Subject Index

Acetic acids, 159 decarboxylation of, 490

Acetone diphenylamine, 74 Acetoxy methyl sulfide, 408 Acetyl 2-amino disulfide

hydrochloride, 326 Acetylarantoin, 312 Acetyl coenzyme, 175, 310 Acetyl disulfide synthesis, 321 Acetylene(s),

reaction with thiones, 222 sulfenyl halide addition, 513 sulfonyl halide addition, 539 thermal reaction with, 56 thiol addition, 145

electron-sharing participation, 149

electrophilic, 148 nucleophilic, 145 oxidative, 153 radicals, 148

thiolation of, 57 a-Acetylenic acids, 502 Acetylenic sulfonium salts, 519 Acetyl lipoic acid, 179 Acetyl phenyl disulfide, 320 Acetylsulfenyl chloride, 323 Acetyl p-toluenethiosulfonate, 325 Acrolein diethyl acetal, 279 Acrylamide, polymerization, 368 Acrylonitrile, 127, 143, 169,219,

221,540,632 Acyl alkyl disulfide, synthesis, 325 Acyl azides, 590

681

Acyl carrier protein, 174 Acyl chloride, 628 Acyl disulfides, 323, 362

mass spectra, 344 preparation, 329

Acylamide sulfones, 586 N-Acylhaloamides,390 Acylimidazole, 676 Acyloxy sulfides, 407 Acyloxysulfonium salts, 411 a-Acyloxythiacyclohexane,409 N-Acylsulfilimines, preparation, 389 l-Adamantylethylmethylsulfonium

perchlorate, 483 Adenosine diphosphate, 313 Alcohols,

acidities, 122 boiling points, 121 bond angles of, 121 bond dissociation energies, 120 carbon disulfide reaction with,

199 reaction with sulfonate esters,

651,669 sulfate diesters of, 656, 658 sulfate monoesters of, 658, 660

Aldehydes, formation, 49 reaction with sulfinic acids, 538,

632 reaction with sulfonyl carbanions,

551 thiol-catalyzed decarbonylation

of, 126

682

Aliphatic alcohols, sulfate diesters of, 656 sulfate mono esters of, 658 sulfonate esters of, 651

Alkali-atoms, spectra of, 20 Alkali polysulfide, 63 Alkanedithiocarboxylic acids, 161 Alkanes, reactions with, 53, 55 Alkanesulfinates, 318 Alkanesulfonates, 541 Alkanesulfonyl chlorides, 319, 351,

513 Alkanethiols, yields in vulcanization,

78 t-Alkanethiols, 317 Alkeneperthiol, formation, 85 Alkanethiols, 3 17 Alkenyl alkyl poly sulfides, 85, 87,

101 Alkenyl dithiocarbamyl disulfides,

109 Alkoxycarbonylalkyl disulfides,

371 Alkoxysulfonium salts, 420, 497

reactions with strong bases, 502 S-Alkoxysulfonium salts, 421 Alkyl aryl disulfides, 321 Alkyl aryl sulfones,

cleavage of bonds, 575 pyrolysis, 577, 578 rearrangements, 564 reduction, 572, 575, 605

Alkylated aromatic compounds, oxidation, 63

Alkylbenzene, 222 Alkyl chlorsulfite, 629 Alkyl 2,6-dimethylbenzenesulfinate,

640 Alkyl disulfides,

conversion to sulfides, 367 reactions with cyanide ion, 359 unsymmetrical, 337

Alkyl halides, elimination in, 499 reaction with thiourea, 123

Alkyl hydrogen sulfates, 662 Alkyl hydrogen sulfides, 659 Alkyl hydrosulfides, 309 Alkylmercaptans, 208, 209 Alkyl polysulfides, oxidation, 351

Subject Index

Alkyl propenyl sulfides, 279 Alkyl sulfates, 123 Alkyl sulfides,

alkylation, 476 formation, 123 introduction of strain, 289 oxidation, 531, 532 reaction with toluenesulfinic

acid,619,620 solvolysis, 476

Alkyl sulfinate formation, 574 Alkyl sulfonates, 474 Alkyl sulfones,

preparation, 538 reduction, 572

Alkylsulfonyl isocyanates, 593 Alkyl sulfoxides,

chlorination of, 445 halogenation, 444

Alkyl thiols, 324 Alkyl p-toluenesulfonates,

hydrolysis, 641 Alkyl trisulfides, 331 Alkylene dihalides, reaction with

alkali polysulfides, 328 Alkynethiolates, 58 Allenes, thiol addition, 145-154,

236 Allenic sulfonium salts, 508, 510 Allenic system, nucleophile

addition, 509 Allenyldimethylsulfonium bromide,

508 Alliin, 309 Allo-ocimene, 82, 100 Allotropes, 40 Allylic amine oxides, 457 Allylic disulfides, desulfuration of,

95 Allylic radicals, 53, 152 Allylic rearrangement in olefins, 111 Allylic sulfide, 519 Allylic sulfones, pyrolysis, 577 Allylic sulfoxides, 396

racemization, 397, 398 Allylic thiols, 329 Allylic units, coupling, 519 Allyl phenyl sulfide, 282 Allyl 2-pyridyl sulfide, 293 Allyl sulfides, uv absorption, 247

Subject Index

Allylthiomethylphosphonate, 293 Aluminium chloride, CoS bond

fission by, 263 Amines,

reaction with dithiocarboxylic acid, 164

reaction with p-nitrophenyl sulfate, 661

Amine oxides, demethylation, 408 Amino acids, sulfur-containing, 313 Aminoalkyl disulfides, 347 Aminoalkyl thiolsulfonates, 350 p-Aminobenzenesulfinic acid, 388 0-Aminobenzenethiol. 318 Amino-carboxyl zwitter ion, 474 Aminodiaryl sulfones, 543 o-Aminodiphenyl sulfides, 565 (j-Aminoethylmercaptans,

oxidation, 157 2-Amino-8-nitrobenzothiophene,269 4-Aminophenol, sulfonation, 538 p-Aminophenyl p-tolyl sulfoxide,

414 Aminophosphines, 355 Aminothiols, interchange of, 358 p-Aminothiophenol, IS 7 Ammonia,45 Ammonium polysulfide, 58 Aminonitrines, 591 Andersen procedure, 395 Anilides, 544 Aniline(s),

acidities, 267 dipole moments, 268, 269

Antabuse, 315 Anthio anions, 352 Antibiotics, 311 Anticoinc:dent spinsets, 12 Aralkyl hydrosulfides, 307 Arenes, Friedel-Crafts reaction, 243 Arenediazonium salts, 328, 605 Arenedithiocarboxylic acids, 161 Arenesulfenyl chloride, 406, 513 Arenesulfinate esters, synthesis, 318 Arenesulfinate salts, preparation of,

361 Arenesulfinic acid(s), 544

preparation, 605 reaction with aryldisulfide, 617

Arenesulfones, addition to

683

quinones, 634 Arenesulfonyl chlorides, 319, 533,

541 reaction with azobenzenes, 635 reaction with dimethyl sulfoxide,

410 reduction, 319, 604

Arenesulfenyl nitrate, 623 Arenesulfonyl phenazine, 635 p-Arenesulfonylated azobenzenes,

635 Arenethiol, isotopic exchange, 367 Aromatic alcohols,

cyclic sulfonate esters, 669 sulfate diesters, 658 sulfate monoesters of, 660 sulfonate esters of, 653

Aromatic hydrocarbons, 49 Aromatization, 50 Arsenites, 356 Arsines, 356 Aryl alkyl ketones, 58 Aryl alkyl sulfones, 541 Aryl3-chloropropyl sulfones, 555 Aryl cyclohexanones, 520 Aryldimethylsulfonium salt, 492 Aryl disulfides,

bonds, 335 conversion to sulfides, 367 reaction with arenesulfinic acid,

617 reaction with pyridine oxide,

623 unsymmetrical,338

(j-Aryl disulfides, 362 6-Arylethyl compounds, E2 reactions

of,500 Aryl ketones, 60 Aryl methyl sulfide, 494 o-Arylmethylated arenesulfinic acid,

606 N-Arylpiperidine, 576 Aryl sulfates,

hydrolysis, 661 Aryl sulfides,

alkylation, 476 halogenation, 385 oxidation, 531

N-Arylsulfilimines, 459 Arylsulfonamide intermediates, 544

684

Aryl sulfonates, rearrangements, 542 Aryl sulfones, 529

cleavage, 575, 576 elimination, 569 preparation, 533, 536 reduction, 574, 575

Arylsulfonium halides, reversion in, 493

Aryl thioesters, cleavage, 496 Asparagus, 310 Aspergillus niger, 389 Atom,

Bohr radius, 23 electron-releasing conjugation,

147 internal distances, 23 kernel radii, 20 spin-exclusion effects, 22

Atomic core, 5, 18-20,27 chemical implications, 27 electrons, 12 van der Waals-like sizes of, 18,20

Atomic kernel, 12, 18 Atomic models, 22 Atomic sulfur, 39-40 Atomic volume curve, 20 Azabicyclobutanes, 516 Azines, reaction with sulfinic acids,

635 Aziridines, 326, 594

reaction with sulfonium ylides, 516

rings, 166 Azobenzenes, reduced by

dithiophosphoric acid, 168 Azo bisdiphenylmethane, 126 Azobisisobutyronitrile, 83, 215 Azobis-l-phenylethane, 216 Azobis-l-phenylpropane,83 Azobis 2-propane derivatives,

decomposition of, 287 Azo compounds,

reaction of sufinic acids, 635 sulfur containing, decompositions

of, 138 Azodicarbonamide, 318 Azodicarboxylate, 329 Azoxybenzenes, arenesulfonyl

chlorides, reaction with, 635

Subject Index

Bacteria, sulfur in, 3 11 Bathochromic shifts, 337, 340, 485 Benzaldehyde, reaction with

sulfites, 642 syn-Benzaldoximes, 257 Benzene,

reaction with sulfides, 515 reaction with sulfinic acids, 635

Benzenediazonium-2-carbo xy late, 211

Benzenesulfinate, rearrangements, 640

Benzenesulfinic acids, addition to acrylonitrile, 632 dipole moments, 606, 607 oxygen exchange, 641 reaction with azobenzene, 635 reaction with phenylbenzenethio-

sulfinate, 621 uv spectra, 610

Benzenesulfinylacetic acid, 401, 409 Benzenesulfonyl chloride, 445 Benzenethiaacetic acid, 409 Benzenethiyl radicals, 152 Benzhydrol, 223 Benzhydrylmercaptan, 204 Benzocyclobutenes, 581 Benzoimidazole, 165 Benzonitrile, 521 Benzophenone, 203 Benzophenone oxime, 413 Benzophenone phenylhydrazone,

204 Benzoquinone, 83 Benzothiazol-2-yl disulfide, 74 Benzothietes, synthesis, 211 Benzothiophene, 581 Benzothioxane formation, 411 Benzotrichloride, 161 Benzoyl disulfide, 329 Benzoyl peroxide, 365 Benzoylthiol, 625 o-Benzylbenzenesulfinic acid, 567 Benzyl chloride oxidization, 67 S-Benzyl-l-cysteine dioxides, 575 Benzyl-I, 4-dihydronicotinamide,

204 Benzyldimethylselenonium ion, 511 Benzyldimethyl sulfonium groups,

495

Subject Index

Benzyldimethylsulfonium salts, 517 Benzylethylmethylsulfonium

perchlorates, racemization, 491

Benzylic sulfides, 496, 532 Benzylic sulfones, 562

pyrolysis, 577, 578 Benzylic sulfoxides, 397,442 2-Benzylidene-4-phenyl-l, 3-dithiol,

