Accessible PTC Catalysts, 125, 128, 275, 280 Charge Density View Of

Index

Accessible PTC catalysts, 125, 128, 275, magnesium peroxide reaction, 369 280 thiocyanate reaction, 366 charge density view of, 267 sulfide displacement, 364 effect on PTC reactions, 274 Acid strength, effect on air oxidations, on thiophenolate displacements, 272 535 Q# as a quantitative description of, Acidity of anions, effect on PTC, 328- 277 332 Acetals, permanganate oxidation of, 505 Acidity of C-H bonds in alkylations, 384 Acetanilide, N-alkylation of, 405 Acidity effect on deuterium exchange, Acetate displacement reactions, 355 440 displacement on poly(vinyl chloride), Acids, transfer from aqueous phase, 183 486 Acrylic acid, polymerization to polyes• Acetone, condensation with aldehydes, ters, 454 432 Activated carbon, catalyst separation by, Acetonitrile, C-alkylation of, 397 296 Acetophenone, C-alkylation of, 390 Active hydrogen compounds, oxidation Acetoxylation, aromatics by electrochemi- of, 535 cal oxidation, 552 Active site density, triphase catalysts, Acety lacetone 225 alkylation of, 385 Active site locus in triphase catalysts, vapor phase alkylation of, 390 218 Acetylenes Active sites of insoluble PTC catalysts carbonylation of, 602 kind of PTC groups attached, 232 oxidation with hydrogen peroxide, 527 crown ether and cryptand groups, 235 PTC dehydrohalogenation, 423 Activity of insoluble catalysts PTC Michael additions to, 430 active site density effect on, 225 trimerization of to aromatics, 616 agitation effect on, 222 oxidation with permanganate, 505 crosslinking effect on, 227 Acid chlorides effect of support composition on, 228 azide reactions with, 359 particle size effect on, 223 borohydride reduction of, 567 Activity of three-liquid phase systems, hydrogenolysis to aldehydes, 609 255

639 640 / Index

Acyl azides from acid chlorides, 359 oxidation with hypochlorite, 508 Acyl cyanides from acid chlorides, 346 oxidation with permanganate, 505 Adenine, N-alkylation of, 403 oxidation with persulfate, 543 Adsorption, for PTe catalyst separation, O-alkylation of, 410 295 periodate oxidation, Ru co-catalyst, Advantages for PTe in industry, 627 550 Aggregation of cation-anion pairs, 87 derivatives for analytical use, 626 Aggregation of anions, kinetic effect, 79 by reduction of aldehydes, 568 Agitation in PTe reactions, 14, 102-104 by reduction of carboxylate salts, 568 choice of, by PTe rate matrix, 322 Aldehydes effect on displacement reactions, 340 by alcohol oxidation, 505 variable in PTe reactions, 319 aldol condensation of, 431 effect on anion transfer rates, 321 alkylation of, 391 effect on side reactions, 321 borohydride reductions of, 565 with insoluble PTe catalysts, 222 by carbonylation of olefins, 601 in C-alkylation, 320 by chromate oxidations, 546 in cyanide displacement reaction, 320 in Darzens condensation reaction, 435 ultrasonic, effect on products, 537 by decarboxylation of halo-acids, 549 Air oxidation using PTe, 534 by diol cleavage with periodate, 549 of diphenylmethanes to ketones, 334 by hydrogenolysis of acid chlorides, free radical type, PTe in, 538 609 olefins to ketones, 540 from olefins with hydrogen peroxide, Alcohols 526 derivatization for analytical use, 626 by olefin oxidation with periodate, 549 from alkyl halides, 356 by oxidation of alcohols, 529 alkylation of sugars, co-catalyst, 178 by oxidation of olefins, 503 borohydride reduction co-catalyst, 565 by oxidations with hypochlorite, 508 co-catalysts for hydroxide transfer, 37- by oxidations with permanganate, 505 40, 177 by oxidations with persulfate, 541 cocatalysts for hydroxide reactions, by periodate oxidation, Ru co-catalyst, 326 550 dehydrohalogenation cocatalyst, 178, by persulfate oxidation of alcohols, 422 543 dihalocarbene generation cocatalyst, reaction, dichlorocarbene, ammonia, 426 429 effect on PTe polymerization, 139 reduction of, with sodium formate, 568 Hel or HBr reactions with, 183 in Wittig reaction, 433 hydroxide ion displacement on RX, Wolff-Kishner reduction of, 572 368 Aldimines, PTe alkylation of, 393 ketones by lithium aluminum hydride, Aldol condensation reactions, 431 568 Alkanes, from alkyl halides, 568 oxidation, bromate and Ru cocatalyst, Alkoxides, by alcohols with hydroxide, 549 37--40 oxidation with carbon tetrachloride, Alkyl structure, effect on displacement, 548 340 oxidation, chromate and dichromate, Alkyl halides 546 borohydride reduction to alkanes, 567 oxidation with hydrogen peroxide, 529 carbonylation of, 595 Index I 641

coupling with olefins and alkynes, 613 C-Alkylation using PTC, 383-388 hydrogenolysis of, 605 C-H acidity and, 384 olefin carbonylation to ketones, 601 chiral products from, 576-591 oxidation with chromate, dichromate, choice of bases for, 325 546 of ketones, 384 reduction, lithium aluminum hydride, polyethylene glycols PTC catalysts, 568 168 Alkyl phosphines from alkylphosphinates, N-Alkylation using PTC, 400--410 568 of amides, 405, 408 Alkyl silanes from alkylsilicon halides, choice of bases for, 325 568 of heterocycles, 400 Alkyl silicon halides, reduction of, 568 polyethylene glycols catalysts for, 166 Alkylation reactions with PTC of sulfonamides, 407 of acetophenone, 390 a-Alkylation using PTC, 410 of acetylacetone in vapor phase, 390 choice of bases for, 325 acidic hydrocarbons, 399 polyethylene glycols PTC catalysts, acidity effect on, 328-332 417 of aldehydes, 391 of sugars, alcohols as co-catalysts, 178 catalyst comparison for, 236 S-Alkylation, 418 chiral alkylations, 577, 583, 586 thiols and dialkyl sulfides from, 362 correlation by Q# of catalyst, 282 S- vs a-Alkylation in PTC reactions, 419 C-C chain polymers by, 474 Alkynes c- vs a-alkylation, 139, 385, 387 bromination of, 256 of diethyl malonate in vapor phase, carbonylation of, 602 390 carbonylation of vinyl bromides, 600 of esters and carboxylic acids, 391 coupling olefins and alkyl halides, 613 of ethyl acetoacetate, vapor phase, 390 oxidation with hydrogen peroxide, 527 hydroxide ion concentration effect, 106 oxidation with permanganate, 505 of imines, amino acid synthesis, 392 trimerization of, to aromatics, 616 insoluble PTC catalysts for, 397 Alkylurethanes by cyanate displacements, mono- vs di-alkylation, 397 371 of nitriles, 395 Allyianisole isomerization, three-phase, of phenylacetonitriles, 99 257 of polymer-bound phenylacetonitrile, Allylbenzene, deuterium exchange of, 493 439 polysulfoxides, selective catalysts, 173 Allylbenzene, isomerization of, 439 PTC variables involved in, 277 Alternating block copolymers by PTC, Q# use to correlate yields, 282 459 rate correlation by "Q#", 281 Alumina solvent-effect on catalyst choice, 284 as co-catalyst for displacements, 363 of sulfones, 397 as PTC catalyst, 249 C- vs a-alkylation in PTC reactions, as support for PTC catalysts, 250 385 Aluminum chloride in alkylation of 2-pyridone, 405 as PTC co-catalyst, 179 catalyst structure effect on, 387 transfer to organic phases, 186 in phenol alkylations, 416 Ambident ions in PTC reactions, 389 solvent effect on, 387 alkylation of desoxybenzoin, 385 in vapor-phase PTC reactions, 390 beta-diketones as, 388 642 I Index

catalyst structure effect on, 139, 387 hydrogenation of nitrobenzene, 571 effect of alkylating agent on, 387 N-alkylation of, 408 hydration effect on, 386 oxidation with hydrogen peroxide, 529 phenoxide and napthoxide as, 416 Anion activation by quaternary salts, 128 PTe alkylation of 2-pyridone, 405 catalyst structure effect on, 11 vapor phase reaction effects, 390 in polyethylene glycol with salts, 162 water effect on, 386 Anion poisoning of PTe reactions, 134 Amides Anion reaction on chloromethyl-poly- N-alkylation of, 401, 405 mers, 495 oxidation by hypochlorite, 512 Anion valence effect on transfer of, 26 periodate oxidation, Ru co-catalyst, Anion-activating catalyst types, 125 550 Anion-cation distance, solvent polarity, reduction of, 568 267 Amines Anion-radical coupling of phenols, 477 by borohydride reduction of azides, Anionic polymerization by PTe, 479 566 Anions, analysis of traces of, PTe in, oxidation of, by hypochlorite, 512 626 oxidation of, by permanganate, 506 Anions, associated with quaternary salt, oxidation with hydrogen peroxide, 529 135 as PTe catalysts, 140 Anions, character of, displacements, 343 by reduction of nitroaromatics, 612 Anions, concentration effect on PTe, 42 by reduction of dialkylamides, 568 Anions, hydration effect on reactivity, Amino acid polymers as PTe catalysts, 340 243 Anions, lipophilicity of, 324 Amino acids Anions, nucleophilicity effect of, 340 chiral, by PTe alkylations, 587 Anions, structure and aggregation of, 79 dichlorocarbene, aldehydes, ammonia, Anions, transfer of to organic phases, 15, 429 23, 322 synthesis of, general, 392 charge density view of, 269 4-Aminopyridinium salts effect of anion hydration level, 40-46 high-stability PTe catalysts, 142, 291 effect of nature of anion on, 310 PTe for divalent anions, 148 effect of stirring on, 102 separation of, by extraction, 293 effect on PTe displacement reaction, Ammonia transfer to organic phases, 188 340 Ammonium or phosphonium groups on phase transfer catalyst role in, 2, 5 resin, 220 with polyethylene glycol, 161 Analysis for trace anions using PTe, solvent effect on, 306, 307 351,622 Applications of PTe in industry, 626- Analysis of PTe reaction kinetics, 51- 630 71 variables in design of, 266 Anhydrous solid-liquid PTe reactions, Aqueous phase volume effect, 246 110 Aromatics compounds Anilines acetoxylation, cyanation of, 552 air oxidation of in basic PTe system, hydrogenation to saturated compound, 535 611 halogenation with HX + hydrogen per, hydroxylation by hydrogen peroxide, 532· 528 Index / 643

