ligand-free coupling of phenols and alcohols with aryl

S-1

Supporting Information

Ligand-free coupling of phenols and alcohols with aryl halides by a

recyclable heterogeneous copper catalyst

Man Wang Bizhen Yuan Tongmei Ma Huanfeng Jiang and Yingwei Li

School of Chemistry and Chemical Engineering South China University of Technology

Guangzhou 510640 China

E-mail liywscuteducn

Table of Contents

General information S-2

Experimental section S-2

Spectra data for the products S-6

1H NMR and 13C NMR spectra of products S-11

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is copy The Royal Society of Chemistry 2012

S-2

1 General Information

Chemicals were purchased from commercial sources All solvents were analytical grade

and distilled prior to use

1H NMR and 13C NMR data were obtained on Bruker Avance III 400 spectrometer using

CDCl3 as solvent and tetrmethylsilane (TMS) as an internal standard Mass spectra were

recorded on a GC-MS spectrometer (Shimadzu GCMS-QP5050A equipped with a 025 mm times

30 m DB-WAX capillary columnin) Powder X-ray diffraction patterns of the samples were

obtained on a Rigaku diffractometer (DMAX-IIIA 3 kW) using Cu K radiation (40 kV 30

mA 01543 nm) XPS data were obtained on Axis Ultra DLD using Mono Al K (14866eV

10mAtimes15KV) as x-ray source Atomic absorption spectroscopy (AAS) was obtained on a

HITACHI Z-2300 instrument

2 Experimental Section

21 Synthesis of MOF-253S1S2

MOF-253 was prepared from hydrothermal reaction of AlCl3middot6H2O (151 mg 0625 mmol)

22rsquo-bipyridine-55rsquo-dicarboxylic acid (153 mg 0625 mmol) and 10 mL

NNrsquo-dimethylformamide (DMF) at 120 C for 24 h The resulting white microcrystalline

powder was then filtered and washed with DMF The solid was washed with methanol via

soxhlet extraction for 24 h and then was collected by filtration and finally dried at 200 C under

vacuum for 12 h

22 Synthesis of MOF-25305CuI

MOF-253CuI was prepared by addition of MOF-253 (1435 mg) to a solution of CuI


S-3

(572 mg 03 mmol) in acetonitrile (5 mL) at 65 degC for 24 h After cooling to room temperature

the resulting solid was soaked in 15 mL of acetonitrile After 24 h the supernatant was decanted

and replaced with fresh acetonitrile The exchanging process was repeated two times after

which the powder was filtered and heated at 150 degC for 12 h under vacuum The molar ratio of

CuI to bpy in MOF-253 was ca 05 as measured by elemental analysis Calcd for

C12H7AlCu05I05N2O5 C 3779 H 185 Al 707 Cu 833 N 734 Found C 3757 H 194

Al 711 Cu 826 N 746

23 General procedure for coupling of aryl iodidesbromides with phenols

Aryl halide (04 mmol) phenol (06 mmol) MOF-25305CuI (008 mmol 20 mol) and

Cs2CO3 (08 mmol) were added to a Schlenk tube under a nitrogen atmosphere at room

temperature The tube was sealed and the mixture was stirred at the desired temperature After

cooling to room temperature the solid catalyst was isolated from the solution by filtration and

washed with ethyl acetate The solution was filtered through a short plug of silica gel and then

washed with copious quantities of ethyl acetate The combined organic phase was concentrated

under vacuum The crude was purified by silica gel chromatography using petroleum etherethyl

acetate as eluent to afford the desired product

24 General procedure for coupling of alcohols with aryl iodides

Aryl iodide (04 mmol) alcohol (2 mmol) MOF-25305CuI (008 mmol 20 mol)

Cs2CO3 (08 mmol) and DMSO (2 mL) were added to a Schlenk tube under a nitrogen

atmosphere at room temperature The tube was sealed and the mixture was stirred at the desired

temperature After cooling to room temperature the solid catalyst was isolated from the solution


S-4

by filtration and washed with ethyl acetate The solution was filtered through a short plug of

silica gel and then washed with copious quantities of ethyl acetate The combined organic phase

was concentrated under vacuum The crude was purified by silica gel chromatography using

petroleum etherethyl acetate as eluent to afford the desired product

25 Recycling of the MOF-25305CuI catalyst

The recyclability of the MOF-25305CuI catalyst was tested for reaction of iodobenzene

with phenol maintaining the same reaction conditions as described above except using the

recovered catalyst The results of three runs are presented in Table S1 Each time the reaction

mixture was allowed to settle down at the end of reaction and the supernatant liquid was

decanted The solid was thoroughly washed with ethyl acetate dried and then reused as catalyst

in the next run

26 Metal leaching test of MOF-25305CuI

To study the leaching of Cu during the reaction after reaction the mixture was hot filtrated

under vacuum The solid was washed with DMSO and the liquid phase was analyzed by AAS