58 Benzyl mercaptan, 126, 129 Benzyl methyl sulfoxide, 401 Benzyl phenyl sulfoxide, 445 Benzyl sulfides, uv absorption, 247 Bicyclohexene, methylmercaptan

added to, 136 cis-Bicyclo (3.3.0) octane, 290 N,N-B is( benzenesulfeny I) toluene­

sulfonamide, 449 Bis (p-bromophenyl) disulfide, 319 Bis ((j-chlor0-{3-alkoxyethyl)sulfox-

ides, 388 Bis-2-chloroethyl sulfide, 511 Bis.fj..chloroethyl sulfide, 256 Bis (cyclopentiadienyl titanium)

pentasulfide, 38 Bis-l, 4-(butylsulfonyl) butane,

577 Bis (2, 6-di-t-butylphenyl) disulfide,

333 Bisdisulfides, 325 1, I-Bis(ethylmercapto)propane,

279 Bis (2-hydroxynaphthyl) sulfide,

565 Bis-2-methylpropyl sulfide,

alkylation, 492 1, 3-Bis(methyIthio )allylIithium,

293 Bis(p-nitrophenyl) disulfide, 335 Bis( 4-nitrophenyI) disulfide,

uv spectra, 339 Bis(2-nitro-4-trifluoromethylphenyl)

sulfoxide, 447 Bis(phenylsulfinyl)methane, 432 Bis( I-propenyl) sulfide, 241 Bis-sulfonium salts, formation, 476 Bis-sulfonyl diazo met hanes, 585 Bis(sulfonyI)-3-haloalkanes, 555 Bis-(sulfonyl) methanes, 529

685

Bis(trichloromethyl) disulfide, 306 Bis( triphenylmethyI) polysulfides,

uv spectra, 340 Bismuth dimethyldithiocarbamate,

74 Blood clotting, 315 Bohr radius, 23 Bond dissociation energies of thiols,

120 Bonds and bonding, 1-32

Ac-S chlorinolysis, 307

antisymmetrization and spin­exclusion, 7

aryl-sulfur, 574 B-O,

energy, 198 bent or banana description, 10,

II C-C, 53

sulfonium group in nucleo­philic additions, 505

C-CI, base catalyzed oxidation, 65

C-H, base catalyzed reactions, 56 cleavage, 500 thermal reactions, 50

chemical orbitals, 9 C-N, energies, 194 C-0,246

cleavage, 654, 655, 656, 657, 666

lengths and angles, 246 C-S, 291,335

carbon disulfide, 189 carbon oxysulfide, 189 cleavage of, 42,260,263,289,

291,305,345,350,385, 574,576

energies, 246, 289 formation, 52 lengths and angles, 246 polarization, 491 stability, 548

C-Si,190 determinantal wave functions, 9 dissociation energies,

sulfides of, 245 thiois, of, 120

686

dithiocarboxylic acid, 163 dithiophosphoric acids, 163 exclusion principle, 2,4,8,9, 12,

19, 21 face-centred, 26, 27 high energy phosphate, 313 hydrogen

sulfides, in, 249 thiols, in, 121

lengths and angles, 26 ethylene sulfates, of, 667 sulfides, of, 246 thiols and alcohols, in, 121

0-H,246 0-0,287 d-orbital problem, I p1T-p1T, 56 Pauli mechanics, 3, 4 representation-independent

terms, 4 S-CI,

cleavage, 242, 244 S-H, 125 S-N, cleavage, 449 S-O, 528, 607, 608

basicity, 426 cleavage, 399, 403, 651,653,

655,660,666 -SO-, molecular interactions,

373 -SS-,

bimolecular radical displace-ment,366

biological relationships, 315 disulfides,335 electronic effects through,

340 energies, 336 length, 333 molecular interactions, 373 neighboring group attack,

369 nucleophilic attack on, 360 polarizations, 337

S-S, 40,332 behaviors as Lewis acid, 45 cleavage of, 42,241,244,305,

352 heterolytic scission of, 45, 54 homolysis, 43,85, 113

Subject Index

photolytic cleaving, 44 rotation, 344 stability of, 40 vulcanization, in, 85, 87, 113

shared-electron-pair, 3 sulfoxide and sulfilimine, 393 sulfur hexafluoride, in, 5-7

Borohydride reduction, 481 Boron organic compounds reacting

with sulfur, 48 Bromination of sulfides, 262 Bromine oxidation, 386 a-Bromobenzyl benzyl sulfone, 559 Bromobenzyl sulfone, 559 3-Bromo-3-butenyl-I-sulfenyl

bromide, 262 2-Bromocyclooctyl butyl sulfide,

511 2-Bromoethyldimethylsulfonium

bromide, 504, 505 2-Bromoethyltrimethylammonium

bromide, 504 N-Bromosuccinimide,445 Br¢msted acids, 417, 486 Br~nsted plots, 569, 655 Brugine, 310 Bunte salts, 206, 329, 347

thioaklyation of thiols by, 326 Butadiene, thiol addition to, 131 I, 3-Butadiene, 82,141 Butadiene sulfones, 582 I, 2-Butadienyl p-tolyl sulfone, 640 2-Butane, isomerization, 131 Butane-2, 3-diol cyclic sulfates, 666 Butanol, boiling point, 121 Butenyl butyl sulfones, 582, 583 Butyl alcohol, 83 t-Butyl benzoylperoxide, 287

decomposition, 287, 288 n-Butyl benzoylsulfinate, 629 n-Butyl chlorosulfonate, 656 t-Butyldimethylsulfonium ion, 497 t-Butylethylmethylsulfonium

perchlorate, 483 t-Butyl hydroperoxide, thiol

reaction with, 155 Butylmercaptan, 155

reaction with 3, 5-dimethylene­cyclohexane, 141

n-Butylmercaptan,

Subject Index 687

oxidation, 156 Carbonyl sulfide photolysis 39 reaction with diacetylene, 146 Carboxyalkyl di;ulfides 37i

Butyl methyl sulfoxide, racemization, Carboxylate ions, alkYl~tion of, 495 398 Carboxylic acids, 49

n-Butyl orthoformate, 656 dissociation constants 486 n-Butyl phenyl sulfide, 243 Carboxylic esters 508 ' n-Butyl s~lfite, 629, 656 rearrangement, 542 t-Butyl thlOsulfonate, 324 o-Carboxyphenyl disulfides, 323

Cabbage, 310 Cannizzaro reaction, 61, 63 Carbanions, 45, 47

cleaving disulfide bonds, 241 non-bonding lobe, 272, 276 reactions with disulfides, 357 reactions with sulfides, 267 reversible formation, 504 stability, 276, 277,499, 504 thiolation of, 57

Carbenes, reaction

disulfides, 362 sulfides, 514 thione, 216

Carbene-like singlet sulfur, 39 Carboalkoxysulfenyl chloride, 325 Carbon, doctrine of tetrahedrally

directed tetravalence, 18 Carbon disulfide,

bonds, 189 formation of, 49, 56 Grignard reaction, 160, 197 reaction with alcohol or phenol,

199 Carbonic acid, sulfur derivatives

199 ' Carbonium ions, 29

reaction with sulfides, 254, 477 stabilization, 27

Carbon monoxide, 145 Carbon oxysulfide bonds, 189 Carbonyl groups,

addition of dithiophosphoric acid to, 172, 173

base-catalyzed reduction of 61 bonding, 190 ' characteristic features, 195

m-Carboxyphenyl methyl sulfoxides, 395

m-Carboxyphenyl methyl-N­tosylsulfilimine, 401

Carboxyphenyl phenyl sulfoxide, 419

Caro's acid, 385 Cassipourine, 311 Catechol cyclic phosphate, 673 Catechol cyclic sulfate, 669, 676 Catenaocta sulfur, 35 Cation, formation of, 43 Cephalexin, 410 CH acids, reacting with sulfur, 48,

59 s-Character rule, 30 Chloramine B, 385 Chloramine T, 389, 391, 457 Chlorinolysis,323 a-Chloroalkyl sulfides, reactions,

255 Chloroalkylsulfinic acids, 634 Chloroamines, reaction with sulfides

481 ' Chlorobenzenesulfinic acids,

uv spectra, 608, 609 l-Chlorobenzotriazole, 385 3-Chloro-l ,-bis-( ethy lmercapto)

propane, 279 2-Chlor0-4-tert-butylcyclohexene

137 ' 4-Chlorobutyl sulfide, 512 2-Chlorocyclohexyl phenyl sulfide,

258 2-Chlorocyclopentyl phenyl sulfide

258 ' Chlorodithio compounds, 328 Chloroethers, solvolysis, 257 Chloroethyl ethyl sulfone, 562 2-Chloroethyl phenyl sulfide, 511 Chloromethylarenes, 161 Q-Chloromethyl ether, 255

688

Chloromethyl sulfene, 560 Chloromethyl sulfide, 410 Chloromethyl sulfoxides, 446 p-Chlorophenyl sulfoxide, 444 Chlorophyll synthesis, 204 Chloroprene, 141 3-Chloropropyl phenyl sulfide, 511 Chlorosulfides, solvolysis of, 257 Chloro sulfones, 555

conversion of, 557 cyclization, 556

a-Chlorosulfone, 585 Chlorosulfonium salts, 262 Chlorosulfoxides, 446 a-Chlorosulfoxides, formation, 532 2-Chlorosulfoxide, 445 Chlorosulfoxonium intermediates,

448 trans-4-Chlorothian-S-oxide, 432 b-Chloroi3,-y-unsaturated sulfones,

540 3{3-Cholestanol p-toluenesulfonate,

653 Cholestanon-3A-3HT-3{3-o1,422 3{3-Cholestanyl methanesulfonate,

653 Chromophores, inherently

dissymmetrical, 342 Cinnamyl phenyl sulfide, 457 Cleland's reagent, 347, 358 Coenzyme A, 310

function of, 174 Compton profiles of hydrocarbons,

17 Configuration of maximum

probability, 7, II Co-ordination diagrams, 19 Cope elimination, 428 Cotton effect, 399 Cumyl chloride, 265 Cupric ammonium hydroxide, 347 Cyanide ions, 45

cleaving disulfide bonds, 242 reaction with disulfides, 358

2-Cyano-4, 4-dimethyloxetane, 221 Cyanogen azide, in sulfilimine

formation, 390 Cyanoisopropyl radicals, 215, 216 Cyclic ethers, 250 Cyclic imines, 250

Subject Index

Cyclic ketosulfoxide, 431 Cyclic sulfate esters, 663 Cyclic sulfides, 239

uv absorption bands, 247 Cyclic sulfonate esters, 663 Cyclic sulfonium ion intermediates,

238 Cyclic sulfonium salts, 483

bridged, 477 Cyclization, 50, 55 Cycloalky1 phenyl sulfoxide, 429 Cyclobutyl sulfones, 556 Cyclodecasulfur,38 Cyclododecasulfur, 37, 38 CycloheptasulfuI,38 I, 4-Cyclohexadiene, 239 Cyclohexane, 50, 223 cis-Cyclohexane-l, 2-diol cyclic

sulfate, 666 trans-Cyclohexane-1, 2-diol cyclic

sulfate, 666 Cyclohexanone, 192

hydrogen sulfide treatment, 191 Cyclohexasulfur, 37 Cyclohexene, 77, 78, 238 Cyclohexenecarboxylic acid, 64 1-Cyclohexenylmercaptan, 192 Cyclohexylammonium benzothiazole-

