65) 6750 4382 1122 25

488 Appendix

H(67A) 6735 5971 1238 27 H(67B) 5777 6335 1617 27 H(68A) 2769 5224 2138 37 H(68B) 2348 6180 2004 37 H(69A) 4276 6847 2230 41 H(69B) 4668 5891 2378 41 H(73) 5498 5512 362 26 H(74) 4598 6226 -259 30 H(75) 3765 7591 -86 25 H(77A) 4038 9083 542 26 H(77B) 3706 8809 1081 26 H(78A) 5709 8932 1752 28 H(78B) 5983 8750 1185 28 H(79A) 7748 8634 1600 32 H(79B) 7301 7641 1393 32 H(85) -460 7435 -57 29 H(87A) -772 6385 538 30 H(87B) -161 6620 1065 30 H(88A) 2171 8576 1553 32 H(88B) 2618 7772 1848 32 H(89A) 596 7190 1909 38 H(89B) 166 8022 1630 38 H(51A) -2486 4047 2032 274 H(51B) -1613 3791 2458 274 H(51C) -1416 3417 1907 274 H(61A) 2821 6843 2857 85 H(61B) 4123 6751 3087 85 H(61C) 3204 5884 3003 85 H(611) 6913 2760 1053 30 H(61D) 7138 1251 906 53 H(61E) 5912 653 793 53 H(61F) 6548 663 1319 53 H(615) 4587 314 1504 37 H(616) 2803 84 1911 43 H(617) 1671 1308 2128 42 H(618) 2278 2724 1893 33 H(71A) 7079 8319 2382 50 H(71B) 7975 7585 2195 50 H(71C) 6559 7339 2179 50 H(81A) 1386 8195 2559 89 H(81B) -11 8319 2484 89 H(81C) 966 9028 2281 89 H(811) -408 8614 -628 32 H(81D) -489 9640 -1206 46 H(81E) 768 10163 -1312 46 H(81F) -184 10639 -970 46 H(815) 1753 11298 -764 31 H(816) 3198 12171 -299 32 H(817) 3895 11644 429 34 H(818) 3282 10225 650 27 ______________________________________________________________________

489

3 Abbreviations

Ac Acetyl

anh. anhydrous

aq aqueous

Ar Aryl

Bn Benzyl

Boc tert-Butyloxycarbonyl

bp boiling point

br broad

Bu Butyl

Bz Benzoyl

C Celsius

calcd. calculated

CMD Concerted metalation-deprotonation

conc. concentrated

COSY Correlation spectroscopy

Cy Cyclohexyl

d day

DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene

DCM dichloromethane

DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

DMA N,N-Dimethylacetamide

DMF N,N-dimethylformamide

DMSO Dimethyl sulfoxide

EI Electron-impact ionization

eq equivalents

et al. et alii

Et Ethyl

EtOAc Ethyl acetate

eV electron-volt

FAB Fast atom bombardment

g gram

h hour

HFIP 1,1,1,3,3,3hexafluoro-2-propanol

490 Appendix

HMBC Heteronuclear multiple bond coherence

HMQC Heteronuclear multiple quantum coherence

HMTA Hexamethylenetetramine

HPLC High performance liquid chromatography

HRMS High resolution mass spectrometry

Hz Hertz

i iso

IR Infrared

IUPAC International Union of Pure and Applied Chemistry

J coupling constant

l litre

lit. literature

m meta

M molecular weight

M+ molecular ion

MDA Methyl diazoacetate

Me methyl

min minutes

mNBA m-Nitrobenzyl alcohol

MOM Methoxymethyl

mp melting point

MS mass spectrometry

MTBE Methyl tert-butyl ether

n.d. not determinable

NBS N-bromosuccinimide

NMP 1-Methyl-2-pyrrolidinone

NMR Nuclear magnetic resonance

NOE Nuclear Overhauser effect

NOESY Nuclear Overhauser enhancement spectroscopy

Nu Nucleophile

o ortho

p para

PAH Polycyclic aromatic hadrocarbon

PE Petroleum ether (40/60)

Ph Phenyl

Phen Phenanthrene

PIDA (Diacetoxyiodo)benzene

Abbreviations 491

PIFA [Bis(trifluoroacetoxy)iodo]benzene

PivOH Pivalic acid

ppm parts per million

Pr Propyl

Py Pyridyl

Rf Retention factor

ROESY Rotating frame Overhauser enhancement spectroscopy

rt room temperature

SEAr electrophilic aromatic substitution

SNAr nucleophilic aromatic substitution

tert tertiary

TFA Trifluoroacetic acid

TFE 2,2,2-Trifluoroethanol

THF Tetrahydrofuran

TLC Thin-layer chromatography

TMS Trimethylsilyl

UV ultraviolet

Vis visible

493

4 References

1 For reviews and monographs on calixarenes, see: a) C. D. Gutsche, Calixarenes,

The Royal Society of Chemistry, Cambridge, 1989; b) J. Vicens, V. Böhmer (Ed.),

Calixarenes, a Versatile Class of Macrocyclic Compounds, Kluwer, Dordrecht,

1991; c) V. Böhmer and M. A. McKervey, Chemie in unserer Zeit 1991, 25, 195-

207; d) S. Shinkai, Tetrahedron 1993, 49, 8933-8968; e) V. Böhmer, Angew. Chem.

1995, 107, 785-818; Angew. Chem. Int. Ed. Engl. 1995, 34, 713–746; e) A. Ikeda

and S. Shinkai, Chem. Rev. 1997, 97, 1713-1734; f) C. D. Gutsche, Calixarenes

Revisited, The Royal Society of Chemistry, Cambridge, 1998; g) Z. Asfari, V.

Böhmer, J. Harrowfield, J. Vicens (Eds.), Calixarenes 2001, Kluwer, Dordrecht,

The Netherlands, 2001; h) Y. K. Agrawal, J. P. Pancholi and J. M. Vyas, J. Sci. Ind.

Res. 2009, 68, 745-768. 2 a) J.-M. Lehn, Angew. Chem. 1988, 100, 91-116; Angew. Chem. Int. Ed. Engl.

1988, 27, 89-112; b) J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 1990, 29, 1304-1319;

c) J.-M. Lehn, Pure & Appl. Chem. 1994, 66, 1961-1966; d) H.-J. Schneider,

Angew. Chem. Int. Ed. Engl. 2009, 48, 3924-3977. 3 For examples, see: a) F. Arnaud-Neu, E. M. Collins, M. Deasy, G. Ferguson, S. J.

Harris, B. Kaitner, A. J. Lough, M. A. McKervey, E. Marques, B. L. Ruhl, M. J.