Aromatic hydrocarbons Benzylic chlorination with hypochlorite, from aryl halides by reduction, 568 520 halogenation by HX + hydrogen perox• Benzylic groups, oxidation of ide, 532 air, 535 oxidation with hydrogen peroxide, 527 hydrogen peroxide, 527 oxidation with permanganate, 506 hypochlorite, 518 Aromatic ketones, air oxidation of, 535 permanganate, 506 Aromatic methyl groups, oxidation of, persulfate, 541 541 Benzyltriethylammonium salt separation, Aromatic with activated halides 292 etherification of, 412 Betaines, as phase transfer catalysts, 152 fluoride exchange with, 353 Beyer-Villiger oxidation of ketones, 533 polychlorinated biphenyls reaction, 419 Bicarbonate ion displacement, 368 substitution on aryl chlorides, 352 Bio-oxidation of PTe catalysts, 293 S-alkylation with thiols, 418 Bisphenol-A, O-alkylations of, 413, 452- Arsonium quaternary salts 470 as phase transfer catalysts, 140 Bisulfide displacements to thiols, 362 polymer-bound for oxidations with H, Bis-binaphthyl crown ethers, as PTe, 156 533 Bis-phenolates, transfer of, 148 Aryl halides Bis-quaternary salts as PTe catalysts, 147 carbonylation of, 595 Block copolymers by PTe, 459 coupling with olefins and alkynes, 614 Bonding of PTe catalysts to silica, 251 hydrogenolysis of, 605 Boranes, PTe hydrogen peroxide oxida- reduction of, 568 tion, 533 Azapropellane-based salts as PTe, 146 Borohydride reductions, 565-569 Azide displacement reaction, 358 of acid chlorides to alcohols, 567 on acid chlorides, 359 of alkyl halides to alkanes, 567 on alkyl halides, 359 alkyl mercury compounds to radicals, on poly(vinyl chloride), 359, 484 568 on sulfonyl chlorides, 359 reduction of azides to amines, 566 Azides, alkyl, reduction to amines, 566 Bromate, oxidations with, 549 Aziridines, carbonylation of, 604 Bromide displacement reactions, 347 Azobenzenes, carbonylation of, 604 catalyst activity comparison in, 238, Azo-nitriles, from of amino-nitriles, 512 251 third liquid phase system of, 254 Barium hydroxide as PTe catalyst, 249 Bromide-chloride exchange reactions, 349 Bases in PTe reaction, selection of, 325 Bromination Benzaldehydes, oxidation of, 548 of aromatics with aq. Hel or HBr, 531 Benzamide, N-alkylation of, 406 of benzylic hydrogens with NaOel, Benzanilide, N-alkylation of, 406 520 Benztriazole, N-alkylation of, 401 of olefins, three-phase systems, 256 Benzyl alcohols, oxidation with NaOel, Bromochloropropane, selective reaction, 509 137 Benzyl chloride, carbonylation products, 2-Bromoethylbenzene, dehydrobromina• 596 tion, 420 Benzylcinchonium salts as chiral PTe, 2-Bromooctane, dehydrobromination of, 577 421 644 I Index

Bromo-groups on aromatics, replacement, Carbon-carbon chain polymers by PTC, 521 474 4-Bromo-2, 6-dimethy lphenol polymers, Carboxylate anion displacements, 355- 415 360 Butyraldehyde, C-alkylation of, 391 Carboxylates, reduction to alcohols, 568 Carboxylic acids Cadmium iodide as a PTC catalyst, 249 alkylation of, 391 Calixarenes by carbonylation of alkyl and aryl, 596 O-methylation of, 415 by carbonylation of alkynes. 602 as phase transfer catalysts, 185 derivatives for analytical use, 626 Caprolactam, N-alkylation of, 401 by hydrolysis of vinylic dibromides, Carbanions, air oxidation of, 535 617 Carbazole, N-alkylation of, 401 by olefin oxidation with periodate, 549 Carbene reactions in PTC systems, 423 by oxidation of alkynes, 505 Carbodimides, by oxidation of thioureas, by oxidation of benzylic methyls, 518 513 by oxidation of olefins, 503 Carbohydrates peracids from, 543 O-alkylation of, 411 Catalysts for PTC (see PTC catalysts) transfer to organic phases, 185 Catalyst concentration and kinetic order, Carbon monoxide in carbonylations, 595 104 Carbon monoxide as reducing agent, 612 Catalyst degradation, insoluble PTC, 246 Carbon number, "C#," correlation of Catalyst selection, criteria for, 266 PTC, 270, 276 Catalyst separation and recycle, 291 Carbon tetrachloride and NaOH as oxi- Catalyst structure dant, 547 and catalyst efficiency. 13. 127, 236, Carbonate ion displacements, 368, 409 284 Carbonyls, borohydride reduction, 565 C vs O-alkylation selectivity, 387 Carbonylation reactions, 595-605 hydroxyethyl-, for alkylations, 391 Carbony lation Catalysts for inverse PTe, 180 of alkynes, 602 Catalysts for PTC (see Phase transfer cata• of aziridines, 604 lysts) of azobenzenes, 604 Catalysts for PTC, 128-180 of chloromethyl groups on polymers, commercial sources of, 304 495 containing hydroxyethyl-, hydroxide, of olefins, 600 286 mechanism, involving PTC, 596 C# description of, 270 of phenol, 605 methyltributylammonium salts as, 285 of thiiranes, 605 phenylacetonitrile alkylations, 236 Carbon-carbon bond formation using quantitative correlations of, 270 PTC Q# description of, 277 alkylation reactions, 383 selection of, 284 chiral phase transfer catalysts for, 576-- separation and recycle of, 291 591 solvent-effect on choice of, 284 Darzen's condensation, 435 stability of quaternary salts in, 288 Michael addition reactions, 429 tetrabutylammonium salts as, 284 Wittig reactions, 433 trioctylmethylammonium salts as, 285 Index / 645

Catalysts for transfer of other species, Chiral quaternary salts as PTC catalyst, 179 146 Cation effect, with polyethylene glycol, Chloride displacement reactions, 347-350 161 Chlorination Cations, transfer to organic phases, 186 of aromatics with aqueous HCI, 531 Cation-anion interaction energies, 85 of aromatics, electrochemically, 552 Cation-anion pairs, aggregation, 87 of benzylic hydrogens with NaOCI, Cation-anion separation in PTC, 85 520 Cation-anion-solvent polarity relations, with carbon tetrachloride and NaOH, 267 547 Cellulose, O-alkylation of, 411 Chloroacetonitrile, Darzen condensation, Cerium co-catalyst, with persulfate, 543, 436 544 Chloroacetylene, from dichloroethylenes, Cesium fluoride as co-catalyst for PTC, 423 179 Chlorobromopropane, selective reaction, Chain length of quaternary salts, effect 137 on transfer, 28, 29 2-Chloroethyl vinyl ether, alkylation, 414 Charge density of cations and anions, 267 Chloroform and NaOH to dichlorocar• Chemical modification of polymers, 484- bene, 423-429 495 Chloromethyl-polymers, displacements, of pendant groups on polymers, 491 495 of terminal positions of polymers, 489 Chloromethylstyrene, in preparation of, Chiral phase transfer catalysis, 576 216 Chiral alkylation, 57&-591 Chloroprene, by dehydrohalogenation of, in amino acid synthesis, 586 422 of ketimines, 587 Choice of PTC catalysts, variables in, of oxindoles, 586 266 of Schiff bases, 589 Choice of solvents for industrial PTC, Chiral epoxidation, Jacobson catalyst, 315 526 Chromate and dichromate, oxidants, 546 Chiral halogenation of olefins, 532 electrochemical regeneration of, 546, Chiral induction with PTC 547 catalyst structure and, 583 transfer to organic phases, 546 effect of reaction conditions on, 583 Chromate as a co-catalyst in perborate, mechanism of, 578 546 Michael addition reactions, 589 Chromium trioxide, transfer by crowns, Chiral insoluble PTC catalysts, 243 547 amino-acid polymers as, 244 Cinchonium salts, as chiral PTC, 577, Chiral catalysts for olefin epoxidation 583 517,526 for chiral amino-acid synthesis, 587 Chiral PTC catalysts Clay, oleophilic, as support for PTC, 249 cinchonium and cinchionidine salts, Cluster-type quaternary salts as PTC, 149 587 Coal, PTC oxidation with permanganate, Darzens reaction, 436 506 Michael addition reactions, 430 Cobalt, as co-catalyst for PTC hydrogen, oxidations with air, 535 571 646 I Index