2-thiolate, 104 N-Cyclohexylbenzothiazole-2-

sulfenamide, 92, 96 Cyclononasulfur, 38 Cyclooctadiene, 222 1, 3-Cyclooctadiene, 220 Cyclooctane, 290 Cyclooctasulfur, 34, 35

cleavage of, 107 conversion from orthorhombic

to monoclinic, 35 formation, 44 stability of, 41

Cyclooctene, 290 Cyclopentadieny1 ylide, 514 Cyclopentanone, 192 Cyclopentenes, 238 1-Cyclopentenylmercaptan, 192 Cyclopentyl sulfones, 556 Cyclopropane, 443, 594, 596 Cyclopropy1sulfonium ylides, 516 Cyclopropyl sulfoxide, 442

Subject Index

Cyclosulfonium intermediates, 411 Cysteamine, 606 L-Cysteine, 342, 606 Cystine, 313, 358

nmr spectra, 343 optical activity, 342 specific rotation, 334

Cytochrome C, 313

Darzens-type condensations,S 54 Dehydrocyclization, 55 Deoxyuridilyl disulfides, 342 Deoxyuridilyl methyl sulfides, 342 Desulfurization, 43 Deuterium-hydrogen exchange rates

in sulfonium salts, 488, 489 Diacetylene, reaction with n-butyl-

mercaptan, 146 N,N-Diacyclcystine derivatives, 358 Dialkenyl polysulfide crosslinks, 84 Dialkyldithiocarbamic acids, 73 Dialkenyl sulfides, formation, 97 Dialkydiphosphoric acid, 449 Dialkyl disulfides, 321

reactions, 345 Dialkylethylenes, 106

sulfuration of, 97 2,2-Dialkylmercaptals, uv absorp­

tions,249 Dialkyl sulfates, 211, 655

sulfonium salts from, 474 Dialkyl sulfides, 385

nucleophilic attack, 475 reactions

diazonium ions, 475 sulfinic acids, 618

spectra, 246 Dialkyl sulfilimines, 392 Dialkyl sulfones, 529 Dialkyl sulfoxides, 385

baSicities, 426 reaction with sulfonylsulfili­

mines, 456 Diallyl disulfide, 337 Diallyl maleate, thiol addition to,

132 Diallylsulfonium salts, 518

Diallyl-N-p-tosylsulfilimine,457 p.p-Diaminodiphenyl sulfoxide,

388 Diarylmethanes, 579 Diaryl disulfides,

analysis, 375 bond strength, 335 cleavage, 361 preparation, 338 reactions, 345

689

reducing sulfoxides, 406 sulfoxide formation from, 385

Diaryl sulfide, 636 Diaryl sulfide dichlorides, 479 N,N-Diaryl sulfonamides, 543 Diaryl sulfones, 541

pyrolysis, 577 rearrangements, 564 reduction, 605

Diarylsulfonylsulfilimines, 449 Diaryl sulfoxides,

oxidation, 447 oxygen exchange, 417

Diaryl thioncarbonates, 212 1,2-Diathiane, 317 1,4,2-Diaxazolinines, 591 Diazo compounds, reaction with

. thiocarbonyl compounds, 216 a-Dlazo-{j-keto sulfone 587 Diazonium compound~, reactions

with sulfinic acids, 635 Diazonium ions,

addition of aromatic sulfinic acids to, 636

reaction with sulfides, 475 Diazosulfides, preparation, 234 a-Diazo sulfones, 585-588 Dibenzo-l,5-cyclooctadiene, 581 Dibenzoyl stilbene episulfone, 563 Dibenzyl disulfide, 337 Dibenzylhydryl tetrasulfide,

crystalline forms, 334 Dibenzyl sulfide, 475

bromination, 262 photolysis, 289

Dibenzyl sulfoxide, 406 S,S-Dibenzyl-N-tosylsulfilimine,

450 Di-n-butyl disulfide, 354 Di-n-butyl sulfate, 656

690

Di-n-butyl sulfoxide, 406 gem-Dichlorides, 196 Dichlorocarbene additions, 553 1,I-Dichloroethylene, 66, 146 1,2-Dichloroethylene, 146 Dichloromethyl sulfonic acids, 557 Dicumyl peroxide in vulcanization,

83 Dicyclohexylcarbodiimide, 422 Dieckman type condensation

reaction, 291 Diels-Alderreaction, 224, 241, 545,

583 Dienes, thiol addition to, 130, 145 1,5-Dienes,

accelerated sulfuration of, 98 reaction with sulfur, 80

Diene and triene groups in vulcan-ization process, 76

Dienic sulfinates, 571 Dienic sulfones, 571 Diethylamine, 199 Diethyl dithiophosphoric acid,

addition to nitriles, 171 1,2-Diethylmercapto-2-ethoxy-

ethylene, 286 Diethyl sulfate, 656 Diethyl sulfide, 501 Diethyl N-p-toluenesulfonyl­

sulfilimine,450 gem-Dihalides, 245 Dihalosulfones, 557,560

reduction, 572 Dihydrobenzothiophene, 573 1,3-Dihydroisothianaphthenes, 581 2,5-Dihydrothiophene, 580 1,2-Dihydro-2,2,4-trimethyl-

quinoline, 74 Dihydroxydiaryl sulfones, 634 4,4-Dihydroxydiphenyl sulfide, 266 4,5-Dihydroxy-l,2-dithianes, 371 Diisopropyl sulfoxide, 405 Diketopiperazines, 311 Dimerization, 48, 50, 56 Di-(p-methoxyphenyl)sulfide, 392 N,N-Dimethylacetamide, bonding,

194 p-Dimethylaminobenzoyl aryl

sulfone, 636 N,N-Dimethylamino groups,

Subject Index

substitution of, 191 p-Dimethylaminophenyl aryl

sulfoxide, 636 Dimethylamino radicals, 152 N,N-Dimethylaniline, reaction with

sulfinic acids, 636 2,3-Dimethyl-l,3-butadiene, 141,

145 1, l-Dimethylbutyl-l,3-dimethylbut-

2-enyl,87 2, 7-Dimethyl-2, 7-<iihydrothiepen-l,

I-dioxides, 580 cis-4,6-dimethyl-l,3-dithiane, 274 4,5-Dimethyl-l,2-dithiole-3-thione,

82 3,5-Dimethylenecyclohexane,

reaction with butyl­mercaptan, 141

Dimethyl formamide, 59 N ,N-Dimethyl-fj-mercapto­

ethylamine, 180 S,S-Dimethyl-N-methylsulfonyl­

sulfilimine, 394 3,5-Dimethyl-4-nitrophenol, 435 2,6-Dimethylocta-2,6-diene, 77, 78

sulfuration of, 89 trans-2,6-Dimethylocta-2 ,6-diene,

80, 100 Dimethylphenylselenonium ion,

511 Dimethylphenylsulfonium ion,

chlorination, 5 11 mono-nitration of, 510

Dimethyl pyrosulfate, 536 2,5-Dimethylquiny1 acetate

oxidation, 424 Dimethyl sulfate, 657 Dimethyl sulfide, 160,455,494,

496,508,593 Dimethyl sulfilimine, pyrolysis, 455 p-Dimethy1sulfoniopheno1, 412 1-Dimethylsulfonio-2-pheny lcyclo­

hexane, 500 Dimethylsulfonium fluorenylide,

514 Dimethyl sulfoxide, 159,245,318,

421,591 catalytic reduction, 404 reaction with arenesulfonyl

chloride, 410

Subject Index

reduction of, 403, 407 refluxing alcohols, 424

Dimethylsulfoxonium ylides, 520 Dimethyl tetrasulfide, 85 3,4-Dimethylthiazolium bromide,

490 2,2-Dimethyl thiochroman-l-oxide,

410 Dimsyl sodium, 437, 438 N ,NI-Di-2-naphthyl-p-phenylene

diamine, 74 2,4-Dinitrobenzenesulfeny I

chloride, 238, 5 12 p-Dinitrophenol, IS 7 2,4-Dinitrophenyl disulfide, 360 2,4-Dinitrophenyl p-toluene-

sulfonate, 655 Diolefins, thiol addition and, 139 2,2-Diphenyl-l,3-benzoxathian-4-

one,211 Diphenyl disulfide, 344

bromination, 364 cleavage, 359 reaction with cyanide ions, 359

t3ft-Diphenyldivinyl sulfide, 241 1,I-Diphenylethylene, formation,

205 Diphenylmethane, 50, 126, 223 Diphenylmethanethiyl radicals,

formation, 223 Diphenyl-l-picrylhydrazyl, 83 Diphenyl sulfate, 658, 669 Diphenylsulfhydrylmethyl radicals,

formation, 223 Diphenyl sulfide, 345, 356

preparation, 243, 289 Diphenyl sulfone, 345, 405

preparation, 531 Diphenyl sulfoxide,

ionization, 414 oxidation, 448 radical cation intermediate, 415 reduction, 405, 407

2,4-Diphenylthietane-l, I-dioxide, 580

2,3-Diphenylthiirene-l, I-dioxide, 560

Diphcnyl-N-tosYlsulfilimine, 452 Diphenyl trithiocarhonate, 205 Dipropylene glycol, 537

691

Di-n-propyl sulfate, 656 2,2-Dipyridyldisulfide, 194 Disproportionation, 367, 371, 372 1, I-Disubstituted cyclopropane,

507 Disulfides, 303-381

(See also Sulfides and Poly­sulfides, etc.)

acyclic, 342 analytical aspects, 374 barriers to rotation, 333 biological significance, 309 bonding and stereochemistry,

331,340 cleavage, 241, 352 energies, 335, 336 hybridization, 336 sp orbitals, 334

chirality, 342 circular dichroism, 341 conjugation, 341 coplanarity, 341 cyclic, 305, 373

preparation, 329 relative reactivity, 373

desulfurizing, 355 dipole moments, 344 excitation energy, 340 Friedel-Crafts acylation, 364 gas chromatography, 375 heterocyclic, 311 hyperconjugative interaction,

337 infrared, Raman, nmr and mass

spectra, 343 irradiation, 366 macrocyclic, 315 melting points, 345 mixed unsymmetrical, 306 molecular orbital treatment, 340 nomenclature, 306 non-coplanarity, 335 S-nucleophilicity, 353 occurrence, 309 odoriferous, 309 optical rotations, 341, 342 oxidation, 348, 350 photoexcitation . 338 physical properties, 331 polarographic reduction, 348

692

polarography, 375 preparation, 316

bromination, by, 262 dithiocarboxylic acids, from,

173 thiol oxidation, by, 155-160,

316 vulcanization, in, 81

pseudoaromatic, 374 reactions, 345-371

carbenes, with, 362 cyanide ion, with, 358 disproportionation, 367, 371,

372 e1ectrophiles, with, 363 expanded octet, 354 heavy metals, 364 homolytic, 364 hydroxyl and alkoxyl ions,