Schwing-Weill and E. M. Seward, J. Am. Chem. Soc. 1989, 111, 8681-8691; b) J.

M. Harrowfield, M. I. Ogden, W. R. Richmond, B. W. Skelton and A. H. White, J.

Chem. Soc., Perkin Trans. 2 1993, 2183-2190; c) A. Casnati, A. Pochini, R.

Ungaro, F. Ugozzoli, F. Arnaud, S. Fanni, M.-J. Schwing, R. J. M. Egberink, F. de

Jong and D. N. Reinhoudt, J. Am. Chem. Soc. 1995, 117, 2767-2777; c) P. Lhoták

and S. Shinkai, J. Phys. Org. Chem. 1997, 10, 273-285; d) J. S. Kim, O. J. Shon, J.

W. Ko, M. H. Cho, I. Y. Yu and J. Vicens, J. Org. Chem. 2000, 65, 2386-2392; e)

A. Arduini, D. Demuru, A. Pochini and A. Secchi, Chem. Commun. 2005, 645-647;

f) O. Danylyuk and K. Suwinska, Chem. Commun. 2009, 5799-5813. 4 For examples see: a) N. Pelizzi, A. Casnati and R. Ungaro, Chem. Commun. 1998,

2607-2608; b) J. Scheerder, M. Fochi, J. F. J. Engbersen and D. N. Reinhoudt, J.

Org. Chem. 1994, 59, 7815-7820; c) A. Casnati, L. Pirondini, N. Pelizzi and R.

Ungaro, Supramol. Chem. 2000, 12, 53-65.

494 Appendix

5 For examples see: a) G. D. Andreetti, J. Chem. Soc., Chem. Commun. 1979, 1005-

1007; b) G. D. Andreetti, A. Pochini and R. Ungaro, J. Chem. Soc., Perkin Trans. 2

1983, 1773-1779; c) L. J. Bauer and C. D. Gutsche, J. Am. Chem. Soc. 1985, 107,

6063-6069; d) A. Arduini, W. M. McGregor, D. Paganuzzi, A. Pochini, A. Secchi,

F. Ugozzoli and R. Ungaro, J. Chem. Soc., Perkin Trans. 2 1996, 839-846; e) A.

Arduini, W. M. McGregor, A. Pochini, A. Secchi, F. Ugozzoli and R. Ungaro, J.

Org. Chem. 1996, 61, 6881-6887. 6 For recent reviews, see: a) W. Sliwa, Croatica Chemica Acta 2002, 75, 131-153; b)

I. Leray and B. Valeur, Eur. J. Inorg. Chem. 2009, 3525-3535; c) W. Sliwa and M.

Deska, ARKIVOC 2008, 1, 87-127; d) E. Shokova and V. Kovalev, Russ. J. Org.

Chem. 2009, 45, 1275-1314; e) S. Siddiqui and P. J. Cragg, Mini-Reviews in

Organic Chemistry 2009, 6, 283-299; f) W. Sliwa and T. Girek, J. Incl. Phenom.

Macrocycl. Chem. 2010, 66, 15-41. 7 For reviews on inherently chiral calixarenes, see: S.-Y. Li, Y.-W. Xu, J.-M. Liu and

C.-Y. Su, Int. J. Mol. Sci. 2011, 12, 429-455. 8 G. McMahon, S. O’Malley and K. Nolan, ARKIVOC 2003, 7, 23-31. 9 V. Souchon, I. Leray and B. Valeur, Chem. Commun. 2006, 4224-4226. 10 a) V. Souchon, S. Maisonneuve, O. David, I. Leray, J. Xie and B. Valeur,

Photochem. Photobiol. Sci. 2008, 7, 1323-1331; b) S. Y. Park, J. H. Yoon, C. S.

Hong, R. Souane, J. S. Kim, S. E. Matthews and J. Vicens, J. Org. Chem. 2008, 73,

8212-8218. 11 X. Zeng, H. Sun, L. Chen, X. Leng, F. Xu, Q. Li, X. He, W. Zhang and Z.-Z.

Zhang, Org. Biomol. Chem. 2003, 1, 1073-1079. 12 S. K. Kim, J. H. Bok, R. A. Bartsch, J. Y. Lee and J. S. Kim, Org. Lett. 2005, 7,

4839-4842. 13 A. Casnati, A. Sartori, L. Pirondini, F. Bonetti, N. Pelizzi, F. Sansone, F. Ugozzoli

and R. Ungaro, Supramol. Chem. 2006, 18, 199 - 218. 14 For a recent review, see: F. Sansone, L. Baldini, A. Casnati and R. Ungaro, New J.

Chem. 2010, 34, 2715-2728. 15 A. Casnati, M. Fabbi, N. Pelizzi, A. Pochini, F. Sansone and R. Ungaro, Bioorg.

Med. Chem. Lett. 1996, 6, 2699-2704.

References 495

16 V. Sidorov, F. W. Kotch, G. Abdrakhmanova, R. Mizani, J. C. Fettinger and J. T.

Davis, J. Am. Chem. Soc. 2002, 124, 2267-2278. 17 R. Cacciapaglia, A. Casnati, L. Mandolini, D. N. Reinhoudt, R. Salvio, A. Sartori

and R. Ungaro, J. Am. Chem. Soc. 2006, 128, 12322-12330. 18 G.-y. Qing, Y.-b. He, F. Wang, H.-j. Qin, C.-g. Hu and X. Yang, Eur. J. Org.

Chem. 2007, 2007, 1768-1778. 19 S. Shirakawa, A. Moriyama and S. Shimizu, Eur. J. Org. Chem. 2008, 2008, 5957-

5964. 20 For a review on calixarenes in metal-based catalysis, see: D. M. Homden and C.

Redshaw, Chem. Rev. 2008, 108, 5086-5130. 21 C. Dieleman, S. Steyer, C. Jeunesse and D. Matt, J. Chem. Soc., Dalton Trans.

2001, 2508-2517. 22 K. Araki, A. Yanagi and S. Shinkai, Tetrahedron 1993, 49, 6763-6772. 23 J. Seitz and G. Maas, Chem. Commun. 2002, 338-339. 24 M. Frank, G. Maas and J. Schatz, Eur. J. Org. Chem. 2004, 2004, 607-613. 25 For reviews, see: a) B. König and M. Hechavarria Fonseca, Eur. J. Inorg. Chem.

2000, 2303-2310; b) W. Sliwa, Chemistry of Heterocyclic Compounds 2004, 40,

683-700; c) S. Kumar, D. Paul and H. Singh, ARKIVOC 2006, 9, 17-25; d) M.-X.