References

(S1) E D Bloch D Britt C Lee C J Doonan F J Uribe-Romo H Furukawa J R Long and

O M Yaghi J Am Chem Soc 2010 132 14382

(S2) H L Liu B L Yin Z Q Gao Y W Li and H F Jiang Chem Commun 2012 48 2033


S-5

Table S1 Reusability of the MOF-25305CuI catalysta

Use 1st 2nd 3rd

Yield ()b 99 96 97

a Reaction conditions iodobenzene (04 mmol) phenol (06 mmol) Cs2CO3 (08 mmol) MOF-25305CuI

(20 mol) DMSO (2 mL) 80 degC 24 h b Determined by GC-MS

4 9 14 19 24 29

2θ (degree)

Inte

nsity (au

)

(a)

(b)

(c)

Figure S1 Powder XRD patterns for MOF-253 (a) fresh MOF-25305CuI (b) and reused

MOF-25305CuI (c)


S-6

3 Spectra Data for the Product

4-methyl-4rsquo-methoxy-diphenylether (3a)

1H NMR (400 MHz CDCl3) δ = 713 (d J = 84 2 H) 698-700

(m 2 H) 689-691(m 4 H) 382 (s 3 H) 234 (s 3 H) 13C NMR (100 MHz CDCl3) δ =

1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)

calcd for C14H14O2(M+) 21426

Diphenylether (3b)

1H NMR (400 MHz CDCl3) δ = 737 (t J = 78 4 H) 713 (t J = 74 2

H) 705 (d J = 84 4 H) 13C NMR (100 MHz CDCl3) δ = 1573 1298 1233 1189

GC-MS (EI) found 170 (M+) calcd for C12H10O(M+) 17021

3-methoxy-diphenylether (3c)

1H NMR (400 MHz CDCl3) δ =731-726 (m 2 H) 702 (t J = 74

1 H) 698-695 (m 2 H) 694 (d J = 88 2 H) 687 (d J = 86 2 H) 378 (s 3 H) 13C NMR

(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557

GC-MS (EI) found 200(M+) calcd for C13H12O2(M+) 20023

4-nitro-diphenylether (3d)

1H NMR (400 MHz CDCl3) δ =819 (d J = 80 2 H) 743 (t J = 80

2 H) 726 (t J = 74 1 H) 709 (d J = 80 2 H) 701 (d J = 80 2 H) 13C NMR (100 MHz

CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7

GC-MS (EI) found 215(M+) calcd for C12H9NO3 (M+) 2152

2-Methyl-diphenylether (3e)

1H NMR (400 MHz CDCl3) δ = 722 (t J =74 2 H) 723 (d J =76 1 H)

715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162

GC-MS (EI) found 184(M+) calcd for C13H12O (M+) 18423

3-Methyl-diphenylether (3f)

1H NMR (400 MHz CDCl3) δ = 733-729(m 2H) 719(t J = 78 Hz

1H) 707 (t J = 74 Hz 1H) 700-698 (m 2H) 691 (d J = 80 Hz 1H) 681(t J = 80Hz 2H)

231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232

1197 1189 1160 215 GC-MS (EI) found 184(M+) calcd for C13H12O (M+) 18423

4-Methyl-diphenylether (3g)

1H NMR (400 MHz CDCl3) δ = 739(t J = 80 Hz 2H) 722 (d J = 80

Hz 2H) 714 (t J = 76 Hz 1H) 707 (d J = 80 Hz 2H) 701 (d J = 80 Hz 2H) 242 (s 3H)

13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208


1-Naphthyl phenylether (3h)

1H NMR (400 MHz CDCl3) δ = 829 (d J =68 1 H) 793 (d J=78

1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8

(d J = 80 2 H) 702 (d J = 78 1 H) 13C NMR (100 MHz CDCl3) δ = 1579 1531 1350

1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027

4-Chloro-diphenylether (3i)

1H NMR (400 MHz CDCl3) δ = 737 (t J = 78 2 H) 731 (d J = 86

2 H) 715 (t J =74 1 H) 703 (d J =86 2 H) 697 (d J =86 2 H) 13C NMR (100 MHz

CDCl3) δ = 1569 1560 1299 1298 1282 1237 1201 1190 GC-MS (EI) found 204

(M+) calcd for C12H9OCl (M+) 20465

4 4rsquo-Dimethyl-diphenylether (3j)