360 nucleophiles and bases, with,

352 phosphorus compounds, with,

355 sulfinic acid, with, 616 sulfite, thiosulfate and sulfinate ions, with, 359 thiolates, with, 357 thiols, with, 357 trialkylboranes, 367

ring siz<!s, 373 -SS-bonds, 335 stereochemical features, 331,

340,344 symmetrical,

change to unsymmetrical, 363 preparation of, 327,329

thermal homolysis, 365 thioalkylation of thiols by, 327 -thiol combination, 346 transfer constants, 366 unimolecular scission, 365 unsymmetrical, 344

analytical aspects, 375 cleavage, 356 disproportionation, 367, 371,

372 electrophilic attack, 364 preparation, 320, 327, 329,

330

Subject Index

uv spectra, 337, 338, 339 Disulfide bridges, formation of, 322 Disulfones, 350

reduction, 320 a-Disulfone, 349 (j-Disulfones, preparation, 542 Disulfoxides, of thianthrene, 401 a-Disulfoxide~, 35 1 2,3,Dithiabutane 2,2-dioxide, 349 Dithiafu1venes, 58 Dithia groups, 3d orbital resonance

effect, 268 1,2-Dithiane, 329, 342, 351

carbanion from, 275 C-S bond cleavage in, 290

1,2-Dithiane, 219 meso-1 ,2-Dithiane-3 ,6-dicarboxylic

acid,361 Dithiin, 310 Dithioacetic acid, spectra, 164 Dithiobenzoic acid, 67

reaction with amines, 165 spectra, 164

Dithiobismorpholine in rubber vulcanization, 73

Dithiocarbamates, in vulcanization, 74

Dithiocarbamyl disulfides, 102 Dithiocarboxylates, preparation,

198 Dithiocarboxylic acid, 66, 160-161

acidity, 163 chemical behavior, 164 disulfides from, 173 physical properties, 162 pKa values, 163 reaction with amines, 164 spectra, 163

gem-Dithiols, formation of, 201 Dithiolanes, C-S bond cleavage, 290 1,2-Dithiolane, 329, 335

reactions, 354 Dithiolane derivatives, 217, 310 Dithiol enzymes, 3 14 1,2-Dithiole-3-one, 311 Dithiole-thiones, formation, 51, 52,

53,82 1,2-Dithiole-3-thiones, 56, 374

formation in vulcanization, 81, 82

Subject Index

1,3-Dithiole-2-thiones, 56 1,2-Dithiolium salts, 374 1,3-Dithiolium salts, 58 Dithiophosphoric acids, 160, 161

addition to carbonyl group, 172, 173

addition to ole fins, 168 photochemical reactions, 170

chemical behavior, 164 pKa values, 163 reaction with hydrazines, 166 spectra, 163 stability, 162

Q-Dithiopyrones, formation, 52 Dithiosulfites, 305 Dithiotheitol, 347, 376 Di-p-tolyl sulfone, 529 Divinyl sulfide, 241

free radical reactions, 285 Doctrine of co-ordination, 18, 19 Doctrine of tetrahedrally directed

tetravalance, 18 n-Dodecylmercaptan, 159 Douglas-Farah reaction, 323 Dualistic character of sulfur, 44

ElcB mechanism, 504 Elastomers, vulcanization, for, 74 Electrons

(See also under Orbitals, etc.) angular dispersion, 29 electrostatic repulsion of, 3 inner-shell, 4-lone-pair, 12 octet rule, 14 overlapping of, 41 polarizable character of, 30 spin-paralleled, 8, 9, II unshared valence-shell, 4 valence-shell, 4

Electron pair acceptors and donors, 27

Electron-proton-electron transfer mechanism, 204

Electron-releasing conjugation of sulfur atom, 147

Electron-sharing conjugation, 135

693

Electron shell, expansion of, 45 Electron spin density, carbon, 288 Electron structure, valence-shell-

electron-pair-repulsion, 22 Elemental sulfur, 33-70

activation of, 40 color, 47 cyclodeca,38 cyclododeca, 37 cyclohepta, 38 cyclohexa, 34, 35, 37 cyclonona,38 cycloocta,

formation, 44 stability of, 41

forms of, 34 Grignard reagent reaction with,

125 molten and vapor, 36 oxidation of, 49 reactions of, 48-67

(See also under those reactions)

acetylenes, with, 57 alkanes, 53, 55 base-catalyzed oxidation of

C-Cl bonds, 65 base-catalyzed with C-H

bonds, 56 Cannizzaro, 61, 63 CH acids, 48,59 classes of substances reacting,

48 CoS bond formation, 52 cyclization, 50, 55 enamines,59 ionic chain mechanism, 54 Markovnikov rule, 54 McMillan-King, 64 mercaptoketones, 61 0lefins,63 oxidations of alkylated

aromatic and heterocyclic compounds, 63

redox, 49, 59 thermal reactions with C-H

bonds, 50 thermal with acetylenes, 56 thiolation of carbanions, 57 thiolization, 62, 66

694

Willgerodt-Kindler, 58, 62, 65,66

reduction of, 49 stabilization of, 43

Ellman's reagent, 358, 376 Enamines, reactions with, 59 Enethiols, formation of, 55 Enethiolization, 56 Enhancement of electrophilic

aromatic substitution, 27 Episulfides,76

preparations, 239 Episulfones, 545, 558

epimerization, 562 formation, 559, 560 thermal decomposition, 563,

580 Episulfonium intermediates, 130 Episulfonium salts, 478, 482, 5lT Episulfoxides, 430 Epoxides, 594 Ethanol, irradiation of, 605 Ethers, hydrogen bonding with

sulfides, 250 Ethoxyacetylene, 146

addition of ethylmercaptan to, 150

addition of thiol, 149

Ethylbenzyl phenyl sulfide, 496 Ethyl (bis-mercapto)-acetates, H-D

exchange reaction, 273 Ethyl n-butanesulfinate, 608

2-Ethyl-1 ,3-dithiane, hydrogen exchange, 274

Ethylene, atomic geometry, 667 Ethylene disulfones, cleavage, 605 Ethylene dithiotosylate, 294 Ethylene sulfate, 665, 667, 673 Ethylenesulfonium ions, 256 Ethyl hydrogen sulfate, 658 Ethylmercaptan, addition to

ethoxyacetylene, 150 I-Ethylmercapto-2-ethoxy-

ethylene, 286 Ethylthioacetylene, IS 0 O-Ethyl thiobenzoate, 201, 217 O-Ethyl thiopropionate, 223 Ethyl p-tolyl sulfoxide, 395, 638 Excited state configuration, 2

Subject Index

Exclusion principle, 2, 4, 8, 9, 12, 19,21

Fatty acid synthetase, 175, 176 Fenton's reagent, 155 Flavin adenine dinucleotide, 179 a-Fluoromethyl methyl sulfoxide, Forms of sulfur, 34-40 Formyl arenesulfonate, 327 Frasch sulfur, 34 Friedel-Crafts reaction, 154, 197,

243,364,533 Fries rearrangements, 542 Furan synthesis, 509 2-Furylmercaptan, 129

Garlic, 309 Gas chromatography, 375 Gliotoxin, 312, 342 Glutathione, 178, 180, 313 Grignard reagents,

cleaving S-C 1 bonds, 242 reaction

carbon disulfide, with, 160, 197

sulfinic acids, with, 638 sulfonate esters with, 542 sulfones, with, 547 thiobenzophenone, with, 205

Grote's test 375 Gyloxalic acid, 409

a-Haloalkyl sulfones, 559 Halogens, sulfide complexation,

252 Halogen molecule, nucleophilic

attack on, 27 Halogeno-alkyl sulfide, 476, 480 Halogen-sulfide complex,

formation, 416

Subject Index

trigonal bypyramidal structure, 253

a-Halosulfides, 245, 530 Halosulfones,

condensations, 554 cyclizations, 555 nucleophilic displacement, 557

a-Halosulfones, 530 (J-Halosulfones, 583 Halosulfonium cations, 386 Halosulfonium salts, 253, 481 N-Halo sulfoximines, 593 Halothiirane dioxides, 545 Halovinyl sulfones, 541 Hammett acidity function, 415 Hammett relationship, 213, 255 Hammett values, 278 Hartree products, 7, 8, 9, 10, II,

12 Helium,

electronic structure, 12 ionization potentials, 3

Hemiketals, 154 2,4,6-Heptanetrione, reaction with

phosphorus pentasulfid,:, 225 Heptasulfane, 45 Hept-2-ene, 77, 78 Heterocyclic compounds, oxida-

tions,63 Hexafluorothioacetone, 206 Hexasulfane, 45 Hexathiepane, 310 Hexathioanes, formation, 64 Hex-I-ene, 98,106 Hex-3-ene, sulfuration of, 98, 99 Hex-3-ene-2-thiol groups, 98 Hoffmann control, 499 Hoffmann-Woodward rules, 563 L-Homocysteine, 606 Homocystine, 313 Hormones, polypeptide, 314 Huckel aromaticity, 562 Hydrazines, reaction with dithio-

phosphoric acid, 166 Hydrazobenzenes, reaction with

dithiophosphoric acid, 166 Hydroaromatics, 346 Hydrocarbons,

Compton profiles of, 17 oxidation of, 49

Hydrodisulfide, 321 Hydrogen,

ionization potentials, 3 Hydrogen bonding,

sulfoxides, 393 thiols, 121

695

Hydrogen peroxide, oxidation by, 456

Hydrogen sulfide, 48 addition to allenes, 1 5 1 addition to olefins, 129 base-catalyzed reduction of

carbonyl groups, 6 1 formation of, 49, 50, 53, 56 reaction with nitriles, 199 reaction with olefin, 86, 124 solubility of sulfur in, 64 treatment of cyclohexanone,

191 Hydrogen-transfer, thiol as reagent,

125 Hydropolysulfides, 305, 307 p-Hydroquinone, 130 Hydrosulfides, 305, 307 Hydrcsulfcnium salts, formation;

480 p-Hydroxyaryl sulfides, 244 4-Hydroxy-l-butanesulfonic acid

sultone, 663 4-Hydroxy-I,2-dithianes, uv

spectra, 371 Hydroxylamine sulfate, sulfilimide

preparation from, 392 Hydroxyl ions, reaction with

disulfites, 360 2-Hydroxy-t-nitro-a-toluene­

sulfonic acid suitone, 675, 676

(J-(2-Hydroxyphenyl)ethanesulfonic acid sultone, 670, 674, 675

4( 5)-( 2-Hydroxyphenyl)imidazole N-sulfate, 662

S-Hydroxy-S-phenylthiosulfonium salts, 480

3-Hydroxy-I-propanesulfonic acid sultone, 664, 666

3-Hydroxypropyl monosulfate, 659 (J-Hydroxy sulfides, preparation,

234 Hydroxy sulfones, 551

696

a-Hydroxy sulfones, 538, 585 {3-Hydroxy sulfones, pyrolysis of

xanthate derivatives, 571 Hydroxythioamides, 61 2-Hydroxy-a-toluenesulfonic acid

smtone, 669, 670, 671, 672 Hypervalent compounds, 2, 6 Hypophosphorous acid, 347

2-( 4(5)-Imidazolyl)phenyl sulfate, 660,662

Imidoyl disulfide, 317 N-Iminopyridinium betaine, 168 Iminosulfonium salts, formation,

481 Insulin, 315 Interatomic distances, 23 Iodine, 83

complexation with sulfides, 252 sulfoxide reactions with, 427

Iodine oxidation, 386 Iodobenzene dichloride,S 31 Iodolactonization, 432 Iodosobenzene,386 Ionic chain mechanism, 54 Iron carbonyl, 404 Iron cobalt carbonyl, 245 Isoamyl nitrite, 209 Isocrotononitrile, 219 Isopropyl monsulfate, 659 Isopropyl sulfoxides, 399 Isothiochromene derivatives, 221