Wang, Chem. Commun. 2008, 4541-4551. 26 M. H. Patel and P. S. Shrivastav, Chem. Commun. 2009, 586-588. 27 For a review on oxacalixarenes, see: W. Maes and W. Dehaen, Chem. Soc. Rev.

2008, 37, 2393-2402. 28 a) N. Sommer and H. A. Staab, Tetrahedron Lett. 1966, 7, 2837-2841; b) P. A.

Lehmann, Tetrahedron 1974, 30, 727-733; c) F. Bottino, S. Foti and S. Pappalardo,

Tetrahedron 1976, 32, 2567-2570. 29 G. W. Smith, Nature 1963, 198, 879. 30 a) H. Kumagai, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato, T. Hori, S. Ueda,

H. Kamiyama and S. Miyano, Tetrahedron Lett. 1997, 38, 3971-3972; b) N. Kon,

N. Iki and S. Miyano, Tetrahedron Lett. 2002, 43, 2231-2234.

496 Appendix

31 For reviews on thiacalixarenes, see: a) P. Lhoták, Eur. J. Org. Chem. 2004, 1675-

1692; b) N. Morohashi, F. Narumi, N. Iki, T. Hattori and S. Miyano, Chem. Rev.

2006, 106, 5291-5316. 32 J. L. Katz, M. B. Feldman and R. R. Conry, Org. Lett. 2004, 7, 91-94. 33 H. Tsue, K. Ishibashi, H. Takahashi and R. Tamura, Org. Lett. 2005, 7, 2165-2168. 34 W. Fukushima, T. Kanbara and T. Yamamoto, Synlett 2005, 19, 2931-2934. 35 Further azacalixarenes: a) A. Ito, Y. Ono and K. Tanaka, J. Org. Chem. 1999, 64,

8236-8241; b) A. Ito, Y. Ono and K. Tanaka, Angew. Chem. Int. Ed. Engl. 2000,

39, 1072-1075. 36 A. Baeyer, Ber. Dtsch. Chem. Ges. 19 1886, 2184. 37 For reviews, see: a) C. Floriani, Chem. Commun. 1996, 1257-1263; b) P. A. Gale, J.

L. Sessler and V. Kral, Chem. Commun. 1998, 1-8; c) P. A. Gale, P. Anzenbacher

Jr and J. L. Sessler, Coord. Chem. Rev. 2001, 222, 57-102; d) W. Sliwa,

Heterocycles 2002, 57, 169-185. 38 P. A. Gale, J. L. Sessler, V. Král and V. Lynch, J. Am. Chem. Soc. 1996, 118, 5140-

5141. 39 V. Král, P. A. Gale, P. Anzenbacher, Jr., K. Jursíková, V. Lynch and J. L. Sessler,

Chem. Commun. 1998, 9-10. 40 R. Pajewski, R. Ostaszewski and J. Jurczak, Org. Prep. Proced. Int. 2000, 32, 394 -

397. 41 a) M.-X. Wang, X.-H. Zhang and Q.-Y. Zheng, Angew. Chem. Int. Ed. Engl. 2004,

43, 838-842; b) M.-X. Wang and H.-B. Yang, J. Am. Chem. Soc. 2004, 126, 15412-

15422. 42 a) C. D. Gutsche, M. Iqbal and D. Stewart, J. Org. Chem. 1986, 51, 742-745; b) B.

Dhawan, S.-I. Chen and C. D. Gutsche, Makromol. Chem. 1987, 188, 921-950. 43 Synthesis of calix[n]arenes: a) C. D. Gutsche and M. Iqbal, Org. Synth. 1990, 68,

234-237; b) C. D. Gutsche, B. Dhawan, M. Leonis and D. Stewart, Org. Synth.

1990, 68, 238-242; c) J. H. Munch and C. D. Gutsche, Org. Synth. 1990, 68, 243-

246. 44 a) A. Ninagawa, H. Matsuda, Makromol. Chem., Rapid Commun. 1982, 3, 65-67;

b) D. R. Stewart, C. D. Gutsche, Organic Preparations and Procedures Int. 1993,

25, 137-139; c) M. A. Markowitz, V. Janout, D. G. Castner and S. L. Regen, J. Am.

References 497

Chem. Soc. 1989, 111, 8192-8200; d) D. R. Stewart and C. D. Gutsche, J. Am.

Chem. Soc. 1999, 121, 4136-4146. 45 a) H. Kämmerer and G. Happel, Makromol. Chem. 1978, 179, 1199-1207; b) H.

Kämmerer and G. Happel, Makromol. Chem. 1980, 181, 2049-2062; c) H.

Kämmerer, G. Happel and B. Mathiasch, Makromol. Chem. 1981, 182, 1685-1694. 46 K. H. No and C. D. Gutsche, J. Org. Chem. 1982, 47, 2713-2719. 47 M. Tashiro, Synthesis 1979, 921-936. 48 a) C. D. Gutsche and J. A. Levine, J. Am. Chem. Soc. 1982, 104, 2652-2653; b) C.

D. Gutsche, J. A. Levine and P. K. Sujeeth, J. Org. Chem. 1985, 50, 5802-5806; c)

C. D. Gutsche and L.-G. Lin, Tetrahedron 1986, 42, 1633-1640. 49 For examples, see: a) J.-D. van Loon, A. Arduini, W. Verboom, R. Ungaro, G. J.

van Hummel, S. Harkema and D. N. Reinhoudt, Tetrahedron Lett. 1989, 30, 2681-

2684, b) A. Dondoni, A. Marra, M.-C. Scherrmann, A. Casnati, F. Sansone and R.

Ungaro, Chem. Eur. J. 1997, 3, 1774-1782; c) E. Pinkhassik, V. Sidorov and I.

Stibor, J. Org. Chem. 1998, 63, 9644-9651. 50 For examples, see: a) K. Iwamoto, A. Yanagi, K. Araki and S. Shinkai, Chem. Lett.

1991, 473-476; b) A. Ikeda, T. Nagasaki, K. Araki and S. Shinkai, Tetrahedron

1992, 48, 1059-1070; c) G. Dyker, M. Mastalerz and K. Merz, Eur. J. Org. Chem.