Cobalt carbonyl, co-catalyst, 595, 601 alcohols, for sugar alkylation, 178 Commercial applications of PTC, 626- alumina as, in sulfide displacement, 630 363 Commercial process for monomers, 414 aluminum chloride as, 179 Commercial PTC processes, solvent cerium, in persulfate oxidations, 543, choice, 315 544 Commercial sources of PTC catalysts, cesium fluoride as, 179 304 chromate and dichromate as, 546 Comparison soluble and insoluble PTC, cobalt carbonyl, for carbonylations, 238,239 595, 601 Complexation, III cobalt as, for hydrogenations, 571 of potassium salts and crown ethers, cuprous salts as, 178 111 effect on PTC polymerization, 139 of inorganics, by polyethylene glycol, formate reductions, ruthenium as, 568 159 gold, for nitric acid oxidations, 547 metal salts as PTC co-catalysts, 178 iodide as, for displacements, 179 with nickel compounds, as catalysts, iodide as, in aldehyde alkylations, 391 517 iron carbonyl as, for carbonylation, Condensations under PTC conditions, 597 429,431 Fe or Cu for hydroxylations, 527, 528 Condensation polymerization by PTC, metal salts and complexes as, 178 452 molybdate for alkyne oxidation with, Condensation reactions 527 aldol reactions, 431 osmium, for persulfate oxidation of, Darzen's reaction, 435 545 polyethylene glycols as PTC for, 167 osmium for periodate oxidations, 549 Copper co-catalyst for hydroxylation of, palladium as, for oxidations, 540 528 palladium as, cyanide displacement, Copper-palladium co-catalysts, 540 346 Cost of common commercial PTC cata• palladium as, for coupling reaction, lysts, 304 614 Counterion effects palladium as, for hydrogenolysis, 607 ambident ion selectivities, 388 ruthenium, in persulfate oxidations, on hydroxide ion transfer, 35 543 on catalyst choice, 323 ruthenium as, hypochlorite oxidn., 518 Coupling alkene, alkyne, alkyl halide, ruthenium as, for hydrogen peroxide, 613 526, 527 Co-catalysts for PTC reactions, 17, 125, ruthenium as, in aniline oxidation, 530 175 ruthenium as, for bromate oxidation, alcohols, for cyanide displacement, 549 178 transition metal and PTC, 594 alcohols, for dehydrohalogenation, transition metal-hydrodebromination, 178,422 606 alcohols, dihalocarbene generation, 426 transition metals, for oxidations, 522 alcohols, for hydroxide reactions, 37- tungstate, molybdate, epoxiation, 523- 40, 177,326 529 Index I 647

Criteria for PTC catalyst selection, 266 for polymerizations, 482 Criteria for solvent selection for PTC, for reduction of aryl halides, 568 305 Cyclohexadiene oxidation by singlet oxy• Cross-link effect on triphase catalysts, gen,539 217,227 Cyclopentadiene, alkylation of, 399 Crown ethers as PTC catalysts, 153-158 Cyclophosphazenes, as PTC catalysts, bound to insoluble supports as PTC, 169 220,235 C- vs O-alkylation in PTC reactions, 385 as catalysts for solid-liquid PTC, 113 in alkylation of 2-pyridone, 405 for dichromate oxidations, 547 catalyst structure effect on, 387 as high-temperature PTC catalysts, 291 in phenol alkylations, 416 by oligomerization of epoxides, 156 solvent effect on, 387 preparation of, 153 in vapor-phase PTC reactions, 390 on quaternary salts, as PTC, 150 C-Alkylation using PTC, 383-388 separation of, by extraction, 293 C-H acidity and, 384 solubilization of potassium salts, 111 chiral products from, 576, 591 transfer, lithium aluminum hydride, choice of bases for, 325 568 of ketones, 384 for transfer of permanganate, 502 polyethylene glycol PTC catalysts, 168 12-Crown-4, preparation of, 154 N-Alkylation using PTC, 400-410 18-Crown-6, preparation of, 154 of amides, 405, 408 Cryptand groups, on insoluble resins, choice of bases for, 325 220,235 of heterocycles, 400 Cryptands as PTC, 153 polyethylene glycols catalysts for, 166 as high-temperature PTC catalysts, 291 of sulfonamides, 407 preparation of, 155 O-Alkylation using PTC, 410 Cuprous salts as co-catalysts for PTC, choice of bases for, 325 178 polyethylene glycol PTC catalysts, 417 Cyanamide, N-alkylation of, 408 of sugars, alcohols as co-catalysts, 178 Cyanate ion, in displacement reactions, 370 Cyanation, electrochemical, aromatics, Darzens condensations, chiral PTC, 435, 552 436 Cyanide displacement reactions, 343-348 Decarboxylation of hydroxy-acids, 549 acid chlorides to acyl nitriles, 346 Decomposition of quaternary salts, 131 alcohols as solvents, co-catalysts, 178 during distillation steps, 295 catalyst comparison for, 164, 238, 239 by Hofmann reaction, 288 catalyzed by PTC on clay supports, of insoluble PTC catalysts, 246 249 by internal displacement, 288 solid-liquid PTC systems, 114, 234 of phosphonium salts, 132 Cyanide, reaction with epoxides, 346 temperature effect on, 290 Cyanoacetate alkylation to polymers, 474 Dehydrochlorination Cyclodextrins as inverse PTC catalysts, of poly(vinyl chloride), 486 180,608 of vinylidene chloride copolymers, 488 for hydrogenation, 571 Dehydrofluorination for olefin oxidation, 540 of poly(vinyJidene fluoride), 488 648 / Index

Dehydrohalogenation Dibromoalkanes alcohols as co-catalysts for, 178 dehydrohalogenation to alkynes, 423 catalysts for, 422 polythioetherfication with, 462 in manufacture of chloroprene, 422 reaction with potassium carbonate, 465 mechanisms of, 107 Dibromocarbene polyethylene glycol catalysts for, 163, addition to olefins, 426 166 generation of from bromoform, 426 three-phase PTC system, 255, 258 Dichlorobenzene, in displacements, 418 Density of active sites on insoluble, cata• 1,4-Dichlorobutene, in displacements, lysts, effect on activity of, 225 358 Derivatization of compounds by PTC for, Dichlorocarbene, other dihalocarbenes, 622 423-428 Design of PTC reactions, variables for, addition to olefins, 423 266 in amino acid synthesis, 429 Desoxybenzoin, alkylation of, 385 analytical use of, 623 Desulfuriation with iron carbonyls, 613 catalyst structure effect on, 138, 139 Deuterium exchange using PTC, 438 catalysts for preparation of, 423 of allylbenzene, 440 chloroform, 423 of chloroform, 101 correlation by Q# of catalyst, 282 of fluorene, 99, 440 hydroxyethyl quaternary catalysts, 423 of heterocycles, 440 in imidazopyridines synthesis, 428 of imidazoles, 440 polyethylene glycols as catalysts, 167, of indenes, 440 423 of ketones, 440 reaction with alcohols, 427 as a measure of acidity, weak acids, reaction with sulfur compounds, 428 440 from sodium trichloroacetate, 429 of phenylacetonitrile, 101 gem-Dichlorocyclopropanes, 412 of pyridines, 440 in alkylation of phenyl acetonitrile , 397 of thiazoles, 440 Dichromate and chromate of thiophenes. 440 oxidations with, 546 of weak acids, 331 transfer to organic phases, 546 Diacyl disulfides, from acid chlorides, Diene reduction to mono-ene, 569 364 Diethyl malonate, vapor phase alkylation, Diacyl peroxides from acid chlorides, 369 390 Diacyl sulfides, from acid chlorides, 364 Diffusion effects with insoluble PTC, 245 Dialkyl carbonates, from carbonate salts, Diffusion of reactants in insoluble PTC, 222 368 Dihaloalkanes, reduction of, 570 Dialkyl peroxides from alkyl halides, 369 Diketones, by oxidation of alkynes, 505 Dialkyl sulfides Dimer by-products in cyanide with acid, from alkyl halides, 362 346 permanganate oxidation of, 506 Diols hypochlorite oxidation of, 514 by cleavage with periodate, 549 Diarylimines, in Michael reactions, 430 cocatalysts, for hydroxide transfer, 37- Diarylmethanes, air oxidation of, 535 40,177 Diaryl sulfides, persulfate oxidation, 541 by olefin oxidation, 533, 545 Dibenzazepine, N-alkylation of, 402 Diphenic acid by phenanthrene oxidation, Dibenzo-18-crown-6, preparation of, 153 527 Index / 649

Diphenylmethane, alkylation of, 399 of ketones to alcohols, 570 Dipolar groups, insoluble PTC supports, of perfluoroalkyl iodides, 570 241 Divalent anions, transfer of, 31, 148 Dipolar polymers, as PTC, 171 Doublet anions in organic phases, 79 Disadvantages for commercial use of Dual PTC, two catalysts simultaneously, PTC,631 125, 175 Displacement reactions using PTC, 339- in vapor-phase PTC alkylations, 390 370 with acetate, 355 Electrochemical PTC reactions, 551 advantages of use of PTC for, 339 acetoxylation of aromatics, 552 with azide, 358 benzyl alcohol oxidation, 511 with bromide, 352 cerium oxidations, 552 with carbonate and bicarbonate, 368 chlorination of aromatics, 552 with carboxylate salts, 355 chromate regeneration, 546, 547 on chloromethylated polymers, 495 cyanation of aromatics, 552 with cyanate anions, 370 dichromate oxidations, 552 with cyanide, 343 hypochlorite regeneration, 511 with fluoride, 353 periodate regeneration, 550 with formate, 355 permanganate regeneration, 501 with hydroxide, 367 reductions with, 571 with iodide, 352 Elimination reactions with PTC, 419 iodide as co-catalyst for, 179 Ephedrine salts, selective catalysts, 152 with nitrite ion, PTC in, 366, 367 Epichlorohydrin on pendant groups on polymers, 491 of phenols, 414 with peroxide anions, 369 O-alkylations with, 411 phosphide and phosphinite anions in, polyetherification with, 457 370 Epoxidation polyethylene glycol catalysts for, 166 with hydrogen peroxide, 523 polysulfoxides and poly sulfides as, 174 by hypochlorite oxidation of olefin, on poly(vinyl chloride), kinetics, 486 514 reaction variables involved in PTC, and Jacobson manganese catalyst, 526 340 and nickel catalysts, 526 solid-liquid, crown-ether catalysts, 113 NaOCI in three-phase PTC system, 256 with sulfides, 363 of olefins, 514, 533, 541 with sulfite, to alkanesulfonates, 366 perfluoroolefins, 515 with superoxide anions, 369 of unsaturated ketones, perborate, 550 temperature effect on, 341 Equivalent conductance quat. solutions, with thiocyanate, 364 80 Disposition of waste material from PTC, Equilibrium features of halide exchanges, 293 347 Distillation for catalyst separation, 294 Ester interchange with PTC, 357 Distribution of quaternary salts, 132 Esterification, betaines as PTC for, 152 Disulfides, from oxidation thiols, 547, Esterification by PTC, analytical use, 622 552 Esterification (see carboxylate salts) Disulfide anion, in displacements, 364 Esters, alkylation of, 391 Dithionite reductions, 569 Ethers of dihaloalkanes to alkenes, 570 for analytical uses, 622 650 I Index