Ketene diethylmercaptal, copolymerization, 285

Ketimines, reactions with, 59 a-Ketocarboxylic acids, 178 Ketones,

reaction with sulfinic acids, 632 sulfoxonium ylides reactions,

519 Ketosulfides, 310 /3-Ketosulfides, uv absorption, 247 Ketosulfones, 576

Subject Index

/3-Ketosulfones, 585 Ketosulfoxides, reaction with

iodine, 409 {3-Ketosulfoxonium ylides, 520 Kornblum reaction, 420, 456

Lactic acid, 180 Lactones, reactions with sulfinic

acids, 633 Lattice energy of sulfur hexa­

fluoride, 15 Lead tetraacetate, 318

oxidation of thiols, 158 Lenthionine, 173 Lewis acids, reaction with

sulfoxides, 417 Lewis bases, 427

attack by, 45 Lewis salts in formation of

sulfonium salts, 478 Limonene, 80 Linalool, 82 Lipoic acid, 174, 178-180

function of, 179 reactivity of, 180

2-Lithio-1,3-dithianes, 274 Lithium,

ionization potentials, 3 reduction of sulfones, in, 574

Lithium acetylides, 242 Lithium aluminium hydride, 90,

235,496,604

Macrocyclic ethers, metal complexes, 251, 252

Maleic anhydride, base-catalyzed addition of thiols, 127, 128

Malformin, 314 Malonates, acidities, 191 Malononitrile,506 Malonyl coenzyme A, 175 Mandelic acid, 180 Manganese dioxide, 318 Mannich-type reactions, 632

Subject Index

Mann-Pope reaction, 389, 391 Markovnikov effects, 513 Markovnikov orientation, 84, 86 Markovnikov's rule, 54, 236

tbiol preparation, in, 124 anti-Markovnikov products, 237 Maximum co-ordination number,

18 McMillan-King reaction, 64 Meerwein reagent, 626 Melting point of elemental sulfur,

35,36 Menthyl alkanesulfinate, 395 Menthyl arenesulfinate, 396 Menthyl (- )-p-iodo benzenesulfina te,

611 Menthyl sulfinates, physical data,

611 Menthyl p-toluenesulfinate, 611,

638 Mercaptals, 232

alkylation, 291 five-membered, 272 H-D or H-T exchange reactions,

270 Mercaptans

(See Thiols) Mercaptoacetic acid, 208

decarboxylation, 273, 274 Mercaptoacetylene, 57 Mercaptobenzoimidazole, 165 2-Mercaptobenzothiazole,73 Mercapto disulfides, 372 Mercaptoethanol, 347 p-Mercapto groups, enhancing

phenol acidity, 266, 267 Mercaptoketones, reactions with,

61 o-Mercaptophenylacetic acid,

oxidation, 317 a-Mercaptosulfonic acid, 206 Mesityl naphthyl sulfones, 567 Mesityl m-tolyl sulfone, 568 Mesityl p-tolyl sulfone, 606 Metal l-alkenetholates, 327 Metal ions cleaving C-S bonds, 263 Metal organic compounds, reacting

with sulfur, 48 Metal-sulfur chelate compounds,

251

Metal-sulfur complexes, 251 2-Methanesulfinylbenzoic acid,

399

697

Methane sulfinyl groups, 443 Methanesulfonamides, 543 Methanesulfonyl bromide, 319 Methanethiophenol, 385 Methionine, enzymic demethylation

of, 408 Methionine sulfoximine, 589 Methosulfates, 482 Methoxide ion, 157 p-Methoxybenzy1carbonium ion,

491 5-Methoxy-2-hydroxy-a-toluene­

sulfonic acid sultone, 672 o-Methoxyphenyl methyl sulfide,

sulfonation, 264 Methylacetylene, 147 Methyl acrylate, 127, 143,219,

237 Methylallyl benzenesulfinate, 640 2-Methylbenzothiophene, 283 a-Methylbenzylamine-platinum

complex, 395 2-( 3-Methylbenzyl)-4,6-dimethyl­

benzenesulfinic acid, 568 2-( 4-Methylbenzyl)-4,6-dimethyl­

benzenesulfinic acid, 606 Methylbenzyl methyl sulfide, 517 a-Methylbenzyl p-toluenesulfinate,

639 a-Methyl benzyl p-tolyl sulfone,

639 2-Methylbut-2-ene, 82 Methyl chlorosulfite, 629 Methylcyclohexene, 77, 78 Methyl-I-cysteine sulfoxide, 404 Methyldiaryl sulfones,

pyrolysis, 579 rearrangement, 567

O-Methyl diaryl sulfones, 565, 568 Methyl dithio-I-naphthoate-S­

oxide, 214 Methylethylphenacylsulfonium

ylide,515 Methyl ethyl sulfide, 483 Methylethyl t-butylsulfonium

perchlorate, 397 2-Methyl-3-ethylthiopropanol, 145

698

Methylene chloride, 66 Methylene dialkylsulfonium salts,

489 5-Methylenenorbornene, 139 Methyl ethylene phosphate, 666 Methyl ethylene sulfate, 673 Methyl fluorosulfonate, 474 Methyl glyoxal, conversion to lactic

acid, 180 Methyl halides, 474 3-Methyl-3-hydroxy-l-butane­

sulfonic acid sultone, 664 N-Methylimidazole,675 Methylmercaptan, addition to

bicyclohexene, 136 Methyl - (3 - mercaptoacrylates,

thiyl radical addition to, 134 p-Methylmercaptostyrene,

copolymerization, 285 Methyl metaacrylate, 169 Methyl methanethiolsulfonate, 349 2-Methylpent-2-ene, 78,87,90

sulfuration of, 88, 90, 91, 92, 96,97,101,102,104,106, 111 accelerated, 105

2-Methylpenta-I,3-diene, 93 Methylpentenyl trisulfides, 94 p-Methylphenylhydrazine, 165 p-Methylphenyl methyl sulfoxide,

402 Methyl phenyl sulfide, 160 I-Methyl-2-propynyl-p-toluene­

sulfinate, 640 Methylstyrene, 168 Methyl sulfide,

bromination, 262 preparation, 362

Methylsulfinyl carbanion, 514 Methyl sulfones, 574 Methyl thiirene dioxide, 560 Methylthiobenzoic acids, 265 o-Methylthio diphenyl ether, 425 Methylthiomethylaniline

derivatives, 459 o-Methylthiophenol,425 p-Methylthiophenol,412 N-( 2,3-Methylthiopropyl)-D-ethyl

carbamate, 156

Subject Index

Methylthiyl radical, epr spectrum, 289

Methyl-p-toluenesulfinate, hydrolysis, 641

Michael additions, 127 Michler's thioketone, 210 Microorganisms, oxidation by, 389 Mitosis, 315 Mold metabolites, 312, 314 Molecules,

branching, 41 intermolecular interaction of, 34 species, 37 S8,34

Molten sulfur, 35 Monoalkyl sulfates, 658, 659,663 Monoaryl sulfates, 661, 663

hydrolysis of, 662 Mononitrophenyl disulfide, 360 Mono-olefins, sulfur reaction with,

76 Monosulfane monosulfuric acid

(See Thiosulfate) Monothiodibenzoylmethane, 203 Morpholine, 58 Mushrooms, 311 Mustard gas, 256, 511

Naphthalene, sulfonylation of, 534 Naphthalenesulfonic acids, 536 (3-Naphthol, 235 I-Naphthol-8-sulfonic acid sultone,

671 2-( I-Naphthylmethyl)-4,

6-dimethylbenzene sulfinic acid,567

Neopentyl p-toluenesulfonate, 652 Nereistoxin, 310 Nickel aluminium alloy, 576 Nitric acid, oxidization with, 385 Nitriles, reaction with hydrogen

sulfide, 199 Nitrile imines, 521 Nitrobenzene, 534 Nitrobenzenesulfenyl chlorides,

hydrolysis, 623

Subject Index

p-Nitrobenzenesulfenyl chloride, 623

reaction with pyridine N-oxide, 624

p-Nitrobenzene sulfonyl chloride, 535

Nitrobenzyl chloride, 210 5-Nitrocoumaramone,671 Nitrogen tetroxide, 385 4-Nitrophenyl disulfide, uv spectra,

339 2-Nitrophenyl phenyl sulfoxide,

photochemical oxidation-reduction, 448

p-Nitrophenyl sulfate, 660 Nitrosobenzene, 318 Nitrostyrene, 571 Nitro sulfones, 552 Nitrosyl chloride, 444 Nitrothiophenoxide anions, 358 N orbornene, thiol addition to, 135 Norbornylene, 238 Nucleofugal groups, 326 Nucleophilicity, 353

trans D. 2 -Octalin, 139 Oc~l~ne,77,78,87,88

Octet expansion, 29 Octet rule, 14 Octosulfane, unsymmetrical

derivative, 45 2-0ctyl sulfide, 619 j3-0ctyl p-toluenesulfinate, 611 Olefins,

addition of thiols, activation energies, 13 I

classification, 219 double bonds, addition to, 631 cis-trans isomerizations, 131 oxidations, 63 reactions,

dithiophosphoric acid, with, 168, 170

hydrogen sulfide, with, 124 sulfonium ylides, with, 516 thiones, with, 2 19

sulfenyl chloride addition to, 238

699

sulfenyl halide addition to, 511, 512

sulfonyl halide addition to, 539 thiol addition to, 127, 237

electrophilic, 129 Markovnikov adducts, 129 nucleophilic, 127 oxidative, 142 radical, 13 I resonance stabilized radicals,

140 stereochemistry of, 134

thiyl radical addition, 289 Olefin bromination, 478 Olefinic sulfides, ozonation, 532 Olefin-sulfur interaction

(See Sulfur-olefin interaction) Oligomerization, 56 Orbitals,

antisymmetrization and spin-exclusion, 7

back-bonding type, 5 bond, 17 chemical, 9 configuration of maximun

probability, 7, II conventional molecular model,S 3d, 2, 40 equivalent, 10 hybrid, 4, 10 in carbanion stabilization, 504 localized, 12 localized molecular, 10, II, 26 penetrating, 21 sp3 d 2 hybrid, I valence shell,S, 8 wave functions and, 7

d-Orbitals, free unoccupied, 40 d-Orbital problem, I Orthothioesters, 232, 244 Oxalic acid, thioamides of, 66 Oxibase scale, 354 Oxidative phosphorylation, 313 Oximes, reaction with DCC-DMSO

complex, 413 17-0ximinosteroids, 413 Oxiranes, 326, 519 j3-0xosulfoxides, 442 Oxy-Claisen rearrangement, 282

700

Oxosulfeneamides, 63 Oxosulfonium salts, formation, 480 Oxothioamides, 61, 63 N-Oxydiethylene benzothiazole

sulfenamide,74 Oxygen hexafluoride, 6 o:-Oxysulfones, 632 Oxytocin, 314, 315, 318

Parachor,393 Paraffins, dehydration products, 50 Pauli mechanics, 3, 4, 8 Pauling radius, 15, 18, 25 Penicillin sulfoxide, 410, 431 Pentacoordinate sulfur intermediates,

654,668,671,672,674, 675

Pentane-I, 5-dicarboxylic acid, 64 Pentane 2, 4-diol, sulfite ester, 612 1, 5-Pentanedithiol, 318 Pentathiepanes, formation, 64 Pentathiepane lenthionine, 310 Pentenyl methyl sulfones, 582 Peptide synthesis, 495 Perchlorate esters, 586 a-Perdeuterotriethylsulfonium

bromide, 501 Peroxides, oxidation of thiols, 157 Perphenyl onium salts, 488 Persulfenyl radicals, 86 Perthiol, effect on olefin, 86 o:-Phenacyl-{j-aryl-<l:, (3-unsaturated

sulfonium salts, 507 Phenacylcarbene, 516 Phenacyldimethylsulfonium ylides,

518 Phenacylsulfonium ylide, 507 Phenols,

acidities, 267 boiling point, 121 carbon disulfide reaction with,

199 cleaving bonds, 244 dissociation constants, 486 hydrogen bonding with sulfides,