2003, 4355-4362. 51 G. D. Andreetti, V. Böhmer, J. G. Jordon, M. Tabatabai, F. Ugozzoli, W. Vogt and

A. Wolff, J. Org. Chem. 1993, 58, 4023-4032. 52 a) W. Verboom, P. J. Bodewes, G. van Essen, P. Timmerman, G. J. van Hummel,

S. Harkema and D. N. Reinhoudt, Tetrahedron 1995, 51, 499-512; b) M. Mascal,

R. T. Naven and R. Warmuth, Tetrahedron Lett. 1995, 36, 9361-9364; c) P. A.

Reddy and C. D. Gutsche, J. Org. Chem. 1993, 58, 3245-3251; d) S. A. Herbert and

G. E. Arnott, Org. Lett. 2009, 11, 4986-4989. 53 K. Iwamoto, K. Araki and S. Shinkai, Tetrahedron 1991, 47, 4325-4342. 54 C. D. Gutsche, B. Dhawan, J. A. Levine, K. H. No and L. J. Bauer, Tetrahedron

Lett. 1983, 39, 409-426.

498 Appendix

55 a) C. D. Gutsche, B. Dhawan, K. H. No and R. Muthukrishnan, J. Am. Chem. Soc.

1981, 103, 3782-3792; b) C. D. Gutsche, B. Dhawan, K. H. No and R.

Muthukrishnan, J. Am. Chem. Soc. 1984, 106, 1981. 56 a) C. D. Gutsche and L. J. Bauer, Tetrahedron Letters 1981, 22, 4763-4766; b) C.

D. Gutsche and L. J. Bauer, J. Am. Chem. Soc. 1985, 107, 6052-6059. 57 a) K. Araki, K. Iwamoto, S. Shinkai and T. Matsuda, Chem. Lett. 1989, 1747-1750;

b) K. Iwamoto, K. Araki and S. Shinkai, J. Org. Chem. 1991, 56, 4955-4962. 58 a) K. Iwamoto, K. Fujimoto, T. Matsuda and S. Shinkai, Tetrahedron Lett. 1990,

31, 7169-7172; b) L. C. Groenen, J.-D. van Loon, W. Verboom, S. Harkema, A.

Casnati, R. Ungaro, A. Pochini, F. Ugozzoli and D. N. Reinhoudt, J. Am. Chem.

Soc. 1991, 113, 2385-2392; c) W. Verboom, S. Datta, Z. Asfari, S. Harkema and D.

N. Reinhoudt, J. Org. Chem. 1992, 57, 5394-5398. 59 C. Jaime, J. de Mendoza, P. Prados, P. M. Nieto and C. Sanchez, J. Org. Chem.

1991, 56, 3372-3376. 60 a) M. Conner, V. Janout and S. L. Regen, J. Am. Chem. Soc. 1991, 113, 9670-9671;

b) A. Ikeda, H. Tsuzuki and S. Shinkai, J. Chem. Soc., Perkin Trans. 2 1994, 1994,

2073-2080; c) A. Arduini, M. Fabbi, M. Mantovani, L. Mirone, A. Pochini, A.

Secchi and R. Ungaro, J. Org. Chem. 1995, 60, 1454-1457. 61 a) H. Goldmann, W. Vogt, E. Paulus and V. Böhmer, J. Am. Chem. Soc. 1988, 110,

6811-6817; b) M. Jorgensen and F. C. Krebs, J. Chem. Soc., Perkin Trans. 2 2000,

1929-1934. 62 a) P. D. J. Grootenhuis, P. A. Kollman, L. C. Groenen, D. N. Reinhoudt, G. J. van

Hummel, F. Ugozzoli and G. D. Andreetti, J. Am. Chem. Soc. 1990, 112, 4165-

4176; b) T. Harada, J. M. Rudzinski, E. Osawa and S. Shinkai, Tetrahedron 1993,

49, 5941-5954. 63 For examples, see: a) S. Shinkai, S. Mori, H. Koreishi, T. Tsubaki and O. Manabe,

J. Am. Chem. Soc. 1986, 108, 2409-2416; b) S. Shinkai, T. Arimura, H. Satoh and

O. Manabe, J. Chem. Soc., Chem. Commun. 1987, 1495-1496; c) T. Arimura, H.

Kawabata, T. Matsuda, T. Muramatsu, H. Satoh, K. Fujio, O. Manabe and S.

Shinkai, J. Org. Chem. 1991, 56, 301-306; d) A. Ikeda, T. Nagasaki and S. Shinkai,

J. Phys. Org. Chem. 1992, 5, 699-710; e) A. Sirit and M. Yilmaz, Turk. J. Chem.

2009, 33, 159-200 (Review).

References 499

64 For reviews on inherently chiral calixarenes, see: a) V. Böhmer, D. Kraft and M.

Tabatabai, Journal of Inclusion Phenomena and Molecular Recognition in

Chemistry 1994, 19, 17-39; b) S.-Y. Li, Y.-W. Xu, J.-M. Liu and C.-Y. Su, Int. J.

Mol. Sci. 2011, 12, 429-455. 65 A. Dalla Cort, L. Mandolini, C. Pasquini and L. Schiaffino, New J. Chem. 2004, 28,

1198-1199. 66 A. Szumna, Chem. Soc. Rev. 2010, 39, 4274-4285. 67 Example of asymmetric functionalization of the upper rim: V. Böhmer, F.

Marschollek and L. Zetta, J. Org. Chem. 1987, 52, 3200-3205. 68 Example of asymmetric functionalization of the lower rim: C.-m. Shu and W.-s.

Chung, J. Org. Chem. 1999, 64, 2673-2679. 69 Example of asymmetric functionalization of the lower rim at upper and lower rim:

M. O. Vysotsky, M. A. Tairov, V. V. Piroshenko and V. I. Kalchenko, Tetrahedron

Lett. 1998, 39, 6057-6060. 70 K. Iwamoto, H. Shimizu, K. Araki and S. Shinkai, J. Am. Chem. Soc. 1993, 115,

3997-4006. 71 a) A. Ikeda, M. Yoshimura, P. Lhotak and S. Shinkai, J. Chem. Soc., Perkin Trans.

1 1996, 1945-1950; b) R. Miao, Q.-Y. Zheng, C.-F. Chen and Z.-T. Huang, J. Org.

Chem. 2005, 70, 7662-7671. 72 a) M. Mastalerz, PhD Thesis, Ruhr-Universität Bochum, 2005; b) M. Mastalerz, W.

Hüggenberg and G. Dyker, Eur. J. Org. Chem. 2006, 3977-3987. 73 W. Hüggenberg Master Thesis, Ruhr-Universität Bochum, 2006. 74 M. Mastalerz and G. Dyker, Synlett 2006, 9, 1419-1421. 75 For a review, see: P. E. Georghiu, Z. Li, M. Ashram, S. Chowdhury, S. Mizyed, A.