1H NMR (400 MHz CDCl3) δ = 720 (d J = 82 4 H) 698 (d J =

86 4 H) 241 (s 6 H) 13C NMR (100 MHz CDCl3) δ = 1554 1325 1302 1187 207


Methoxybenzene (3k)

1H NMR (400 MHz CDCl3) δ = 750 (t J = 86 2 H) 719-712 (m 3 H)

395 (s 3 H) 13C NMR (100 MHz CDCl3) δ = 1599 1297 1208 1141 551 GC-MS (EI)

found 108(M+) calcd for C7H8O (M+) 10814

anisole (3l)

1H NMR (400 MHz CDCl3) δ = 716 (t J = 84 2H) 679 (t J = 86 3H)

O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)


n-butyl phenyl ether (3m)

1H NMR (400 MHz CDCl3) δ = 729-723 (m 2 H) 694-688 (m 3

H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C

NMR (100 MHz CDCl3) δ = 1592 1294 1205 1145 676 314 193 139 GC-MS (EI)

found 150 (M+) calcd for C10H14O (M+) 15022

n-octyl phenyl ether (3n)

1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293

261 227 141 GC-MS (EI) found 206(M+) calcd for C14H22O (M+) 20632

4-methyl phenetole (3o)

1H NMR (400 MHz CDCl3) δ =708 (d J = 84 2 H) 681 (d J = 86 2

H) 404-399 (m 2 H) 229 (s 3 H) 141 (t J = 80 3 H) 13C NMR (100 MHz CDCl3) δ =

1568 1300 1299 1143 634 205 149 GC-MS (EI) found 136 (M+) calcd for C9H12O

(M+) 13619

4-nitrophenetole (3p)

1H NMR (400 MHz CDCl3) δ = 821-818 (m 2 H) 696-692 (m 2 H)

O

O

O

O

O2N


S-10

413 (m J = 70 2 H) 147 (t J = 70 3 H) 13C NMR (100 MHz CDCl3) δ = 1640 1414

1259 1144 644 146 GC-MS (EI) found 167 (M+) calcd for C8H9NO3 (M+)16706

1-(cyclopentyloxy)benzene (3q)

1H NMR (400 MHz CDCl3) δ =731-727 (m 2 H) 694 (t J = 80 3 H)

429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100

MHz CDCl3) δ = 1578 1294 1205 1161 754 319 238 GC-MS (EI) found 162(M+)

calcd for C11H14O (M+) 16223

1-(Phenoxymethyl)benzene (3r)

1H NMR (400 MHz CDCl3) δ =747 (d J=72 2 H) 741-738 (m 2

H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)


1-(Phenoxyethyl)benzene (3s)

1H NMR (400 MHz CDCl3) δ =726-716 (m 7H) 687-681 (m

3H) 410 (t J =76 2H) 302(t J = 80 2 H) 13C NMR (100 MHz CDCl3) δ = 1578 1372

1284 1280 1275 1255 1197 1135 675 348 GC-MS (EI) found 198 (M+) calcd for

C14H14O (M+) 19826

O

O

O


S-11

4 1H NMR and 13C NMR Spectra of products


S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-2

1 General Information

Chemicals were purchased from commercial sources All solvents were analytical grade

and distilled prior to use

1H NMR and 13C NMR data were obtained on Bruker Avance III 400 spectrometer using

CDCl3 as solvent and tetrmethylsilane (TMS) as an internal standard Mass spectra were

recorded on a GC-MS spectrometer (Shimadzu GCMS-QP5050A equipped with a 025 mm times

30 m DB-WAX capillary columnin) Powder X-ray diffraction patterns of the samples were

obtained on a Rigaku diffractometer (DMAX-IIIA 3 kW) using Cu K radiation (40 kV 30

mA 01543 nm) XPS data were obtained on Axis Ultra DLD using Mono Al K (14866eV

10mAtimes15KV) as x-ray source Atomic absorption spectroscopy (AAS) was obtained on a

HITACHI Z-2300 instrument

2 Experimental Section

21 Synthesis of MOF-253S1S2

MOF-253 was prepared from hydrothermal reaction of AlCl3middot6H2O (151 mg 0625 mmol)