by PTe reactions, 368, 410 insoluble PTe catalysts for, 237 oxidation of, with permanganate, 505 reduction with, 568 polyethers, 457 Free energy of halide transfer, 24 polyethylene glycol as catalysts, 166 Free radical oxidation, use of PTe in, at polymer terminal positions, 490 538 Ethoxylated quaternary salts as PTe, 150 Free radicals from alkylmercury cpds., Ethyl acetate, solvent for hypochlorite, 568 509 Functionalization of insoluble PTe, 216 Ethyl acetoacetate, vapor phase alkyl• Fundamentals of PTe, 23-120 ation,390 Ethylene oxide oligomerization to, 156 Generation of quaternary salts in situ, Extraction into organic phases 140 anion effect on, 310 Glycerol, transfer to organic phases, 185 hydroxide, 35, 271 Glycidyl ethers by PTe etherifications, picrate, 273 411 quaternary bromides, 272 Glycols, co-catalysts for hydroxide ion, quaternary picrates, 273 37-40 quaternary salts, 26 Gold, co-catalyst, 547 solvent effect on, 309 Guanidinium bis-quaternary salts, PTe, Extraction processes for separation of, 144, 148 291 Guidelines Extraction of anions (see transfer) exploring new PTe reactions, 326 Extraction mechanism of PTe, 89 choice of insoluble PTe catalysts, 299 kinetics of, 91 PTe catalyst choice, 284 mechanism of, 49 screening new PTe reactions, 332 early criteria for distinguishing, 97 Halide displacement and exchange, 347 Factors in choice of PTe catalysts, 284 Halide ions Favorski reaction, 391 charge to volume ratio, 24 Ferrate, oxidations with, 550 free energy of transfer to organics, 24 Ferricyanide, oxidations with, 550 ionic radius effect on transfer, 24 Fluoalkylation of, 399 Haloacetylenes, by dehydrohalogenation, deuterium exchange of, 438 423 Fluoride displacements with PTe, 347- Halogenation of aromatic hydrocarbons, 354 531 aromatic halides, 353 Halo-acids, decarboxylation of, 549 sulfonyl chlorides, 354 Hard-soft cations and anions, effect of, Fluorinated alcohols, O-alkylation of, 412 267 Fluorobenzene, from cyclopentadiene, Heck reaction, 613 428 Hectorite clay, support of PTe catalyst, Fluorouracil, N-alkylation of, 403 249 Formaldehyde Heterocycles, deuterium exchange on, reductions with, 571 440 transfer to organic phases, 186 Heterocyclic quaternary salts as PTe, Formate 142, 145 displacement reactions with, 355 Hexaalkyldisilanes by PTe reactions, 165 Index f 651

Hexaalkylguanadinium salts as PTC, 144 oxidations with, 521 Hexamethy lenetetraamine, N -alkylation transfer to organic phases, 521 of, 410 use with W, Ru, Fe co-catalysts, 527 Higher-temperature PTC catalysts Hydrogenation using PTC systems, 570, 4-aminopyridinium salts, 291 605 crown ethers, 291 aromatics to saturated compounds, 611 cryptands, 291 olefins, selective, 609 polyethylene glycols and ethers, 291 Hydrogenative de halogenation of PCBs, TDA-l, 287, 291 258 Hofmann degradation of quaternaries, Hydrogenolysis of alkyl and aryl halide, 288 605 Hydration of anions, during PTC, 41 Hydrolysis of alkyl halides, 368 ambident ions, effect on, 386 during malonic ester alkylation, 392 anion transfer effect, 40-46 of polymers, 495 catalyst activity effect, 270 polyesters, 465 hydroxide, kinetic factor, 106 polyethylene glycols PTC catalysts, hydroxide ion transfer, 37 166 Hydrazinobetaines, as PTC, 153 vinylic dibromide to carboxylates, 617 Hydrideopentacyanocobaltate co-catalyst, Hydroquinone, oxidation of, 512, 539, 571 547 Hydrides, transfer to organic phases, 186 Hydroxide ion in PTC systems, 282, 383 Hydrocarbons, acidic, alkylation of, 399 alcohols as co-catalysts for, 326 Hydrogen bonding, effect on transfer, 29 betaines as catalysts for, 152 Hydrogen bromide, aqueous counterion effect on, 36 brominations with, 531 dehydrohalogenation mechanisms with, transfer to organics, 183 \07 Hydrogen chloride, aqueous displacements reactions of, 367 chlorinations with, 531 early criteria for mechanisms of, 97 transfer to organics, 183 effect of PTC structure on transfer, 35 Hydrogen chloride gas, exchange on effect of stirring on, \02 RBr, 350 effect of water concentration on, 36 Hydrogen peroxide enhancement by alcohol co-catalysts, alkyne oxidations with, 527 37---40 epoxidation of olefins, 533 factors affecting, 32 epoxidation with Jacobson catalyst, hydration as a kinetic factor in, \06 526 hydration effect on ambident ions, 387 epoxidation with nickel catalysts, 526 hydration of, reactivity, transfer, 319 olefin oxidations with, 526 hydroxy ethyl-quaternary salts PTC, oxidation of alcohols, 529 286 oxidation of aromatic amines, 529 inverse PTC mechanism for, \08 oxidation of aromatic hydrocarbons, mechanistic types with, 89-108 527 polyethylene glycols as catalysts, 287 oxidation of benzylic groups, 527 isomerization of olefins, 439 oxidation of ketones to lactones, 533 quaternary structure, stability and, 289 oxidation of olefins, 522 Q# to optimize catalysts for, 278 oxidation of ole fins to diols, 533 reverse, PTC mechanism for, \06 652 / Index

selection of base for reactions of, 325 Imidazoles selectivity values for, 35 N-alkylation of, 401 transfer by hydroxyalkyl salts, 151 deuterium-hydrogen exchange, 440 transfer to organic phases, 92, 271 Imidazole-based quaternary salts as PTe, Hydroxyls on polymers, activity rise, 146 493 Indene, alkylation of, 399 Hydroxyacids, decarboxylation of, 549 deuterium-hydrogen exchange, 438 Hydralkylation reactions, 391 Indoles 2-Hydroxyethyl groups, in catalysts for, N-alkylation of, 401 423 carbonylation of aziridines, 604 for hydroxide transfer enhancement, Industrial use of PTe, variables in, 266 151,286 Industrial PTe, solvent choices, 315 ephedrine-based as PTe, 152 Industrial use of PTe techniques, 626 Hydroxyl groups on crown ethers, effect, Inorganic reagent concentration effects, 241 15, 51-71 Hydroxylation, of olefins and aromatics, Inorganic polar surface, aid to PTe, 252 523, 528, 532 Inorganic solids as supports for PTe, Hypobromite oxidations using PTe, 508 228, 248, 250, 251 Hypochlorite ion, transfer of, 510 Insoluble PTe catalysts, 20, 207-300 Hypochlorite oxidations using PTe, 508 acetate displacement reactions, 357 alcohols, 508 active site density effect, 225 aldehydes, 508 activity of liquid-third-phase, 253 amides, 512 alkylation of phenylacetonitrile, 236 amines, 512 amino acid polymers as, 243 benzylic hydrogens, Ru co-catalyst, arsonium groups on, for oxidations, 518 533 chlorination of benzylic hydrogens, choice of, for PTe reactions, 299 520 comparison with soluble catalysts, 238, dialkyl sulfides, 514 239 nickel catalysts for, 517 crosslinking effect on, 227 nitriles, 512 crown ethers and cryptand groups on, ole fins , 514 235 olefins to epoxides, 515 cyanide displacement reactions with, oxidation of quinones, 512 234 perftuoroolefins, 515 degradation of, during reactions, 246 phenanthrene, 515 dipolar functions on, as PTe, 241 polynuclear aromatic hydrocarbons, effect of agitation on, 222 518 effect of catalyst quantity on rate, 231 thioamides, 512 effect of particle size of, 223 thioureas to carboximides, 513 effect of porosity on activity, 229 Hypochlorous acid, species present in, effect of ratio of reactant volumes, 246 508 effect reagent size on diffusion in, 245 factors affecting reactivity of, 300 hypochlorite oxidations, kinetics, 510 Ibuprofen, alkylation of phenylacetates, inorganic solid supports, 248 392 kind of PTe groups attached, 232 Index I 653

kinetic equations for, 247 Iodide anion PTe reactions polyethylene glycol as active group, displacement by bromide, 352 240 displacement reactions, 347 polyethylene glycol in fonnation of, catalyst comparison for, 238, 251 256 Iodide ion "poisoning" effect, 323 quaternary salt groups on, 232 kinetics of, 64 quaternary salts on clays as, 249 phenylacetonitrile alkylation, 396 selenium, for oxidations, 533 Ion pairs in chiral PTe, 81, 577 silica and alumina as, 250 correlation with Q#, 283 solvent effect on, 230 Ion-effect on kinetics of PTe reactions, spacer chain effect on activity, 230 87 thiocyanate displacement reactions, Ion-exchange resins, as PTe catalysts, 365 295 three-liquid phase systems, 255 Iron carbonyl use of, to facilitate separation, 296 co-catalyst for carbonylation, 597 Insoluble PTe catalysts (see Triphase and reduction of nitroaromatics, 611 polymer-bound PTC) reductions with, using PTe, 572 Intercalated salts on clay as PTe, 250 Iron co-catalysts, for oxidation, 527, Interfacial area in PTe, rate effect, 98 528 Interfacial catalyst-rich layers in PTe, 99 Isobutyraldehyde, C-alkylation of, 391 Interfacial concentration of PTe agents, 99 Isocyanates, from cyanate displacement, Interfacial mechanism of PTe 370 deuterium exchange in chlorofonn, 101 Isocyanates, from acyl azides, 359 early criteria for distinguishing, 97 Isomerization of olefins kinetics for Makosza mechanism, 94, allybenzene, 271 95 catalyst structure effect on, 274 mechanistic details of, 92 hydroxide ion concentration effect, 106 modified PTe mechanism for, 89 three-phase PTe system, 257 Interfacial tension, effect on PTe rate, 98 Isotactic anionic polymerization by PTe, Intrinsic rate, organic-phase reactions, 2 479 vs. mass-transfer rates, 51-71 Inverse micelles, mechanism of transfer, Jacobson catalyst, stereospecific epoxida• 9 tion, 526 Inverse PTe cyclodextrin as catalyst, for olefins, Ketirnines, alkylation, amino acid synthe• 540 sis, 393, 588 cyclodextrins as, 180 Ketocarboxylic acids, carbonylation of, hydrogenolysis of alkyl halides, 608 597 hydroxide ion in, 108 Ketols by olefin oxidation, 503 metal salts and complexes as, 181 Ketone alkylation pyridine-N-oxide as, 182 alcohol oxidation with pennanganate, reduction of aryl halides, 568 505 tetramethylammonium salts as, 182 alkylation of, 384 transfer of organics to water, 179 Beyer-Villiger oxidation, 533 Iodide co-catalyst for PTe displacement, borohydride reduction, 565 65, 179, 358, 391 chiral alkylation of, 577 654 / Index