H. Tran, H. Al-Saraierh and D. O. Miller, Synlett 2005, 6, 879-891. 76 S. Chowdhury and P. E. Georghiu, J. Org. Chem. 2002, 67, 6808-6811. 77 O. G. Barton, B. Neumann, H.-G. Stammler and J. Mattay, Org. Biomol. Chem.

2008, 6, 104-111. 78 W. Hüggenberg, A. Seper, I. M. Oppel and G. Dyker, Eur. J. Org. Chem. 2010,

6786-6797.

500 Appendix

79 a) H. Hopf, H. Greiving, P. G. Jones and P. Bubenitschek, Angew. Chem. Int. Ed.

Engl. 1995, 34, 685-687; b) H. Hopf, H. Greiving, C. Beck, I. Dix, P. G. Jones, J.-

P. Desvergne and H. Bouas-Laurent, Eur. J. Org. Chem. 2005, 567-581. 80 a) S. Kanamathareddy and C. D. Gutsche, J. Org. Chem. 1996, 61, 2511-2516; b)

M. Vézina, J. Gagnon, K. Villeneuve, M. Drouin and P. D. Harvey,

Organometallics 2001, 20, 273-281; c) J. Gagnon, M. Vézina, M. Drouin and P. D.

Harvey, Can. J. Chem. 2001, 79, 1439-1446. 81 L. C. Groenen, B. H. M. Ruel, A. Casnati, P. Timmerman, W. Verboom, S.

Harkema, A. Pochini, R. Ungaro and D. N. Reinhoudt, Tetrahedron Lett. 1991, 32,

2675-2678. 82 S. Shimizu, A. Moriyama, K. Kito and Y. Sasaki, J. Org. Chem. 2003, 68, 2187-

2194. 83 C.-m. Shu, T.-s. Yuan, M.-c. Ku, Z.-c. Ho, W.-c. Liu, F.-s. Tang and L.-G. Lin,

Tetrahedron 1996, 52, 9805-9818. 84 G. Hennrich, M. T. Murillo, P. Prados, H. Al-Saraierh, A. El-Dali, D. W.

Thompson, J. Collins, P. E. Georghiou, A. Teshome, I. Asselberghs and K. Clays,

Chem. Eur. J. 2007, 13, 7753-7761. 85 M. Larsen and M. Jørgensen, J. Org. Chem. 1996, 61, 6651-6655. 86 A. Sartori, A. Casnati, L. Mandolini, F. Sansone, D. N. Reinhoudt and R. Ungaro,

Tetrahedron 2003, 59, 5539-5544. 87 M. Larsen, F. C. Krebs, M. Jørgensen and N. Harrit, J. Org. Chem. 1998, 63, 4420-

4424. 88 A. M. Sanseverino and M. C. S. de Mattos, J. Braz. Chem. Soc. 2001, 12, 685-687. 89 I. R. Robertson and J. T. Sharp, Tetrahedron 1984, 40, 3095-3112. 90 E. E. Schweizer and A. T. Wehman, J. Chem. Soc. C 1971, 343-346. 91 a) N. Miyaura and A. Suzuki, Chem. Rev. 1995, 95, 2457-2483; b) A. Suzuki,

Journal of Organometallic Chemistry 1999, 576, 147-168; c) H. Gröger, J. Prakt.

Chem. 2000, 342, 334-339; d) A. Suzuki, Chem. Commun. 2005, 4759-4763. 92 a) J. K. Stille, Angew. Chem. Int. Ed. Engl. 1986, 25, 508-524; b) M. A. J. Duncton

and G. Pattenden, J. Chem. Soc., Perkin Trans. 1 1999, 1235-1246. 93 a) E. Negishi, A. O. King and N. Okukado, J. Org. Chem. 1977, 42, 1821-1823; b)

E. Negishi, T. Takahashi and A. O. King, Org. Synth. 1988, Coll. Vol. 8, 430-434.

References 501

94 K. Tamao, K. Sumitani and M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374-4376. 95 For reviews on syntheses of biaryls, see: a) J. Hassan, M. Sévignon, C. Gozzi, E.

Schulz and M. Lemaire, Chem. Rev. 2002, 102, 1359-1470; b) O. Reiser, Chemie in

unserer Zeit 2001, 35, 94-100; c) L. Yin and J. Liebscher, Chem. Rev. 2007, 107,

133-173. 96 B. Liégault, D. Lee, M. P. Huestis, D. R. Stuart and K. Fagnou, J. Org. Chem.

2008, 73, 5022-5028. 97 D. R. Stuart and K. Fagnou, Science 2007, 316, 172-175. 98 For reviews on direct arylations see: a) F. Kakiuchi and N. Chatani, Adv. Synth.

Catal. 2003, 345, 1077-1101; b) L.-C. Campeau and K. Fagnou, Chem. Commun.

2006, 1253-1264; c) L.-C. Campeau, D. R. Stuart and K. Fagnou, Aldrichimica

Acta 2007, 40, 35-41; d) D. Alberico, M. E. Scott and M. Lautens, Chem. Rev.

2007, 107, 174-238. e) G. P. McGlacken and L. M. Bateman, Chem. Soc. Rev.

2009, 38, 2447-2464; f) L. Ackermann, R. Vicente and A. R. Kapdi, Angew. Chem.

2009, 121, 9976-10011; for reviews on direct arylation of heteroaromatic

compounds see: a) T. Satoh and M. Miura, Chem. Lett. 2007, 36, 200-205; b) I. V.

Seregin and V. Gevorgyan, Chem. Soc. Rev. 2007, 36, 1173-1193; c) T. Harschneck

and S. F. Kirsch, Nachrichten aus der Chemie 2010, 58, 544-547 99 L.-C. Campeau, M. Parisien, A. Jean and K. Fagnou, J. Am. Chem. Soc. 2006, 128,

581-590. 100 a) D. Garcia-Cuadrado, A. A. C. Braga, F. Maseras and A. M. Echavarren, J. Am.

Chem. Soc. 2006, 128, 1066-1067; b) D. García-Cuadrado, P. de Mendoza, A. A.

C. Braga, F. Maseras and A. M. Echavarren, J. Am. Chem. Soc. 2007, 129, 6880-

6886; c) M. Lafrance, C. N. Rowley, T. K. Woo and K. Fagnou, J. Am. Chem. Soc.

2006, 128, 8754-8756. 101 S. I. Gorelsky, D. Lapointe and K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848-

10849. 102 B. S. Lane, M. A. Brown and D. Sames, J. Am. Chem. Soc. 2005, 127, 8050-8057. 103 O. Daugulis, A. Lazareva, Org. Lett. 2006, 8, 5211-5213.