250

Subject Index

Phenonium ions, 211 Phenoxide, eliminations, 504 Phenoxide ions, stabilization, 487 Phenylacetylene, 150

addition of sodium p-tolyl mercaptide, 145

reactions with, 58 thiol addition, 153,237

Phenyl allenyl sulfide, 283 Phenylbenzenethiolsulfinate, 621 Phenyl benzyl sulfoxides, oxygen

exchange, 414 Phenyl disulfide, 306 Phenyl dithiobenzoate, 205 o-Phenylenediamine, reaction with

p-toluenedithioc arb oxylic acid, 165

o-Phenylene sulfite, 642 Phenylethyl phenyl sulfoxide, 445 Phenyl ethyl sulfoxides, 399 Phenyl glyoxal, 420 Phenylhydrazine, reaction with

thiones, 203 Phenyl lithium, 242

reaction with thiobenzophenone, 205

Phenylmagnesium bromide, 205 (3-Phenylmercaptoethyl chlorides,

277 Phenyl methyl sulfone, 553 Phenyl methyl sulfoxides,

ionization, 414 Phenylsulfinate, oxygen

displacement, 572 Phenyl sulfinate esters, 537 Phenylsulfonylfluorene, carbanion,

572 Phenyl-sulfur linkages, 405 4-Phenyltetrahydrothiopyranoxides,

444 p-Phenylthiobenzophenone, 197 Phenyl thioisocyanate, 171 N-Pheny lthio-N-pheny lally 1-

sulfonamide, 457 Phenyl p-toluenesulfonate, 654 Phoroglucinol,235 Phosphate bonds, high energy,

313 Phosphate esters, 667 Phosphines, reduction by, 319

Subject Index

Phosphine compounds, cleaving disulfide bonds, 242

Phosphonium ylides, 515 Phosphoric acid, 159 Phosphorus compounds, reaction

with disulfides, 355 Phosphorus pentoxide in sulfilimine

formation, 391 Phosphorus organic compounds

reacting with sulfur, 48 Phosphorus pentasulfide, 161, 225 Phosphorus pentoxide, 458 N-Phthaloylmethionine sulfoxide,

402,419 2-Picoline, 655 Piperidine, 443 Piperylene, 141, 145 Planck's doctrine of energy

quantization, 20 Polarography, 375 Poly halogenated ethylenes, reaction

with thiolate anions, 146 Polymeric sulfur, 35 Polymeric sulfur elastomers, 36 Polymerization, 56 Polyolefins, cyclic, 239 Polysulfides (see also Sulfides,

Disulfides, etc.) bonding and stereochemistry,

331 cleavage, 244, 370

crosslinks, thermal decomposition of, 113 vulcanization, in, 84, 89

cyclic, 373 decomposition in vulcanization,

100 desulfuration, 113 fragmentation reactions, 42 infrared, raman, nmr and mass

spectra, 343 nomenclature, 306 nucleophilic attack, 45 physical properties, 331 preparation, 49, 51, 316

thiol oxidation, 316 vulcanization, in, 81, 85,86,

87 reactions, 345-371 reduction, 346

701

thermal decomposition of, 105 uv spectra, 341 vulcanization, in, 76, 79, 101

Polysulfide chains, 52 Polysulfide polymers, relaxation of,

357 Polysulfones, pyrolysis, 582 Polythionates, 332 Potassium cyanide, reaction with

thiones, 210 Potassium permangate, 455 Principal of local electrical

neutrality,16 Propane-2-thiol, 83 Prop argyl bromide, 508 Propargylic sulfonium salt,

isomerization, 508 3-Propenylmercaptan, 151 Propenylbenzene, 220 Propyl bromides, 279 n-Propyl 2-butyl sulfoxide, 428 Propylmercaptan, reaction with

styrene, 142 Prop-2-ynyl phenyl sulfide, 283 Proteins,

interaction with cyanide ion, 359 interaction with sulfite ion, 360 structure, 369

Pro,ton transfer, 27 Pryor's relative S-basicities, 354,

355 Pummerer rearrangement, 430 Pummerer-type reactions,

sulfoxides, of, 407 Pummerer type sequence, 510 Pyridine, 83

pKT values, 193 Pyridine N-oxide, 168,623 4-Pyridyl disulfide, 358 Pyrophosphate, 157 Pyruvic acid, 178,310

Quinoids, 318 Quinoline, pKT values of, 193 Quinones, reactions with sulfinic

acids, 634

702

S-Radicals, 43 Ramberg-Backlund reaction, 545,

550,553,557 Ramsay-Parsons-Weisskopf coulomb

cutoff potential, 22 Raney nickel, 576 Redox reactions, 49, 59 Resonance, 12

no-bond, 26 RNA viruses, 312 Ribonuclease, 3 14 Rubber,

'mix', 73 oxidation of, 113 stereoregular, 76 synthetic, 97

vulcanization, 73 vulcanization of (See under

Vulcanization)

Schonberg rearrangement, 212,213 Selenium, dehydration with,S I Selenium compounds, 253 Sigmatropic rearrangement,S 18 Slater's rules, 21 Smiles rearrangement, 538, 564 Sodium benzenesulfinates, 625

oxidation, 613 reaction with sodium

bromoacetate, 625, 626 Sodium benzoate, 629 Sodium bromoacetate, 625, 626 Sodium carboxylate, 629 Sodium phenylethylthiolate, 58 Sodium sulfide, 604 Sodium sulfite, 604 Sodium p-toluenesulfinate, 628 Sodium N-p-toluenesulfonyl

chloramide, 389, 391,457 Sodium p-tolylmercaptide,

addition to phenylacety­lene, 145

Sodium triphenylmethide, 501 Sommelet rearrangement,S 17 Spin-exclusion effects, 22 S piro-annelation, 5 16

Subject Index

Sporidesmin, 312 Stearic acid in vulcanization, 74 S tereoregularity, 76 Stevens rearrangement, 5 17 Stilbene, 345, 442, 578 Stilbene oxide, 507 Styrene, 132, 142, 168, 540 Substituent-hybridization effects,

25 Sulfanes, 64 Sulfanyl cations, 46 Sulfate(s), hydrolysis, 676 Sulfate diesters of aliphatic

alcohols, 656 Sulfate esters,

cyclic, 663, 669 hydrolysis, 675

Sulfate monoesters, of aliphatic alcohols, 658 of aromatic alcohols, 660

Sulfenyl halides, thioalkylation of thiols with, 321

Sulfenylphthalimides, 321 Sulfenamides, 62

thioalkylation of thiols with, 320

Sulfenes, cycloadditions, 544 formation, 213 stability, 214

Sulfenic acid, 349 Sulfenyl chlorides, 154 321

addition to olefins, 238 reduction, 319

Sulfenyl halides, 350 addition to acetylenes, 513 addition to elefins, 511, 5 12 hydrolysis of, 605

Sulfenyl succinimides, 321 Sulfenyl sulfinate, 352 Sulfenyl sulfite, 352 Sulfenyl sulfur, nucleophilic

substitution, 363 Sulfenyl thiocarbonates,

thioalkylation of thiols by, 325

Sulfenyl thiocyanates, 322, 323 thioalkylation of thiols with,

322 Sulfenyl thiolcarbonate, 326

Subject Index

Sulfides, 231-302 (See also Disulfides and

Polysulfides, etc.) alkylation of, 474 aromatic,

metal complexes, 251 preparation, 243 uv spectra, 249

bicyclic, 239 bond energies, 245, 289 bond lengths and angles, 246 chlorinolysis, 480, 496 complexation with halogens,

252, complexation with metals, 251 crosslinked in vulcanization, 90,

91,96,101,102, lOS, 109, 110, III, 112

cyclic, 233, 239 dielectric relaxation data, 344 donor properties, 249 electronic spectra, 246 electrochemical oxidation, 532 electroreduction, 348 elimination of thiol from, 131 fluoroalkyl, 305 hydrogen bonding, 249 intramolecular alkylation, 477 intramolecular proton transfer,

501 intravalence shell transition, 247 low boiling, 532 nomenclature, 306 nucleophilic attack, 475 oxidation of, 351, 386

forming sulfones, 529 forming sulfoxides, 385 mechanism, 530

ozonolysis, 532 physical properties, 245-253 preparation, 48, 51, 232-245,

331,510 addition of sulfenyl chlorides to olefins, 238 addition reactions, 236 addition to acetylenes, 236 addition to olefins, 237 alkylation, 232 cycloaddition, 240 disulfide cleavage, 241

ionic mechanism, 236 organic, 291

703

reactions of thiols, 232 sulfones, from, 573 vulcanization, in, 101, 114

reactions, 253-291 anchimeric effect, 256, 258 benzene, 515 bromination, 262 carbanions, 267 carbenes, with, 514 chloroamines, with, 481 cleavage of CoS bond, 289 decarboxylation, 269 decomposition, 286 Dieckman-type condensation,

291 electron accepting and

sharing, 255 electron-releasing conjugation,

265 electrophilic aromatic

substitution, 263 elimination and isomeriza-

tion, 277 EPR spectra, 288 free radical, 284 Hammet relationship, 255 hydrogen abstraction, 284 hydrogen exchange, 269 neighboring group effects

of sulfide group, 256 nucleophilic substitution,

255 3d-orbital conjugations,

275,276,278,280,281 3d-orbital overlapping, 271,

272 ring tautomerism, 258 stereochemistry, 259

structure and, 265 substitution with CoS bond

cleavage, 260 sulfide group, effect of, 254 sulfinic acid, 616 transannular participation,

258 reduction, 346 sulfonium salts formed from,

479

704

unsymmetrical,233 nomenclature, 306

uv spectra, 247, 248, 278 vulcanization, in, 76

Sulfide groups, effects of, 254 Sulfide-halogen complexes, x-ray

crystallography, 253 Sulfilimines, 167,383

basicity, 453 bonds, 393 Ei reactions, 453 hydrogen bonds, 393 isomerization, 457 optically active, 391 oxidation, 455 pKa values, 453 preparation, 384, 389 reactions, 449-459

dithiophosphoric acid, 168 S-N bond cleavage, 449, 450

reduction, 449 stereochemistry, 401 stereomutation, 402 sulfoximines from, 589 sulfur-nitrogen linkage, 394 unsubstitued, 392,452

Sulfilimine nitrogen, 453 Sulfinates, dipole moments, 607 Sulfinate displacements, 537 Sulfinate esters, 537 Sulfinate ions, reactions with

disqlfides, 359 Sulfinate salts, 350

condensation reactions, 351 Sulfines, formation, 213, 214 Sulfinic acid(s), 349, 604-637

acidity, 612 aldehydes added to, 538 disproportionation, 35 1, 613 hydrolysis, 641 oxidation, 613 preparation, 350, 604-606 Raman spectra, 609 reactions, 612

addition to olefinic double bonds, 631

aldehydes, 632 azo, diazonium and azine

compounds, with, 635 dialkyl sulfides, with, 618

Subject Index

N,N-dimethy1aniline, with, 636

disulfides, sulfides, with, 616 Grignard reagents, 638 lactones, 633 Mannich-type, 632 quinones, with, 634 thio1s, with, 624 thiosulfate, with, 622 thiosulfinates, with, 620

rearrangements, 639 salts, 537 spectrography, 607 structure, 606 uv spectra, 610

Su1finic acid group, electron­withdrawing effect, 612

Sulfinic anhydrides, 351, 623 Sulfinic esters,

hydrolysis, 641 reactions wtih hydrazine, 643 rearrangements, 639 structure, 606, 611 uv spectra, 610

Sulfinylbenzoic acids, pKa's, 433

Sulfinylphenols, pKa's, 433

Sulfinylcarbanions, 437 nucleophilic substitutions, 551 sulfoxide formation, with, in,