chromate oxidation of, 546 insoluble catalysts, effect on, 247 condensation with aldehydes, 432 intrinsic rate-limited steps in, 57, 68 decarboxylation of hydroxy-acids to, Langmuir effects in, 486 549 limiting cases of, 54 deuterium-hydrogen exchange in, 438 Makosza interfacial mechanism, 94 olefin carbonylation of, with R-I, 601 mass-transfer limited reactions, 51-71 by olefin oxidation, 527 non-steady state, 74 by oxidation of alcohols, 529 ole fins isomerization, 99 oxidation of, carbon tetrachloride, 547 phenol-O-alkylation, 417 oxidation of with hydrogen peroxide, phenylacetonitrile alkylation, 99, 396 533 poisoning, co-catalysis by iodide, 65 oxidation of, with hypochlorite, 508 2,4,6-tribromophenol alkylation, 413 by persulfate oxidation of alcohols, solid-liquid displacement reactions, 543 113 reduction of with dithionite, 570 thiocyanate displacements, 365 reduction, lithium aluminum hydride, 568 Lactams, N-alkylation of, 401 Wolff-Kishner reduction, 572 Lactones, Beyer-Villiger oxidation of, Keto-aldehydes by alkyne oxidations, 527 533 Kinetics, of solid-liquid PTC reactions, Langmuir kinetics with PVC, 486 cyanide displacement reactions, Leaving group choice in displacements, 114---119 322,340 Kinetic order of PTC reactions, 51, 105 Lignin, O-alkylation, epichlorohydrin, in solid-liquid PTC, 119 411 Kinetics of PTC reactions, 51-119 Liquid crystalline polyethers by PTC, 460 air oxidations, 538 Liquid-liquid phase transfer catalysis, 49 analysis of, 71 Liquid-solid PTC reactions, 108-119 bromide-chloride exchanges, 351 Lithium aluminum hydride carbonylation of benzyl chloride, 596 reductions with, 568 catalyst concentration kinetic order, transfer with crown ethers, 568 104 LiI to aid in transfer of, 568 of chiral alkylations, 577, 581 Low-temperature oxidation with PTC, condensation polymerization, 454 512 dependence on ion-pairing, 82 deuterium exchanges, 99, 440 MacrocycIic and macrobicycIic com• dichromate oxidation of xylene, 546 pounds, 153 displacement reactions, 357 MacrocycIic polyethers, s-l PTC cata• displacements, poly(vinyl chloride), lysts, 109 485 Macroporous resins, for insoluble PTC, effect of interfacial tension on, 98 216,229 effect of ion-pair aggregation on, 87 Magnesium peroxide, with acid chlo• effect of stirring and agitation, 102- rides, 369 104 Makosza interfacial mechanism, 89, 92, extraction mechanism for, 51 94,99, 100 extraction mechanism kinetics for, 91 Malonate esters fractional kinetic orders in, 51-71, 87 carbonylation ethyl chloroacetate, 600 hypochlorite oxidations, 509, 510 minimization of hydrolysis in, 392 Index / 655

Michael additions, 430 Methacrylate polymers, as insoluble• vapor phase alkylation of, 390 PTe, 228 Malonic acids, conversion to aldehydes, Methyl acrylate, dihalocarbene addition 549 to, effect of catalyst structure on, Malononitrile, alkylation of, 397 139 Manganesecarbonyls, co-catalyst, 515, 617 Methylation of deoxybenzoin Manganese catalyst, for epoxidation, 526 catalyst structure in, 277 Manganese dioxide, complexation of, 501 correlation by Q#, 281 Manufacture of dinitriles by PTe, 344 Methylene chloride, S-alkylation with, Mass transfer to organic phases, 23 419 effect on kinetics of PTe, 51-71 Methyltributylammonium salts kinetics of, 65, 68 separation of, by extraction, 292 relationship to agitation, 102 as PTe catalysts, 285 Material safety data, PTe catalysts, 293, Michael additions using PTe, 429 303 acetylenes, 430 Mechanisms of PTe reactions, 48-119 allylphenylsulfones as addends, 431 Brandstrom-Montonari mechanism, 49 chiral phase transfer catalysts in, 589 chiral induction, 577 chiral PTe, 430 early criteria for distinguishing, 97 malonate esters as addends, 430 extraction mechanism, 89 phenyl acetonitrile as addend, 430 extraction mechanisms of, 49 thiophenols as addends, 430 interfacial mechanism details, 89, 92 trichloromethylate anion in PTe, 139 involving hydroxide reactions, 89-108 Microwave heating in PTe reactions, 17, kinetic order to distinguish, 105 412 liquid-liquid reactions, 49 Modification of polymers by PTe, 452- Makosza interfacial mechanism, 89, 495 92,99 Modified interfacial mechanism, 89 polymerization by PTe, 453 deuterium exchange in chloroform, 101 reverse PTe mechanism, 106 kinetics of, 96 sequence of steps in, 48 mechanistic details of, 95 solid-liquid PTe, 109 Molecular weight variation in polymers, Starks extraction mechanism, 49 454 Membrane reactors, for PTe, 302 Molybdate co-catalyst, for oxidations, Mercaptans, by NaSH displacements, 362 523,527,529 Mercury alkyls, borohydride reduction, Monomers from O-alkylations, 414 568 Morpholine-based salts as PTe, 145 Metal carbonyl anions, transfer, 595 Multisite phase transfer catalysts, 148 Metal co-catalysts for oxidation, 522 Metal oxides supports for insoluble PTe, Naphthalene, persulfate oxidation of, 544 250 Naproxen by PTe alkylation, 392 Metal salts Naphthoquinone by persulfate oxidation, complexation with polyethylene glycol, 544 159 Napthoxide anion, as ambident ion, 416 as co-catalysts, 178 Neopentyl alcohol, O-alkylation of, 412 as inverse PTe, 181 Nemst layer on insoluble catalysts, 222 Metals and metal hydrides, transfer of, Nickel compounds as co-catalysts, 517, 186 526 656 I Index

Nickel cyanide co-catalyst, 602 Omega phase, definition, in s-I PTC, 116 Nitric acid, oxidations with, 547 Optically active catalysts (see Chiral) Nitriles Organic phase polarity, effect on PTC, hypochlorite oxidation of, 512 29,31 alkylation of, 395 Organic phase volume, insoluble PTC, reduction of, 568 246 Nitrite Organic reactant size, in insoluble PTC, analysis for traces of with PTC, 367 245 displacement reactions, 366 Organic solvents for PTC reactions, 131 oxidation with, 367 ion-aggregation effect on, 81 Nitrobenzene, hydrogenation of, 571 polarity effects on PTC, 267 Nitro-compounds, reduction of, 570, 612 transfer of PTC catalysts into, 24 Nitrogen heterocycles, N-alkylation of, Organophilicity of PTC catalysts, 270 401 Osmium co-catalyst for oxidations, 545, Non-steady-state kinetics in PTC, 74 549 Nylon-66, modified, as a PTC catalyst, Oxidations using PTC, 500 365 of acetals with permanganate, 506 by air or oxygen in PTC systems, 537 Olefins of alcohols, benzylic and allylic, 543 bromination of, 256 of alcohols with bromate, 549 carbonylation of, 600, 601 of alcohols with hydrogen peroxide, catalysts for epoxidation of, 515 529 coupling, alkynes and alkyl halides, of alcohols with hypochlorite, 508 613 of alcohols with permanganate, 505 de hydro halogenation of, 422 of aldehydes with hypochlorite, 508 dihalocarbene addition to, catalyst, 139 of aldehydes with permanganate, 506 dihalocarbene additions, 423 of alkynes with hydrogen peroxide, epoxidation with hydrogen peroxide, 527 523 of alkynes with permanganate, 505 epoxidation with hypochlorite, 515 of amides with hypochlorite, 512 halogenation with HX and oxidant, 532 of amines with hypochlorite, 512 isomerization of, 167,331 of amines with permanganate, 506 isomerization, kinetics of, 99 of aromatic amines, 529 isomerization in three-phase PTC, 257 of aromatic hydrocarbons, 527 oxidation to diols and epoxides, 541, of benzylic groups, 506, 518, 541 545 of carbanions by air, 535 oxidation to ketones, 540 with carbon tetrachloride + NaOH, oxidation, chromate or dichromate, 546 547 oxidation with hydrogen peroxide, with chromate and dichromate, 546 522, 533 of coal with permanganate, 506 oxidation with hypochlorite, 514, 518 of dialkyl sulfides, 514 oxidation with periodate, 549, 550 electrochemical, with PTC systems, oxidation with permanganate, 503 551 from Wittig reactions, 434 epoxidation of olefins, 533 Ole fins , fiuoro-, oxidation of, 256, 515 with ferrate and ferricyanide, 550 Oligomeric ethers by PTC O-alkylation, free radical type, PTC in, 538 415 halo-acids to aldehydes, 549 Index / 657