502 Appendix

104 a) M. Lafrance and K. Fagnou, J. Am. Chem. Soc. 2006, 128, 16496-16497; b) B.

Liégault, D. Lapointe, L. Caron, A. Vlassova and K. Fagnou, J. Org. Chem. 2009,

74, 1826-1834. 105 J.-P. Leclerc, M. André and K. Fagnou, J. Org. Chem. 2006, 71, 1711-1714. 106 Z. Marcinow, A. Sygula, A. Ellern and P. W. Rabideau, Org. Lett. 2001, 3, 3527-

3529. 107 a) H. A. Reisch, M. S. Bratcher and L. T. Scott, Org. Lett. 2000, 2, 1427-1430; b)

X. H. Cheng, S. Höger and D. Fenske, Org. Lett. 2003, 5, 2587-2589; c) Y.

Avlasevich, S. Müller, P. Erk and K. Müllen, Chem. Eur. J. 2007, 13, 6555-6561;

d) S. Pascual, P. de Mendoza and A. M. Echavarren, Org. Biomol. Chem. 2007, 5,

2727-2734. 108 For reviews see: a) L. J. Gooßen, N. Rodrìguez and K. Gooßen, Angew. Chem. Int.

Ed. Engl. 2008, 47, 3100-3120; b) S. M. Bonesi, M. Fagnoni and A. Albini, Angew.

Chem. Int. Ed. Engl. 2008, 47, 10022-10025. 109 a) L. J. Gooßen, G. Deng and L. M. Levy, Science 2006, 313, 662-664; b) A.

Voutchkova, A. Coplin, N. E. Leadbeater and R. H. Crabtree, Chem. Commun.

2008, 6312-6314; c) C. Wang, I. Piel and F. Glorius, J. Am. Chem. Soc. 2009, 131,

4194-4195. 110 O. G. Barton, PhD Thesis, Universität Bielefeld, 2008. 111 J. N. Moorthy and S. Samanta, J. Org. Chem. 2007, 72, 9786-9789. 112 a) R.-Y. Kuo, C.-C. Wu, F.-R. Chang, J.-L. Yeh, I.-J. Chen, Y.-C. Wu, Bioorg.

Med. Chem. Lett. 2003, 13, 821-823; b) M. Lafrance, N. Blaquière and K. Fagnou,

Chem. Commun. 2004, 2874-2875. 113 M. Carril, R. SanMartin, I. Tellitu and E. Domínguez, Org. Lett. 2006, 8, 1467-

1470. 114 a) G. Dyker, J. Org. Chem. 1993, 58, 234-238; b) J. J. González, N. García, B.

Gómez-Lor and A. M. Echavarren, J. Org. Chem. 1997, 62, 1286-1291. 115 D. E. Ames and A. Opalko, Tetrahedron 1984, 40, 1919-1925. 116 T. Satoh, M. Miura and M. Nomura, Journal of Organometallic Chemistry 2002,

653, 161-166. 117 D. Kuck, A. Schuster, R. A. Krause, J. Tellenbröker, C. P. Exner, M. Penk, H.

Bögge and A. Müller, Tetrahedron 2001, 57, 3587-3613.

References 503

118 V. B. Kumbhar, A. R. Joseph, A. D. Natu, R. S. Kusurkar and M. V. Paradkar, J.

Chem. Res. 2007, 590-593. 119 a) C. D. Gutsche and P. F. Pagoria, J. Org. Chem. 1985, 50, 5795-5802; b) Z.-T.

Huang and G.-Q. Wang, Chem. Ber. 1994, 127, 519-523; c) S. Kumar, H. M.

Chawla and R. Varadarajan, Tetrahedron Lett. 2002, 43, 2495-2498. 120 K. H. No and M. Hong, J. Chem. Soc., Chem. Commun. 1990, 572-573. 121 P. Kuhn, D. Sémeril, C. Jeunesse, D. Matt, P. J. Lutz, R. Louis and M. Neuburger,

Dalton Trans. 2006, 3647-3659. 122 A. Yoshida, K. Goto and T. Kawashima, Bull. Chem. Soc. Jpn. 2006, 79, 793-795. 123 a) G. Dyker, M. Mastalerz and I. M. Müller, Eur. J. Org. Chem. 2005, 3801-3812;

b) G. Hennrich, M. T. Murillo, P. Prados, K. Song, I. Asselberghs, K. Clays, A.

Persoons, J. Benet-Buchholz and J. De Mendoza, Chem. Commun. 2005, 2747-

2749. 124 C. Huynh and G. Linstrumelle, Tetrahedron 1988, 44, 6337-6344. 125 a) S. J. Havens and P. M. Hergenrother, J. Org. Chem. 2002, 50, 1763-1765; b) Y.

Kuramochi, A. S. D. Sandanayaka, A. Satake, Y. Araki, K. Ogawa, O. Ito and Y.

Kobuke, Chem. Eur. J. 2009, 15, 2317-2327. 126 I. V. Alabugin, K. Gilmore, S. Patil, M. Manoharan, S. V. Kovalenko, R. J. Clark

and I. Ghiviriga, J. Am. Chem. Soc. 2008, 130, 11535-11545. 127 L.-C. Campeau, P. Thansandote and K. Fagnou, Org. Lett. 2005, 7, 1857-1860. 128 C. E. Miller, J. Chem. Ed. 1965, 42, 254-259. 129 B. Klenke and W. Friedrichsen, J. Chem. Soc., Perkin Trans. 1 1998, 3377-3379. 130 a) S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki, M. Kondo and T.

Okamoto, Chem. Lett. 1987, 2109-2112; b) S. Kajigaeshi, T. Kakinami, M.

Moriwaki, S. Fujisaki, K. Maeno and T. Okamoto, Synthesis 1988, 545-546. 131 A. Dondoni, C. Ghiglione, A. Marra and M. Scoponi, J. Org. Chem. 1998, 63,

9535-9539. 132 R. B. Bedford, S. L. Hazelwood (née Welch), M. E. Limmert, D. A. Albisson, S.

M. Draper, P. N. Scully, S. J. Coles and M. B. Hursthouse, Chem. Eur. J. 2003, 9,

3216-3227. 133 F. Sannicolo, Gazz. Chim. Ital. 1985, 115, 91-95.

504 Appendix

134 T. Yamato, T. Furukawa, S. Saito, K. Tanaka and H. Tsuzuki, New. Chem. Lett.

2002, 26, 1035-1042. 135 S. Nahm and S. M. Weinreb, Tetrahedron Letters 1981, 22, 3815-3818. 136 M. S. Malamas, W. F. Fobare, W. R. Solvibile, F. E. Lovering, J. S. Condon, A. J.