387 Sulfinyl chloride, 406

reduction, 319 Sulfinyl function, dissymmetric

nature of, 399 Sulfinyl groups,

carbanion addition to, 479 electron-withdrawing effect,

432 phenol acidity and, 268

Sulfinyl halides, hydrolysis of, 605 reduction of, 604

Sulfinylsuifonamides, 390, 391 Sulfinyl sulfone, 349, 351,626

formation, 614 hydrolysis, 615

N-Sulfinyl-p-toluenesulfonamide, 402,419

Subject Index

Sulfites, reaction with benzaldehyde, 642

Sulfite ions, reaction with disulfides, 359

Sulfolane, 432, 546 Sulfonamides, 391,543 Sulfonate esters, 586

aliphatic alcohols, of, 651 aromatic alcohols, of, 653,669 cyclic, 663, 669 hydrolysis, 675,676 reactions, 541

Sulfondiimines, 392 Sulfones, 527-602

acidity, 547 base-catalyzed hydrogen-

deuterium exchange, 549 condensations, 553 configuration, 549 formation of, 27, 253, 592,

625 melting points, 530 metallation, 546 3d-orbital conjugations, 280 physical properties,S 28 preparation of, 529-546

aromatic sulfonylation, 533, 535

Fries rearrangements, 542 oxidation of sulfides and sulfoxides, 529 rate enhancement, 534 sulfonyl halides to olefins,

539 via sulfinates, 537

pyrolysis of, 577 reactions, 546-588

Diels-Alder, 584 eliminations, 569 halosulfone cyclization, 555 metallation, 546 nature of carbanions, 546 nucleophilic, 45,551,583 Ramberg-Backlund,557 reduction, 572 Smiles rearrangements, 564

reduction of, 572 resonance stability, 548 saturated, 569 small ring, preparation, 544

705

stability,S 8 2 Truce-Smiles rearrangements,

579 Sulfone imines (See Sulfoximines) Sulfone-stabilized carbanion, 558 Sulfonic acid, 349

formation, 348 Sulfonic acid derivatives, reactions

with organometallic reagents, 541

Sulfonic anhydrides, 351 Sulfonium compounds, formation,

253, 254 Sulfonium group,

as leaving group in displacement reactions, 491

electrophilic aromatic substitu-tion,510

elimination, 499,500,501 in anion stabilization, 486 in displacement reactions, 491 nucleophilic additions to C-C

multiple bonds, 505 Sulfonium ions, 260, 498 Sulfonium methylide, 414 Sulfonium picrate, 482 Sulfonium salts, 473-525

addition of hydroxide ion, 506 addition to alkenes, 497 alkaline hydrolysis, 494 bimolecular elimination, 498 characterization, 482 dealkylation, 508 definition, 474 deuterium-hydrogen exchange,

488,489 dissociation of, 482, 491 electron-accepting conjugative

property, 486 eliminations, 502, 507 heterolysis, 497 hydride attack on, 496 hydrogen species in displace-

ments, 496 malononitrile addition, 506 4-membered ring, 477 nuclear halogenation, 5 11 nucleophilicity, 498,505,506 pKa data, 488, 490 preparation, 27,474-482

706

alkylation of sulfides, by, 474

aromatic electrophilic substitution, by, 478 carbanion addition to sulfinyl group, 479 oxidative, 481 sulfides, from 479

pyramidal inversion in, 483 reactions, 485

electronic effects of sulfonium substituent, 485

nucleophiles, with, 493 strong bases, with, 502 sulfonium group in anion

stabilization, 486 rearrangements, 510, 5 17 resonance, 487,489 reversion in, 492 solvolysis, 491 stabilization of carbanions, 488 structure of, 482 stereochemistry, 482 sulfonium group in elimination

reaction, 497 uv spectra, 484, 485

Sulfonium substituent, electronic effects of, 485

Sulfonium ylides, 167,491,513 nuclear spin polarization, 517 reactions, 168,515,516 structure, 514

Sulfonylacetic acids, 550, 552 Sulfonylaldehyde, 554, 586 N-Sulfony1amines, 566 Sulfonyl azides, 390, 590 Sulfonyl bromides, 533 Sulfonyl carbanions,

addition to vinyl ketones, 552 alkylated, 552 assymmetry, 549 halogenations, 553 hybridization, 550 orbital calculations, 550 reaction with acetylenes, 55 1

Sulfonyl carboxylic acids, 633 Sulfonyl chlorides, 533

polymerization of styrene by, 540

Subject Index

reduction of, 124, 604 Sulfonyl 1,2-dipheny1ethanes,

dehydrohalogenation of, 570

a-Sulfonyl ether, 587 Sulfonyl fluorides, 542 Sulfonyl groups,

inductive effect, 583 infrared spectra, 529 reduction of, 573 resonance contribution, 549

Sulfonyl halides, addition to olefins, 539 reaction with alcohol, 650

Sulfonyl iodides, 541 Sulfonylimidazoles, 675 Sulfonyl isocyanates, 390 Sulfonylium ions, 534 N-Sulfonylmethylurethanes, 585 Sulfonylphosphorus ylides, 546 SulfonylsulfUimines

reaction with dialkyl sulfoxides, 456

reaction with phenylmagnesium bromide, 452

N-Sulfonylsulfilimines, 393, 449, 455

N-Sulfonylsulfoximines, 455 Sulfoxldes, 383-449

amino-substituted,395 asymmetric induction, 389 basicity of S-O bond, 426

neighboring group effect, 431

pyrolysis,428 chromophore,399 configuration, 396, 397 electron-withdrawing effect of

SO group, 432 epimerization of, 480 halogenation, 444 Hammett acidity function, 415 hydrogen bonds, 393 iodine oxidation of, 404 isomorphous to sulfones, 401 kinetic isotope effect, 446 Kornblum reaction, 456 molecular association with

phenols, 427

Subject Index

nucleophilic attack, 424 nucleophilic substitution, 418,

435 optically active, 384, 389, 393 3d-orbital conjugations, 280 oxidation, 447

forming sulfones, 529 mechanism, 530

oxidative-reductive reaction, 410

oxygen exchange reactions, 399,414

photochemical racemization, 398

photo-induced isomerization, 398

pKa values, 426 preparation, 27, 253, 384, 407,

592,605 Pummerer rearrangement, 407,

408,409,430 racemization, 397, 416, 450 reactions, 403-449

basicity of S-O bond, 426 carbonyl or nitroso compounds, 418 dithiophosphoric acid, 168 electron-withdrawing effect

of SO group, 432 hydrogen isotopic exchange,

444 iodine, with, 427 methylene compounds, with,

514 oxygen transfer, 406 thiols, 405 Wolf-Kischner, 427

S-O bond cleavage, 403 Kornblum reaction, 410 oxygen exchange, 414 Pummerer-type reactions,

407 reduction, 403

spectroscopic analysis, 430 stereochemistry, 395 stereomutation, 398 sulfilimines from, 391 thermal racemizations, 397

Sulfoxide bonds, nature of, 393

Sulfoxide compounds, thiol reduction of, 167

Sulfoximines, 588-596

707

acylation and sulfonylation, 592 preparation, 455, 589,605 reactions, 592

Sulfoxonium yHdes, 519, 594 Sulfur,

electronegativity, 190 neighboring group

participation, 511 Sulfur atoms,

donor strength, 249 nucleophilicity of, 476

Sulfur-bromine complexes, 263 Sulfur chlorides, reaction of arenes

with,243 Sulfur containing azo compounds,

decomposition of, 138 Sulfur dichlOride, 406

electrophilic additions, 239 Sulfur-I, 5-diene reaction, 80 Sulfur-3, 8-diene reactions, 81 Sulfur diimide reagent, 418 Sulfur dioxide, 545

condensation with, 605 Sulfur-fluorine, intranuclear

distance, 24, 26 Sulfur heterocycles, 81 Sulfur hexafluoride,

bonding, 507 configuration of maximum

probability, 13 ionic model, 14 lattice enery, 14 localized orbitals for, 12 molecular orbitals, 5 Pauling radius, 15, 18 sulfur-fluorine intranuclear

distance, 24, 26 wave function, 14

Sulfuric acid, esterification of alcohol, 658, 659

Sulfuric-carboxylic acid anhydrides, 663

Sulfurization, bases formed during, 47 natural reactions, 49

Sulfur monochloride. 328

708

Sulfur-olefin interaction, 76 accelerated, 89 allylic rearrangement, III autocatalysis, 82 composition of polysulfides, 78 free-radical or polar chain

mechanism, 83, 84 kinetics and mechanism of, 82 mono-compounds, 76 other olefins produced, 78 pathways, 115 sulfur donors, 101

Sulfur organic compounds reacting with elemental sulfur, 48

Sulfur-oxygen linkage, 384 Sulfur redox reactions, 49 Sulfur stripping reactions, 312 Sulfuryl chloride, 445

Tetraalkylthiuram disulfides, 101, 102

vulcanization, in, 73 Tetracyanoethylene, 341 Tetrahydrothiophene, 243, 573 Tetramethylene disulfide, 243 Tetramethylene sulfide, 616 Tetramethylene sulfoxide, 159,405 Tetramethylethylendiamine, 275 Tetramethylhexathioadamantane,

173 Tetramethylsuccinonitrile, 215 Tetramethylthiourea, 102 Tetramethylthiuram disulfide, 96,

365 Tetraphenylethylene, 50 Tetrasulfides, 307

unsymmetrical,85 Tetrathiacyclooctane, 275 Tetrathianes, formation, 64 1,2,4, 6-Tetrathiepane, 310 Thermal broadening, 341 Thermal homolysis of disulfides,

365 6-Thiabicycloheptane, 289 Thiachromane, 283 Thiacoumarane, 283 Thiacyclobutane, 289 1-Thiacyclobutane-3-carboxylic

Subject Index

acid,396 Thiacyclohexane, dehydrogenation

of,52 Thiacyclohex-3-ene-l, I-dioxide,

582 Thiacyclopentane-l-oxide, 406 Thiamine, 490 Thiamine pyrophosphate, 178 Thian-l-oxides, isomerization,

398 Thianthrene monoxide, 406 Thianthrene-5-oxide, 415 Thiapyryllium salts, 481 endo-4-Thiatricyclo (5,2, 1,02,6)

dec-8yl-p-nitrobenzoate, 259 Thiazole-sulfenamides, 105 ThiazoIines, 358 Thietane, 544 Thietane derivatives, 219, 222 Thietane dioxides, 573, 580 Thiete dioxides, 544 Thiirane derivatives, 217 Thiirane dioxide, 559 Thiiranium salts, 511 Thiirene dioxides, 529, 545 Thioacetals, 244

halogenation of, 496 Thioacetamides, 66 Thioacetanilide, 373 Thioacetic acid, 124

addition to 2-chloro-2-butane and 2-acetylthio-3-

chlorobutane, 135 Thioacetophenone, 205, 216 Thioadamantanone, 196 Thioaldehydes, 61, 62, 196 Thioaldehyde-S-oxide, 214 Thioalkylation of thiols, 320

with Bunte salts, 326 with disulfides, 327 with sulfenamides, 320 with sulfenyl halides, 321 with sulfenyl thiocarbonates,

325 with sulfenyl thiocyanates, 322,

327 with thiosulfonates or

thiosulfinates, 323 Thioamides, 164

formation of, 49,59, 165, 199

Subject Index

oxalic acid, of, 66 Thio anions, 352 Thioanisole, H-D exchange reactions,

264 Thiobacilli, oxidation by, 50 Thiobenzoic acid, 202 Thiobenzophenone, 203, 215

irradiation, 223, 241 photoreaction, 219 reaction with

acetylenic compounds, 221 Grignard reagents, 205 olefins, 219, 220 phenyllithium, 205

reduction, 204, 223 Thiocamphor, 196,209 Thiocarbonates, cyclic, 200 Thiocarbonate esters, sulfides from,