hydrogen peroxide for, 521 Oxygen, singlet, generation of, PTC, 539 hydroxy-acids to aldehydes, 549 Oxygen carriers, use as PTC for oxida• hypochlorite, nickel catalysts for, 517 tion, 538 hypochlorite, polynuclear aromatics, Oxygen, oxidations with, using PTC, 518 534-540 hypochlorite and hypobromite, 508 Oxygen transfer to organic phases, 188 hypochlorite of perftuoroolefins, 515 of ketones with hypochlorite, 508 Palladium compounds of amlonic acids to aldehydes, 549 with copper, air oxidation co-catalyst, naphthalene, 544 540 with nitric acid, 547 co-catalyst for coupling reactions, 614 of nitriles with hypochlorite, 512 co-catalyst for hydrogenolysis, 607 of olefins, 503 co-catalyst, cyanide on vinyl halides, of olefins, with hydrogen peroxide, 346 243, 522, 526, 533 Parameters, quantitative, PTC catalysts, of olefins, with air, Ru, Pd, Rh, Cu, 270 540 Q-number to define "accessibility", of olefins, with amino-acid polymer, 277 243 Particle size effect, solid-liquid PTC, of olefins to epoxides, 514, 515 114, 223 of olefins to ketones, with air, 540 Patents for commercial uses of PTC, 627 of ole fins with periodate with Os, 549 PCB destruction by thiol S-alkylations, of olefins to epoxides, diols, 541 419 oxidation of ketones to lactones, 533 Pentaerythritol, etherification of, 256 with perborate, 550 Peptides, for transfer of inorganics, 172 with periodate, 549, 550 as insoluble PTC, 243 with persulfates, 540 Perftuoralkyl iodides pH dependence in hypochlorite, 508 sulfite displacement on, 366 of phenanthrene with hypochlorite, 515 reduction with dithionite, 570 of phenols with permanganate, 506 Perftuoroolefins, epoxidation of, 515 with polyethylene glycol catalysts, 167 Periodate, oxidations using PTC, 549 of polyethylene with permanganate, for decarboxylation of halo-acids, 549 506 for decarboxylation of malonic acid, of quinones by hypochlorite, 512 549 with singlet oxygen, using PTC, 539 electrical regeneration of, 550 with sodium nitrite, 367 in oxidation of alcohols, 550 of sulfides with permanganate, 506 in oxidation of aldehydes, 550 of sulfides with persulfate, 542, 544 in oxidation of amides, 550 with superoxide, 551 in oxidation of hydroxy acids, 549 of thioarnides with hypochlorite, 512 in oxidation of olefins, 550 of thioureas with hypochlorite, 513 Permanganate anion of triarylformazans, permanganate, 506 transfer to organic phases, 501 of triazolines with permanganate, 506 transfer by polyethylene glycols, 160 using "oxygen carriers" as PTC, 538 electrochemical regeneration of, 501 of weak acids, with KOH and air, 331 solubility of in organic solvents, 502 Oxidative coupling of phenols, 476 Permanganate oxidations using PTC, 500 Oxidative replacement of Br by CI, 352 of acetals, 505 658 / Index

of alcohols, 505 reductions with, 565 of aldehydes, 505 temperature effects on, 17 of alkynes, 505 Phase transfer catalysts, 123-258 of amines, 506 accessibility character of, 274-277 of benzylic groups by, 506 accessible type, 128 of coal, 506 acetate displacement reactions, 356 of ethers, 505 agitation effect on decomposition 0, of olefins, 503 134 of phenols, 505 4-aminopyridinium salts, stable PTC, of polyethylene, 506 143 of sulfides, 506 amino-acid polymers as, 243 of triarylfonnazans, 506 anion activation by, 127 of triazolines, 506 arsonium salts as, 140 Peroxide ion displacements using PTC azapropellane-based, 146 369 betaines as, 152 Per-carboxylic acids by persulfate, 543 bis-quaternary salts for, 147 Persulfate, 540 calixarenes as, 185 conversion of acids to peracids, 543 catalyst comparison for cyanide PTC, olefins to diols and epoxides, 541 164 oxidation of alcohols, 543 characteristics of common catalysts, oxidation of benzylic hydrogens, 541 304 naphthalene oxidation, Ce-cocatalyst, characteristics which affect use, 123 544 chiral, 576-591 sulfides oxidation, Ce cocatalyst, 544 chloride-bromide exchange reactions, polymerization initiation with, 481 350 sulfides to sulfoxides and sulfones, 542 choice of, 266 Pharmaceuticals by PTC O-alkylations, clay and inorgnaic supports for, 249 412 cluster-type quaternary salts for, 149 Pharmaceuticals by pheny lacetonitriles, commercial sources of, 124, 304 396 cost and availability, 124 Pharmaceuticals by PTC N-alkylation, co-catalysts for, 177 402 crown ethers as, 153 Phase transfer catalysis (see also PTC) crown-ether substituted quaternary, 150 analytical chemistry use of, 622 cryptands as, 153 anion activation in, 11 C# description of, 270 basic concepts of, 1 for deuterium-hydrogen exchange, 440 displacement reactions using, 339 in dichlorocarbene reactions, 423 fundamentals of, 23, 48 dipolar polymers as, 171 general steps in, 23, 48 displacement reactions, 342, 344 industrial perspectives in, 626 distribution into organic phases, 24, kinetics for extraction mechanism, 51 126 mechanisms for, 23, 48 dual PTC catalysts, 176 organic solvents in, 16 effect of size of, 276 physical chemistry of, 23, 48 ephedrine-based quaternary salts as, rate matrix for, 5 152 reaction types with, 3 ephedrine-based salts as, 430 reactive type catalysts for, 11 ethoxylated cyclophosphazenes, 169 Index I 659 ethoxylated quaternary salts as, 150 soluble polymers with polar groups, ethoxylated triazines as, 169 171 fractional kinetic orders in, 87 special types of, 20 generation of, in situ, 140 stability of, 124, 132 guanidinium salts, high stability, 144 structure effect on efficiency, 127 heterocyclic quaternary-onium salts, structure effect on selectivity, 137 142 structure of, effect on selectivity, 135 high-temperature, 287 structure-activity relationships of, 267 hydrazinobetaines as, 153 substituted quaternary salts as, 151 hydroxyl-substituted, as PTe, 151 sulfides as, via sulfonium salt for, 362 imidazole-based, 146 sulfonium salts as, 140 insoluble catalysts for PTe, 207-258 tetraalkylarnmonium salts as, 125 inverse, cyclodextrins for, 180 tetrazolium salts as, 147 kinetic order of PTe reactions in, 104 toxicity of, 124 macrocyclic and macrobicyclic ethers, tris(3,6-dioxaheptyl)amine as, 157, 165 153 types of, 18 morpholine-based, 145 volume to charge ratio effect in, 23 multisite catalysts, 148 Phase transfer catalyst structure, effects on organophilicity of, 270 counter ion of, selection of, 323 phosphonium salts as, 140 air oxidations using PTe, 536 piperidine-based, 145 aniline halogenation, 532 in polyetherification reactions, 463 aromatics halogenation, 532 polyesterification, 465 carbonylation, 603 polyethylene glycols and ethers as, C vs O-alkylation, 387 157, 162 dehydrohalogenation, 487 in polymerization reactions, 455 hydrogenolysis of bromides, 606, 607 polypode ethers as, 168 poly (vinyl chloride) reactions, 485 polysiloxanes as, 175 product distributions, 530, 542 poly sulfides as, 174 reductions with iron carbonyl, 612 polysulfones as, 175 PTe, improvement commercial pro- polysulfoxides as, 173 cesses, 626 poly(amides) as, 171 PTe functional groups, on supports, 220 poly(sulfoxides) as, 171 PTe in industrial processes, 293 poly(vinylpyrrolidone) as, 172 PTe process design, 319 quantitative correlations of, 270 PTe rate matrix, 5-8 quaternary salts as, l25-153 anion placements in, 325 quaternary salts on clays, 249 and choice of agitation, 322 quinine and quininium salts as, 430 Phase transfer reactions quinuclidine-based quaternary salts, acidity of anions effect, 328-332 146 advantages for industrial uses, 627 Q# description of, 277 agitation effect on, 319 recovery and recycle of, 124, 188, 291 condensation, commercial utility of, selection of, 284 432 selenonium salts as, 140 condensations, 429 separation and recycle of, 124, 188, C-alkylations, 383 291 dehydrohalogenation, 419 siloxane-substituted salts as, 153 displacement reactions with, 432 660 I Index

effect of solvent on, 305 Phosphide ion displacements using PTC, guidelines, of new reactions, 327 370 kinetic orders in, 105 Phosphinite ion displacements using kinetics of, 49 PTC,370 optimal water concentrations in, 318 Phosphonium quaternary salts as PTC, oxidations using PTC, 500--552 140 oxidative coupling of phenols, 476 bound to insoluble supports, 220 polymerization, polymer chemistry, decomposition from hydroxide, 289 452--495 in Wittig reactions, 434 polymerizations by, 452--495 Phosphate co-catalyst for epoxidation, poly(vinyl bromide), 489 523 poly(vinyl chloride), 486 Photochemistry in PTC poly(vinylidene fluoride), 488 oxidations with singlet oxygen, 572 PTC dihalocarbene generation, 427 polymerization, 483 quick screening of, 332 reductions using PTC, 572 reductions using PTC, 565-572 thiocyanate reactions with, 366 using strong bases, 383 Phthalimide, N-alkylation, 401, 408 variables in design of, 266 Pinacol, co-catalyst with hydroxide, 38 Wittig reaction, 433 Piperazines, N-alkylation of, 402 Phenanthrene Piperidine-based salts as PTC, 145 oxidation to diphenic acid, 518, 527 Poisoning effect of iodide ion, 64, 323 oxidation to phenanthrene epoxide, Polarity of organic solvents, effect on, 515 131,270 Phenetoles by PTC O-alkylation, 412 Polyamides by PTC polymerization, 454 Phenols Polycarbonate formation using PTC, 464 carbonylation of, 605 Polycarbonates from PTC displacement, alkylation of, 143 369 O-alkylation of, 411, 412 Polychloro-aromatics, dehalogenation of, C-vs O-alkylation, catalyst, 139 258 oxidation to quinones with oxygen, Polyesters by PTC polymerization, 454 539 catalyst effect on molecular weight, 465 oxidation with permanganate, 505 from acrylic acid, 454 oxidative coupling by PTC, 476 Polyethers, by PTC polymerizations, 457 nitrite reaction on aryl halides, 367 from bis-phenol-A, 413 Phenolphthalein polythiocarbonates, 471 Polythioethers by PTC polymerization, Phenothiazine, N-alkylation of, 402 457 Phenoxide anion, as ambient ion, 416 Polyethoxylated compounds as PTC, 168 Phenylacetic acid, C- and O-alkylation, Polyethylene oxidation with permanga• 392 nate, 506 Phenylacetone, alkylation of, 384 Polyethylene glycols as PTC catalysts, Phenylacetonitrile alkylation, 395 157-168 comparison of catalysts for, 236 anion effect on, 161 hydroxide concentration effect on, 106 bound to insoluble supports, 220 in Michael addition to acetylenes, 430 catalysts for O-alkylation of, 411 Phenylethyl bromide dehydrobromination, catalyst for dihalocarbene reaction, 167 255 catalysts for condensation reaction, 167 Phosgene, in PTC polymerizations, 465 catalysts for C-alkylations, 167 Index / 661