Robichaud, US Patent 7732457. 137 C. Bonini, L. Chiummiento, M. Funicello, M. T. Lopardo, P. Lupattelli, A. Laurita

and A. Cornia, J. Org. Chem. 2008, 73, 4233-4236. 138 H. Plieninger, G. Ege and M. I. Ullah, Chem. Ber. 1963, 96, 1610-1617. 139 Reviews on hypervalent iodine reagents in general: a) P. J. Stang and V. V.

Zhdankin, Chem. Rev. 1996, 96, 1123-1178; b) A. Varvoglis, Tetrahedron 1997,

53, 1179-1255; c) V. V. Zhdankin and P. J. Stang, Chem. Rev. 2002, 102, 2523-

2584; d) T. Wirth, Angew. Chem. Int. Ed. 2005, 44, 3656-3665. 140 Reviews on PIFA: a) G. Pohnert, J. Prakt. Chem. 2000, 342, 731-734; b) X.-Y.

Han, Synlett 2006, 17, 2851-2852. 141 a) M. D. Hossain and T. Kitamura, Bull. Chem. Soc. Jpn. 2006, 79, 142-144; b) T.

K. Page and T. Wirth, Synthesis 2006, 18, 3153-3155. 142 a) J. S. Swenton, K. Carpenter, Y. Chen, M. L. Kerns and G. W. Morrow, J. Org.

Chem. 1993, 58, 3308-3316; b) J. S. Swenton, A. Callinan, Y. Chen, J. J. Rohde,

M. L. Kerns and G. W. Morrow, J. Org. Chem. 1996, 61, 1267-1274. 143 a) A. E. Fleck, J. A. Hobart and G. W. Morrow, Synth. Commun. 1992, 22, 179-

187; b) A. McKillop, L. McLaren and R. J. K. Taylor, J. Chem. Soc., Perkin Trans.

1 1994, 2047-2048; c) O. Karam, J.-C. Jacquesy and M.-P. Jouamnetaud,

Tetrahedron Lett. 1994, 35, 2541-2544. 144 a) K. V. Rama Krishna, K. Sujatha and R. S. Kapil, Tetrahedron Lett. 1990, 31,

1351-1352; b) A. Callinan, Y. Chen, G. W. Morrow and J. S. Swenton,

Tetrahedron Lett. 1990, 31, 4551-4552; c) Y. Kita, T. Takada, M. Gyoten, H.

Tohma, M. H. Zenk and J. Eichhorn, J. Org. Chem. 1996, 61, 5857-5864. 145 T. Takada, M. Arisawa, M. Gyoten, R. Hamada, H. Tohma and Y. Kita, J. Org.

Chem. 1998, 63, 7698-7706. 146 a) Y. Kita, M. Arisawa, M. Gyoten, M. Nakajima, R. Hamada, H. Tohma and T.

Takada, J. Org. Chem. 1998, 63, 6625-6633; b) Y. Kita, M. Egi, T. Takada and H.

Tohma, Synthesis 1999, 5, 885-897.

References 505

147 T. C. Bruice, N. Kharasch and R. J. Winzler, J. Org. Chem. 1953, 18, 83-91. 148 B. Miller and M. P. McLaughlin, J. Org. Chem. 1982, 47, 5204-5207. 149 A. Fischer and G. N. Henderson, Can. J. Chem. 1983, 61, 1045-1052. 150 M. Mastalerz, G. Dyker, U. Flörke, G. Henkel, I. M. Oppel and K. Merz, Eur. J.

Org. Chem. 2006, 4951-4962. 151 Y. Kita, H. Tohma, M. Inagaki, K. Hatanaka and T. Yakura, J. Am. Chem. Soc.

1992, 114, 2175-2180. 152 J. Guillon, J.-M. Leger, C. Dapremont, L. A. Denis, P. Sonnet, S. Massip and C.

Jarry, Supramol. Chem. 2004, 16, 319-329. 153 H. Gilman and B. J. Gaj, J. Org. Chem. 1957, 22, 447-449. 154 R. M. McKinlay and J. L. Atwood, Angew. Chem. Int. Ed. Engl. 2007, 46, 2394-

2397. 155 M. Parisien, D. Valette and K. Fagnou, J. Org. Chem. 2005, 70, 7578-7584. 156 T. Takada, M. Arisawa, M. Gyoten, R. Hamada, H. Tohma and Y. Kita, J. Org.

Chem. 1998, 63, 7698-7706. 157 H. Hamamoto, G. Anilkumar, H. Tohma and Y. Kita, Chem. Eur. J. 2002, 8, 5377-

5383. 158 For reviews on tetrazines see: a) M. J. Hearn and F. Levy, Org. Prep. Proced. Int.

1987, 19, 215-248; b) N. Saracoglu, Tetrahedron 2007, 63, 4199-4236; c) G.

Clavier and P. Audebert, Chem. Rev. 2010, 110, 3299-3314. 159 Y.-H. Gong, P. Audebert, G. Clavier, F. Miomandre, J. Tang, S. Badre, R. Meallet-

Renault and E. Naidus, New J. Chem. 2008, 32, 1235-1242. 160 For a review on the coordination chemistry of tetrazines see: W. Kaim, Coord.

Chem. Rev. 2002, 230, 127-139. 161 a) W.-J. Wang and J.-S. Wang, Mol. Cryst. Liq. Cryst. 2005, 440, 147-152; b) C.-J.

Hsu, S.-W. Tang, J.-S. Wang and W.-J. Wang, Mol. Cryst. Liq. Cryst. 2006, 456,

201-208. 162 a) A. Pinner, Chem. Ber. 1893, 26, 2126-2135; b) A. Pinner, Chem. Ber. 1897, 30,

1871-1890.

506 Appendix

163 a) N. O. Abdel-Rahman, M. A. Kira and M. N. Tolba, Tetrahedron Lett. 1968, 9,

3871-3872; b) P. Audebert, S. d. Sadki, F. Miomandre, G. Clavier, M. C. Vernières,

M. Saouda and P. Hapiot, New. J. Chem. 2004, 28, 387-392. 164 V. M. Tsefrikas, S. Arns, P. M. Merner, C. C. Warford, B. L. Merner, L. T. Scott

and G. J. Bodwell, Org.Lett. 2006, 8, 5195-5198. 165 R. Stolle, J. Prakt. Chem. 1906, 278-300. 166 N. Biedermann and J. Sauer, Tetrahedron Lett. 1994, 35, 7935-7938. 167 O. R. Gautun and P. H. J. Carlsen, Molecules 2001, 6, 969-978. 168 Reviews: a) D. L. Boger, Tetrahedron 1983, 39, 2869-2939; b) D. L. Boger, Chem.