235 Thiocarbonic acids, preparation,

199 Thiocarbonyl compounds,

Diels-Alder reaction, 224 reaction with diazo compounds,

216 reaction with nucleophiles, 201 reactions with organometallics,

214 Thiocarbonyl groups,

bon dings, 190 characteristic features, 195 polarizability of electrons, 208 reverse polarization, 206

Thiocarboxylic acids, 65, 197 Thiocarboxylic amides, formation

of,65 Thio-Claisen rearrangement, 282,

283 Thiocyanates, thioalkylation of

thiols by, 327 Thiocyanate ions, formation of, 46 Thiocyclohexanone, 192, 202 Thiocyclopentanone, 192 Thioesters, 209 Thioethers, reactions of, 42 Thioglycolic acid, 347 Thioglycosides, hydrolysis, 260 Thioketyl radicals, 205 Thioketals, 130,244 Thioketones,57

aliphatic,55 aromatic, 196, 197

709

Diels-Alder addition reaction, 241 enethiol form, 209 heterocyclic, 196 photochemical reactions, 240 preparations, 196 reactions or, 42, 207

Thiol(s), 62,119-187 acidities, 122, 128 addition reactions, 236 addition to acetylenes, 145,236

electron-sharing participation, 149

electrophilic, 148 nucleophilic, 145 oxidative, 153 radicals, 148

addition to al1enes, 145-154 free radicals, 15 1 nucleophilic, 145

addition to butadiene, 131 addition to dial1y1 maleate, 132 additions to dienes, 130, 145 addition to dio1efins, 139 addition to olefins, 127, 237

activation energies, 131 e1ectrophilic, 129 Markownikov adducts, 129 nucleophilic, 127 oxidative, 142 radical, 13 I resonance stabilized radicals,

140 stereochemistry, 134 thiy1 radicals, 144

alkylation, 232 base-catalyzed addition to

maleic anhydride, 127, 128 biological function, 120, 174,

180 boiling points, 121 bond angles in, 121 bonds and bonding, 120, 121 co-oxidation, 142 electrophilic addition, 236 free radical addition, 154, 237 hydrogen transfer and, 125, 144 molecular ionization potential,

122

710

nucleophilicity of anion, 122

oxidation to disu1fides, 155-160, 316

oxidation by peroxides, 157 physical properties, 120 preparation of, 49,51,123-125

addition to ole fins, by, 124 diarylthiocarbonates, from,

125 Markovnikov's rule, 124 nucleophilic substitution, by,

123 reduction, by, 124

reactions disulfides, with, 357 fragmentation, 42 sulfinic acids, with, 624

reduction, 235 reduction of sulfoxide

compounds, 167 reoxidation, 346 substitution on aromatic

systems, 154 thioalkylation of, 320

Bunte salts, with, 326 disulfides, with, 327 sulfenamides, with, 320 sulfenyl halides, with, 321 sulfenyl thiocarbonates, with,

325 sulfenyl thiocyanates, with,

322 thiocyanates, with, 327 thiosulfonates and sulfinates,

with,323 yields in vulcanization, 77

Thiolacetic acid, 130, 137 Thiolates, reaction with disu1fides,

357 Thiolate anions, 221

oxidation, 317 reaction with poly halogenated

ethylenes, 146 Thiolate ions, stability of, 29, 204 Thiolation, 52

acetylenes, of, 57 base-catalyzed, 57

Thiol catalysis of disproportion­ation,327

Subject Index

Thiol-disulfide interactions, 314, 357 Thiol esters, sulfide preparation

from, 233 Thiolization, 62, 66 Thiolutin, 311 Thiomethoxymethyl nitrone, 413 Thion-carbonates, 199 Thiones, 189-229

ionic reactions, 201 monomeric, 55 no-bond resonance, 224 photoreactions, 218 predominancy of form, 194 preparation, 49, 56, 196-20 I radical reactions, 214 reactions with carbenes, 216 reactions with electrophiles, 208 reaction with nucleophiles, 201 thiocarbonyl compounds, in, 193

Thionium ions, 130 Thionosulfites, cyclic, 332 Thionyl chloride, 130,388 N, N-Thionylimidazole, 388 Thiophenes, 232, 310

formation of, 51, 52, 53, 56 vulcanization, in, 81, 82

sulfonylation, 533 Thiophene I, I-dioxides, 572 Thiophenols,

preparation, 212 reaction with trimethylsulfoxon-

ium iodide, 160 Thiophilicity, 353, 355 Thiophosgene, 199,481 Thioprene, addition of thiols, 155 Thiopropynylic rearrangements, 283 Thiosulfate, formation of, 45 Thiosulfate ions, reaction with

disulfides, 359 Thiosulfate salts, condensation

reactions, 351 Thiosulfinate, 349, 350

disproportionation, 620, 623 oxidation, 349 reaction with sulfinic acids, 620,

622 Thiosulfonate, 349, 350

aromatic, 323 reduction, 320 thioalkylation of thiols with, 323

Subject Index

unsymmetrical, 323, 349 Thiosulfonium salt, 476, 497 Thioureas, 123, 195 Thioxanthene-1O-oxide, 396 Thiuram trisulfide, 108 Thiyl radicals, 53

addition to methyl-(j-mercapto­acrylates, 134

addition to olefins, 144, 289

Titanium dioxide, 74 p-Toluenedithiocarboxylic acid, 165 Toluenesulfenylpiperidine, 443 0-Toluenesulfinate rearrangement,

640 p-Toluenesulfinate, 395 a-Toluenesulfinic acid, 571 o-Toluenesulfinic acid, uv spectrum,

608 reaction with alkyl sulfides, 619,

620 reaction with benzoylthiol, 625

3-Toluenesulfinylbutyric acid, 399 p-Toluene sulfone, elimination, 569 p-Toluenesulfonic acid, 586 p-Toluenesulfonyl azide, 585 Toluenesulfonyl derivatives

reduction, 605 N-p-Toluenesulfonylsulfilimine,

394,449 p-Toluic acid, 50 p-Tolyl aIkyl-N-tosylsulfllimines,

451 d-p-Tolyl p-aminophenyl sulfoxide,

399 p-Tolyl-a-chloromethyl sulfone, 554 p-Tolyl methyl sulfide, 264 p-Tolyl methyl N-tosylsulfilimine,

418 p-Tolyl methyl p-tosylsulfilimine,

450 p-Tolyl phenyl sulfoxides, 415 p-Tolyl propenyl sulfone, 582 3-p-Tolylsulfonyl-2-butanol

derivatives, 569 N-Tosylsulfilimine, 403 2,4,6-Triadamantyl-benzenethiol,

316 Trialkylalummium, 388 Trialkylboranes, reaction with

disulfides, 243, 367 Trialkylethylenes, 104, 107 Trialkyloxonium salts, 476 Trialkylsulfonium sulfate, 475 TriaIkylsulfoxonium salts, 594 Triarylmethanol ions, 477 Triaryl sulfide, homolysis, 495 Triarylsulfonium bromide, 495 Triarylsulfonium salts, 479, 494 Trichloroethylene, 146

711

a, a, a-Trichloromethyl sulfones, 557

Trichiorosilane, reduction by, 404 a-Trichlorosulfides, 261 Triethylamine, 83 Triethyl orthoacetate, 198 Triethylphosphite, 242 Triethylsulfonium hydroxide, 498 Triethylsulfonium iodide, 482 Trifluoromethanesulfenyl chloride,

238 Trifluoromethyl radicals, 152 2,4, 6-Triisopropylphenyl groups,

323 2, 4, 6-Triisopropylphenyl

thiosulfonate, 324 Trimethylamine oxide, 160 Trimethylene dithiotosylate, 294 Trimethylene sulfate, 665 Trimethyloxonium fluoborate, 594 Trimethylsulfonium bromide, 483 Trimethylsulfonium iodide, 492 Trimethylsulfonium salts, 515 Trimethylsulfoxonium iodide, 519 Trimethylvinylsilane, 286 2, 4, 6-Trinitrobenzenesulfonates,

482,511 Triphenylphosphine, 95, 242, 355,

586 1, I, 3-Triphenylthietane, 221 Triplet state, 40 Trisulfides, 310

cyclic, 335 stereochemical features, 344

Trithiocarbonate S, S-dioxides, 631 Trithiolanes, formation, 64 Trithiones, formation of, 51 Trithio-orthoesters, 197 Trivalent phosphorus compounds

reducing sulfoxides, 407

712

Truce-Smiles rearrangement, 547, 579

Ureas, 195

Valence, doctrine of, 18 Valence shells, 256, 269

expansion, 336 sulfonium salts, 490

Valence-shell electron pair repulsion model, 22

Valence-shell-inner shell electron model,28

Vapor of sulfur, 35 Vasopressins, 314, 315,358 vicinal Dinitro compounds, 572 Vinylammonium salts, 505 Vinyl chromophores, 337 Vinyl ketones, addition of sulfonyl

carbanions, 552 Vinylmercaptans, 55 Vinyl methoxysulfonium salts,

additions to, 510 Vinyl polymerization, 365 Vinylpyridine, 169 Vinyl sulfide,

free radical reaction, 285 preparation, 236

Vinyl sulfone(s), 443, 529, 582-584 additions to, 546 bonds, 583 epoxidation, 554 isomerization, 582 nucleophilic addition, 583 Q values, 286 reduction, 573

Vinylsulfonium salts, nucleophilic addition, 505

Vinyl sulfoxide, 443 Vinylthiols, oxidation, 317 Vulcanates,

structural features, 75

Subject Index

Vulcanizates, overcure of polyiso­prene, 93

Vulcanization, 52, 71-118 acceleration, 83, 365 accelerators, 73, 74 accelerator-activator system, 89 active sulfurating agents, 103 active sulfurating agents, nature

of, 104 agents, 74 antioxidants, 74 antiozonants, 74 course of, 103 elastomers, 74 fillers, 74 formation of rubber-bound

intermediates, 109 ingredients, 103 intermolecular crosslinks, 75 maturing of network of cross-

links, 112 mechanism, Markovnikov

orientation, 84, 86 organic accelerators of, 73 polysulfide crosslinks,

maturation, 112 processing aids, 74 reaction pathways, 115 sulfur-I, 5-diene reaction, 80, 98 sulfur-olefin reactions, 76

accelerated, 89 kinetics and mechanism, 82 pathways, 115 sulfur donors, 101

synthetic rubbers, of, 73

Wagner-Meerwein rearrangement, 135, 238

Walden inversion, 389 Wave functions,

determinantal, 9 orbitals and, 7

Willgerodt-Kindler reaction, 58,62, 65,66,199

Wolff rearrangement, 587 Wolf-Kischner reaction, 427,576

Subject Index

Xanthates, synthesis of aromatic thiols by, 123

Ylides, formation, 253 Ylide-ylene intermediates, 408

Zeisel-type dealkylations, 480 Zinc accelerators, in vulcanization,

lOS, 106, 107, 112, 113

713

Zinc-accelerator-thiolate complexes, in vulcanization, 95

Zinc activators, in vulcanization, 97, 98, 100

Zinc benzothioIe-2-thiolate, 95 Zinc carboxylate, 107, 114 Zinc dimethyldithiocarbamate, 100 Zinc dimethylperthiocarbamate, 109 Zinc dimethylthiocarbamate, 109 Zinc oxide, 94, 100

vulcanization, in, 74, 104, 112 Zinc sulfide, 90

vulcanization, in, 92, 94, 105, 110

Zinc thiolate, 107