catalysts for dehydrohalogenations, 166 functionalization of resins for, 216 catalysts for displacement reaction, 166 macroporous resins for support of, 216 catalysts for hydrolysis reactions, 166 microporous resins for support of, 216 catalysts for N-alkylation reaction, 166 molar scale, 210 catalysts for olefin isomerization, 167 polyethylene glycol groups on, 220 catalysts for oxidation reactions, 167 polymer support, preparation, 211 catalysts for O-alkylations, 416 pore size of insoluble resins for, 216 catalysts Williamson ether synthesis, porosity effect on activity of, 229 166 preparation of polymer-bound, 210 cation effect on, 162 quaternary onium salts on, 220 comparison with other catalysts, 164 solvent effect on, 230 complexes with metal salts, 159 spacer chain effect on activity, 230 effect of molecular weight, 164 spacer chains in, 219 formation of three-phase systems, 256, styrene-divinylbenzene supports for, 420 211 high-temperature PTC catalysts, 291 suspension polymerization procedure, in hydroxide transfer reactions, 287 216 on insoluble PTC supports, 240 Polymers, chemical modification, 484- preparation of, 157 495 quaternary-groups on, as PTC, 150 Polymerization by PTC reactions, 452- separation, third-layer formation, 293 495 solvent effects on, 162 acrylic acid to polyesters, 454 third-phase formation with, 162 anionic polymerizations, 479 transfer of inorganic salts, 159 carbon-carbon chains by, 474 Polymerization, of phosgene, diphenols, catalyst effect on molecular weight, 139 465 Polymer backbone modification using condensation polymerization, 452 PTC,484 dibromoalkanes in, 465 Polymers, as supports for insoluble PTC free-radical polymerizations, 481 218-230 mechanisms for, 453 active site density effect, 225 phosgene in, 465 active site location on, 218 polyamides, 454 agitation effect on activity, 221 polycarbonates from, 464 characteristics affecting activity, 220 polyesters, 454 chloromethylstyrene in preparation, polyethers, 457 216 polyphenylene oxides, 477 comparison with soluble PTC, 208, polyphosphonates, 454 210 polysulfonates, 454 components of, 211 polysulfones, 454 cross-linking effect on, 227 polythiocarbonates from, 464 crown ethers on, 220 polythioesters, 454 cryptands on, 220 polythioethers, 457 diffusion effect in, 209 Poly-C-alkylation, 474 effect of catalyst quantity on rate, 231 radical anions in, 187 effect of particle size, 223 redox initiators for, 482 effect on ambident ion selectivity, 416 solvent effect on condensations, 468 functionalization of, 216 thiophosgene in, 467 662 / Index

Polymer-end functional groups, reaction, Potassium carbonate as base in PTC, 325 489 Potassium hydroxide as a base in PTC, Polymer-modification by PTC reactions, 325 452-495 Potassium metal, transfer with TDA-l, Polynuclear aromatics oxidation, 527, 165 535, 544 Potassium permanganate, transfer of, 502 Polyphenylene oxide, end-capping, 490 Potassium salts, solubilization, crowns, Polyphenylene oxides, oxidative cou• III piing, 476 Product selectivity, effect of catalyst, Polyphosphonates by PTC polymeriza• 135, 139 tion, 454 Propionaldehyde, C-alkylation of, 391 Polypode polyetbers as PTC catalysts, Protein fragments, as insoluble PTC, 243 168 Purines, N-alkylation of, 403 Polysiloxanes as PTC catalysts, 175 Pyrazole, N-alkylation of, 401 Polysulfide-links in rubber, scission of, Pyridines, deuterium-hydrogen exchange, 489 440 Polysulfides as PTC catalysts, 174 Pyridine-N-oxide as inverse PTC, 182 Polysulfonates by PTC polymerization, Pyridones, ambident ions in alkylation, 454 416 as PTC catalysts, 175 Pyridones, selective O-alkylation of, 416 Polysulfoxides as PTC catalysts, 173 2-Pyridone, N- and O-alkylation of, 405 Polythiocarbonates, PTC polymerization, Pyrrole, N-alkylation of, 401 464 Polythioesters by PTC polymerization, Quadrupole ions, effect on PTC kinetics, 454 87 Polythioethers, by PTC polymerization, Quantitative parameters PTC catalysts, 461 270,277 Poly(2,6-dimethylphenol), capping of, Quaternary ammonium salts, 124-153 490 accessible type, 128 Poly(amides), by PTC polymerization, adsorbed on clays, 249 171 aggregation of, in organic phases, 80 Poly(methyl methacrylate), hydrolysis, anion activation by, 128 495 anion, effect on catalyst activity, 135 Poly(sulfoxides), as PTC catalysts, arsonium salts, as PTC, 140 171 bases for dehydrohalogenations, 107 Poly(vinyl bromide), reactions of, 489 bound to insoluble supports, 220 Poly(vinyl chloride), in displacements, carbonylation, 603 485 cation-anion-solvent effects, 267 acetate displacement, 486 concentrations at interfaces, 99 azide displacement on, 486 containing hydroxyetbyl groups, 286 azide displacement reactions with, 359 crown-ether substituted, as PTC, 150 dehydrochlorination of, 486 decomposition of, temperature on, 290 kinetics of, 486 distribution into organic phases, 126 Poly(vinylpyrrolidone), as PTC catalyst, ethoxylate-substituted, as PTC, 150 172 extractability, of, 28, 272, 309, 501 Pore size, of resins for support of PTC, for dehydrohalogenation, 107 216,229 heterocyclic, as PTC catalysts, 142 Index / 663

hydroxy-substituted as PTC, 151 Reaction variables in PTC reactions, 12 in situ generation of, 140 Reactions catalyzed by phase transfer, 3 insoluble supports, 232 Reactions catalyzed by insoluble PTC, ionization constants of, 83 212 permanganate salts, extractability, 501 Reactive-inverse PTC catalysts, 183 phosphonium salts, as PTC, 140 Recovery of phase transfer catalysts. 188, Q-number correlations with, 283 291 stability of during PTC reactions, 131, Recycle of insoluble PTC catalysts, 124, 288 246 structure effect on air oxidations, 536 Redox polymerization by PTC, 482 structure, allylbenzene isomerization, Reductions using PTC, 565-572 274 borohydride for, 565 structure effect on decomposition of, of dihaloalkanes to alkenes, 570 290 dithionate anion for, 569 structure effect on displacements, 485 electrochemical, 552 structure effect on hydrogenolysis, formate salts for, 568 606,607 hydrogen, using PTC, 605 structure effect, picrate extraction, 309 lithium aluminum hydride for, 568 structure effect on rates, 13 nitroaromatics to anilines, 570 structure effect on transfer, 521 of nitrobenzene, effect of catalyst, 611 structure effects on distribution, 26, 29 nitrobenzene, variable products by, 571 structure, effect on halogenation, 532 of nitrogen compounds, using PTC, structure, on hydroxide transfer, 35 610 structure, on product distributions, 530 of perfluoroalkyl iodides, 570 structure-activity relationships of, 267 photochemical, using PTC, 572 third liquid phase formation with, 255 polyethylene glycols as PTC, 167 sulfonium salts, as PTC, 140 with sulfur-containing anions, 569 Quinuclidine-based salts for PTC, 146 Removal of phase transfer catalysts, 124, Q-number, to describe catalysts, 277-282 188 Q-number, on ambident ion alkylation, Resin supports for insoluble PTC, 219 386 Resin-bound phase transfer catalysts (see Polymer-bound catalysts) Radical initiated polymerizations using, Rhodium, as co-catalyst for carbonyla• 481 tion,601 Radical-anions, transfer of, 187 Rhodium, as co-catalyst for oxidation, Rates (see Kinetics) 540 Rate enhancement in three-phase PTC, Ring substitution degree, insoluble PTC, 258 225 Rate increase by use of dual catalysts, Robinson, annelations, chiral, 430 176 Ruthenium compounds, as co-catalysts, Rate matrix for PTC reactions, 5 540 Rates of PTC reactions aromatic hydrocarbons, 527 effect of anion hydration on, 42 bipyridine complex, 518 ionic strength effects on, 43 bromate oxidations, 549 using insoluble PTC catalysts, 248 hydrogen peroxide oxidations, 526, Reactants, size effect, insoluble PTC, 530 245 hypochlorite oxidations, 518 664 / Index