Rev. 1986, 86, 781-793. 169 a) T. Sasaki, K. Kanematsu and T. Hiramatsu, J. Chem. Soc., Perkin Trans. 1 1974,

1213-1215; b) M. J. Haddadin, S. J. Firsan and B. S. Nader, J. Org. Chem. 1979,

44, 629-630; c) S. Satish, A. Mitra and M. V. George, Tetrahedron 1979, 35, 277-

285; d) M. J. Haddadin, B. J. Agha and M. S. Salka, Tetrahedron Lett. 1984, 25,

2577-2580; e) D. R. Soenen, J. M. Zimpleman and D. L. Boger, J. Org. Chem.

2003, 68, 3593-3598; f) E. C. Constable, C. E. Housecroft, M. Neuburger, S.

Reymann and S. Schaffner, Eur. J. Org. Chem. 2008, 1597-1607. 170 R. A. Carboni and R. V. Lindsey, J. Am. Chem. Soc. 1959, 81, 4342-4346. 171 a) W. E. Smith, J. Org. Chem. 1972, 37, 3972-3973; b) L. F. Lindoy, G. V. Meehan

and N. Svenstrup, Synthesis 1998, 1029-1032. 172 S. W. Johnson, S. Connelly, I. A. Wilson and G. W. Kelly, J. Med. Chem. 2008, 51,

6348-6358. 173 E. Van Heyningen, J. Org. Chem. 1961, 26, 3850-3856. 174 a) S. K. Sharma, M. Tandon and J. W. Lown, Eur. J. Org. Chem. 2000, 2095-2103;

b) L. Colombo, C. Gennari, M. Santandrea, E. Narisano and C. Scolastico, J. Chem.

Soc., Perkin Trans. 1 1980, 136-140; c) H. M. Chang, K. Y. Chui, F. W. L. Tan, Y.

Yang, Z. P. Zhong, C. M. Lee, H. L. Sham and H. N. C. Wong, J. Med. Chem.

1991, 34, 1675-1692. 175 A. O. Fitton, A. Rigby and R. J. Hurlock, J. Chem. Soc. (C) 1969, 230-233. 176 M. H. Klingele and S. Brooker, Eur. J. Org. Chem. 2004, 3422-3434. 177 S. Xun, G. LeClair, J. Zhang, X. Chen, J. P. Gao and Z. Y. Wang, Org. Lett. 2006,

1697-1700.

References 507

178 Reviews on oxadiazoles: a) Ž. Jakopin and M. Sollner Dolenc, Curr. Org. Chem.

2008, 12, 850-898; b) H. Rajak, M. D. Kharya and P. Mishra, International Journal

of Pharmaceutical Sciences and Nanotechnology 2009, 2, 21-58; c) R. R. Somani

and P. Y. Shirodkarb, Pharma Chemica 2009, 1, 130-140; d) D. S. Musmade, N. S.

Dighe, S. R. Pattan, M. S. Sanap, P. A. Chavan, M. S. Kedar, S. K. Tambe and P. J.

Shirote, Pharmacologyonline 2010, 108-116. 179 W. T. Flowers, D. R. Taylor, A. E. Yipping and C. N. Wright, J. Chem. Soc. (C)

1971, 1986-1991. 180 G.-W. Rao and W.-X. Hu, Bioorg. Med. Chem. Lett. 2006, 16, 3702-3705. 181 L. I. Robins, R. D. Carpenter, J. C. Fettinger, M. J. Haddadin, D. S. Tinti and M. J.

Kurth, J. Org. Chem. 2006, 71, 2480-2485. 182 L. I. Belen'kii, S. I. Luiksaar, N. D. Chuvylkin and M. M. Krayushkin, Russ. Chem.

Bull. 2000, 49, 886-893. 183 a) K.-P. Hartmann and M. Heuschmann, Tetrahedron 2000, 56, 4213-4218; b) J.

Rebek, S. Gu, S. Biros, US Patent 7579350, 2006. 184 F. Sansone, S. Barboso, A. Casnati, M. Fabbi, A. Pochini, F. Ugozzoli and R.

Ungaro, Eur. J. Org. Chem. 1998, 897-905. 185 a) J.-D. van Loon, A. Arduini, L. Coppi, W. Verboom, A. Pochini, R. Ungaro, S.

Harkema and D. N. Reinhoudt, J. Org. Chem. 1990, 55, 5639-5646; c) R. H.

Vreekamp, W. Verboom and D. N. Reinhoudt, J. Org. Chem. 1996, 61, 4282-4288;

d) M. Segura, B. Bricoli, A. Casnati, E. M. Muoz, F. Sansone, R. Ungaro and C.

Vicent, J. Org. Chem. 2003, 68, 6296-6303. 186 X. H. Sun, W. Li, P. F. Xia, H.-B. Luo, Y. Wei, M. S. Wong, Y.-K. Cheng and S.

Shuang, J. Org. Chem. 2007, 72, 2419-2426. 187 M. Jørgensen, M. Larsen, P. Sommer-Larsen, W. Batsberg Petersen and H. Eggert,

J. Chem. Soc., Perkin Trans. 1 1997, 2851-2855. 188 a) F. L. Scott and P. A. Cashell, J. Chem. Soc. C: Organic 1970, 2674-2677; b) M.

G. Rosenberg and U. H. Brinker, J. Org. Chem. 2003, 68, 4819-4832. 189 S. Trosien, Master Thesis, Ruhr-Universität Bochum, 2011. 190 a) H. E. Gottlieb, V. Kotlyar and A. Nudelmann, J. Org. Chem. 1997, 62, 7512-

7515; b) G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A.

508 Appendix

Nudelman, B. M. Stoltz, J. E. Bercaw and K. I. Goldberg, Organometallics 2010,

29, 2176-2179. 191 G. M. Sheldrick, Acta Cryst. 2008, A64, 112 192 W. L. Armarego and C. Chai. Purifcation of Laboratory Chemicals.

Butterworth Heinemann, 5th edition, 2004. 193 E. E. Sch weizer, A. T. Wehman, J. Chem. Soc. C. 1971, 343-346. 194 K. Auwers, T. Makovits, Chem. Ber. 1908, 45, 2332.

anellated calix[4]arenes - ruhr-universit¤t bochum

Documents