22rsquo-bipyridine-55rsquo-dicarboxylic acid (153 mg 0625 mmol) and 10 mL

NNrsquo-dimethylformamide (DMF) at 120 C for 24 h The resulting white microcrystalline

powder was then filtered and washed with DMF The solid was washed with methanol via

soxhlet extraction for 24 h and then was collected by filtration and finally dried at 200 C under

vacuum for 12 h

22 Synthesis of MOF-25305CuI

MOF-253CuI was prepared by addition of MOF-253 (1435 mg) to a solution of CuI


S-3







Al 711 Cu 826 N 746
















S-4











in the next run




References





S-5


Use 1st 2nd 3rd

Yield ()b 99 96 97



4 9 14 19 24 29

2θ (degree)

Inte

nsity (au

)

(a)

(b)

(c)


MOF-25305CuI (c)


S-6





1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)


Diphenylether (3b)







(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557





CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-3







Al 711 Cu 826 N 746
















S-4











in the next run




References





S-5


Use 1st 2nd 3rd

Yield ()b 99 96 97



4 9 14 19 24 29

2θ (degree)

Inte

nsity (au

)

(a)

(b)

(c)


MOF-25305CuI (c)


S-6





1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)


Diphenylether (3b)







(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557





CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-4











in the next run




References





S-5


Use 1st 2nd 3rd

Yield ()b 99 96 97



4 9 14 19 24 29

2θ (degree)

Inte

nsity (au

)

(a)

(b)

(c)


MOF-25305CuI (c)


S-6





1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)


Diphenylether (3b)







(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557





CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-5


Use 1st 2nd 3rd

Yield ()b 99 96 97



4 9 14 19 24 29

2θ (degree)

Inte

nsity (au

)

(a)

(b)

(c)


MOF-25305CuI (c)


S-6





1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)


Diphenylether (3b)







(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557





CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-6





1562 1557 1508 1320 1301 1204 1178 1148 556 207 GC-MS (EI) found 214(M+)


Diphenylether (3b)







(100 MHz CDCl3) δ = 1586 1559 1502 1297 1225 1209 1176 1149 557





CDCl3) δ = 1634 1547 1427 1303 1259 1254 1205 1171

O

MeO

O

O

MeO

O

O2N


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-7




715 (t J = 76 1 H) 707-700 (m 2 H) 689 (d J = 74 3 H) 223 (s 3 H) 13C NMR (100

MHz CDCl3) δ = 1580 1545 1315 1301 1297 1272 1241 1224 1199 1173 162





231(s 3H) 13C NMR (100 MHz CDCl3) δ = 1575 1573 1400 1298 1295 1242 1232





13C NMR (100 MHz CDCl3) δ = 1579 1548 1329 1303 1297 1228 11921184 208




1 H) 768 (d J = 82 1 H) 761-751 (m 2 H) 747-736 (m 3 H) 718 (d J = 74 1 H) 712

O

O

O

O


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-8


1299 1279 1269 1266 1260 1259 1234 1232 1222 1186 1136 GC-MS (EI) found

220 (M+) calcd for C16H12O (M+) 22027










Methoxybenzene (3k)




anisole (3l)


O

O

O

O

Cl


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-9

389-387 (m 2H) 129 (t J = 80 3H) δ = 1591 1295 1206 1146 633 149 GC-MS (EI)




H) 395 (t J = 86 2 H) 181-171 (m 2 H) 154-144 (m 2 H) 097 (t J = 74 3 H) 13C




1H NMR (400 MHz CDCl3) δ = 729-725 (m 2 H) 694

-688 (m 3 H) 395 (t J = 74 2 H) 181-174 (m 2 H) 147-126 (m 10 H) 089 (t J = 80 3

H) 13C NMR (100 MHz CDCl3) δ =1592 1294 1205 1145 679 319 294 293 293






(M+) 13619



O

O

O

O

O2N


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-10





429-424 (m 1 H) 205-200(m 2 H) 185-182(m 2 H) 154-144 (m 4 H) 13C NMR (100





H) 736 (d J=72 1 H) 732-729 (m 2 H) 701-696 (m 3 H) 508 (s 2 H) 13C NMR (100

MHz CDCl3) δ = 1588 1371 1295 1286 1280 1275 1210 1149 699 GC-MS (EI)






C14H14O (M+) 19826

O

O

O


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-11



S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-12


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-13


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-14


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-15


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-16


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-17


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-18


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-19


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-20


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-21


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-22


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-23


S-24


S-25


S-26


S-27


S-28


S-29


S-24


S-25


S-26


S-27


S-28


S-29


S-25


S-26


S-27


S-28


S-29


S-26


S-27


S-28


S-29


S-27


S-28


S-29


S-28


S-29


S-29


ligand-free coupling of phenols and alcohols with aryl

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