periodate oxidations, 550 Size of quaternary cations on transfer, persulfate oxidation, 543 126 Sodium borohydride (see Borohydride) Sodium formate (see Formate salts) Salcomine, as an oxygen transfer agent, Sodium hydroxide, as a strong base, 539 325 Schiff bases, chiral alkylation of, 589 Sodium metal, transfer of, with TDA-l, Screening of new PTe applications, 332 165 Sebacic acid, in polymerizations, 455 Solid-liquid PTe reactions, 108-119 Selectivity in PTe reactions, 137 kinetics of, 113 in acetate on bromochloral, 356 omega phase formation in, 116 bis-quaternary salts for alkylation, 147 polyethers as catalysts for, 109 catalyst structure effect on, 135, 139 water effect in, 110 hydrogenation unsaturated ketones, 609 Solubilization of catalyst plus anions, 307 hydroxy-substituted saIts, hydroxide, Solubilization (see Transfer), 568 151 Soluble polymers containing polar group, polysulfoxides for alkylation, 173 171 structure effect of catalyst on, 135, 139 Solvents, and their effects in PTe, 16, in transfer of anions, 24, 27 131 Selenonium salts as PTe catalysts, 140 alkylation of deoxybenzoin, 312 Separation and recovery of PTe catalyst, anion solvation, 306 124, 188 anion transfer effect of, 29, 31, 132, adsorption methods for, 295 307 of aminopyridinium catalysts, 293 bromide displacements, effect of, 312 of benzyltriethylammonium catalysts, cation-anion distance effect on, 267 292 chiral alkylations, effect of, 583 of crown ethers, 293 criteria for selection of, 305 distillation processes for, 294 C vs O-alkylation selectivity, 387 extraction processes for, 291 dielectric constant and, 307 of methyltributylammonium catalysts, diffusion of, through insoluble PTe, 292 231 of polyethylene glycols, 293, 295 displacement reactions, effect on, 340 for recycle of PTe catalysts, 291 distribution of quaternary salts, 132 of TDA-l as PTe catalyst, 293 effect on insoluble-PTe activity, 230 with tetrabutylammonium catalysts, examples for choice of, 311 292 hydrogen bonding effect of, 30 using three-liquid-phase PTe system, in hypochlorite oxidations, 509 255 industrial process considerations, 315 Silica, as support for PTe catalysts, 250 ion-pair separation effect, 306 adsorption of PTe catalysts on, 295 leveling effect in, 29 with chemically bound PTe groups, polarity of, 307 251 in polycondensations, effect of, 468 Silochrome as support for insoluble PTe, quaternary salt transfer effect, 309 250 reactivity effect of, 305 Siloxane-substituted quaternary salts, 153 screening of, 318 Singlet oxygen generation, 539 solubilization of PTe ion pairs, 307 Index / 665

stabilization of transition state, 306 Substitution reactions (see also Displace- transfer of salts with PEGs, effect, 162 ment reactions) trifluoroethoxide displacements, 312 cyanide displacements, 234 use of no solvents in PTC, 314, 316 iodide as co-catalyst for, 179 Solvent-swelling of insoluble PTC, 230 phase transfer catalysts for, 151 Solvent-free PTC, 314, 316, 401 polyethylene glycols as catalysts, 166 Spacer chains in insoluble-PTC catalysts polysulfoxides and polysulfides as, 174 effect, triphase catalyst activity, 219, Sulfide displacement reactions, 362 230 with acid chlorides, 364 synthesis of, 219 dialkyl sulfides from, 362 effect on activity, 230 PTC systems for, 362 Special quaternary ammonium salts as PCB removal with, 364 PTC, 142 Sulfide reduction of nitroaromatics, 570 Stability of PTC catalysts Sulfides, dialkyl- or diaryl- Stability of salts in PTC nitric acid oxidation to sulfoxides, 547 guanidinium salts, 144 oxidation by perrnanganate, 506 insoluble PTC catalysts, 246 oxidation with hypochlorite, 514 4-aminopyridinium salts, 143 persulfate oxidations of, 541, 544 simple quaternary saits, 131, 288 as phase transfer catalysts, 362 phosphonium salts, 132 Sulfinate salts, bis-, in polymerization, Stereoselective PTC (see Chiral) 456 Sterically hindered phenols, O-alkylation, Sulfite displacements, alkanesulfonates, 413 366 StericaIly hindered thiols, S-alkylation, Sulfonamides, N-alkylation of, 407 418 Sulfones in PTC reactions Stirring effect in PTC reactions, 102- alkylation of, 397 104 by perrnanganate on sulfides, 506 Stoichiometric phase transfer reactions, by persulfate oxidation of sulfides, 541 533 Sulfonium salts as PTC catalysts, 140 Strong base reactions using PTC (see Hy• generation in situ, as PTC catalyst, 141 droxide) Sulfonyl azides from sulfonyl chlorides, Structure of phase transfer catalysts, and 359 effect of Sulfonyl chlorides, in polymerizations, accessibility relationship effects, 281 455 choice of, effect of, 284 Sulfonyl fluorides, sulfonyl chlorides, distribution into organic phases, 26 354 effect, C vs O-alkylation select., 387 Sulfoxides effect on transfer, 24 by hypochlorite oxidation sulfides, 514 effect on picrate extraction, 309 by nitric acid oxidation of sulfide, 547 effect on PVC displacements, 487 by perrnanganate oxidation sulfides, hydroxide ion transfer, 35 506 quaternary salt PTC catalysts, 267 by persulfate oxidation of sulfides, selectivity effect of, 137, 138 541,544 size relationship effects, 276 Superoxide anion, oxidations with, 369, Suberonitrile manufacture, PTC process, 551 344 Suppliers of common PTC catalysts, 304 666 / Index

Surface activity of PTC catalysts, 98 Thioetherification by PTC reactions, 418 Surface layers of salts, ion transfer, 115, Thiol groups on polymers, reactions of, 116 494 Swelling of insoluble PTC catalysts, 230 Thiolates, in Michael reactions, 431 Synergy from use of two PTC catalysts, Thiols 176 oxidation to disulfides, 552 from NaSH displacements, 362 TDA-l, [see tris(3,6-dioxaheptyl)amine], Thiol-carboxylic acids from thiiranes, 605 165 Thiophenes, deuterium exchange in, 440 Teflon solid support for insoluble PTC, Thiophenol, Michael additions in, 430 250 Thiophenols, oxidation of, 547 Tellurite, in oxidation of thiols, 552 Thiophosgene, in polymerization, 467 Temperature effects on PTC reactions, 17 Thiophosphinic, oxidation. 514 on displacement reactions, 341 Thioureas, oxidation of, 513 quaternary salt decomposition, 290 Third-layer (liquid) systems inPTC, 10,252 Terminal polymer positions, reactions, for dehydrohalogenation, 258, 420 489 interfacial systems in s-I PTC, 99 Tertiary alcohols from boranes, 533 omega phase in s-l PTC reactions, 116 Tertiary amides, reduction of, 568 polyethylene glycol catalyst for, 162, Tert-butyl chloride, PTC displacements, 417 365 for separation of PTC catalysts, 293 Tetraalkylammonium or phosphonium Toluenes, nitro-substituted, oxidation, salts (see Quaternary salts) 537 Tetraarylporphyrins with Mn as PTC. 515 Toxicity of common PTC catalysts, 304 Tetrabutylammonium salts, 284 Trace water effects on solid-liquid PTC, in third-liquid phase PTC systems, 253 114 separation of, 291 Transfer to organic phases Tetramethylammonium salts as inverse of acids, 183 PT, 182 agitation and stirring effect on, 102 Tetrazolium salts as PTC catalysts, 147 aluminum chloride, 186 Theobromine, N-alkylation of, 403 ammonia, 188 Theophylline, N-alkylation of, 403 anion hydration effect on, 40-46 Thiadiazoles, from thioamides, 513 anion Iipophilicity and, 324 Thiazoles, deuterium exchange in, 440 anion structure effect on, 25, 310 Thia-crown compounds as phase transfer, anion valence effect on, 26 362 of anions, 322 Thiiranes, carbonylation of, 605 of carbohydrates, 185 Thioamides, oxidation of, 512 catalysts for, 23 Thiocarbenes, generation of, 429 of cations, 186 Thiocresylate displacement reactions, 238 charge density view of, 269 Thiocyanate in PTC displacements, 364 of chromate and dichromate, 546 comparison of catalysts for bidentate crown ethers for, III ion, selectivity of, 364 divalent anions in, 31, 148 kinetics of, 365 effect on PTC displacements, 340 Thioesters, alkylphosphinate, reduction, extraction constants for, 26 568 of formaldehyde, 186 Index I 667

of glycerol, 185 Trichloroacetate to dichlorocarbene, 429 of HCI and HBr from aqueous phases, Trihaloacetamides, N-alkylation of, 408 183 Trioctylmethylammonium PTe, separa- of hydrogen peroxide, 521 tion, 294 of hypochlorite anion, 510 Trioctylmethylammonium salts as PTe, of ion pairs, 23--46 285 of metals and metal hydrides, 186 Triphase catalysis (see also Insoluble omega phase formation in, 116 PTe catalysts) of oxygen, 188, 539 active site density effect on, 225 permanganate by polyethylene glycol, active site location on, 218 501 agitation effect on reactivity with, 222 of permanganate by quaternary salts, catalyst parameters effect, 221 501 catalyst quantity effect, 231 of permanganate with crown ethers, chloromethylstyrene in preparation, 502 216 polarity of organic phase, effect, 29 comparison with soluble PTe, 208, of polyethylene glycol, 160 210 of quaternary ammonium bromides, crosslinking effect on, 227 272 crown ethers on, 220 of quaternary ammonium picrate, 273 cryptands on, 220 of radical anions, 187 diffusion effect in, 209 of rose bengal, singlet oxygen with, functionalization of resins for, 216 539 macroporous resins for support of, 216 selectivity constants for, 24 microporous resins for support of, 216 in solid-liquid PTe reactions, 116 molar scale, 210 soluble polar polymers for, 171 particle size effect on activity, 223 solvent effect on, 306, 307 polyethylene glycol groups on, 220 of species other than anions, 21 polymerization procedure effect on, stirring effect on, 102 218 TDA-l as PTe catalyst for, 165,287 pore size of insoluble resins for, 216 of water, 185 porosity effect on activity, 229 Transfer step, mechanisms for, 2, 7 preparation and types of, 210, 211 Transfer-rate limited reactions, 276 quaternary onium salts on, 220 Transition metal, on hydrodebromination, solvent effect on, 230 606 spacer chain effect on activity, 219, Transition metal-PTe co-catalysis, 594 230 Trialkylmethanols, from boranes, 533 styrene-divinylbenzene supports for, Triarylformazans, oxidation of, 506 211 Triazines, alkylated, 370 suspension polymerization procedure, Triazines, ethoxylated, as PTC catalyst, 216 169 tabular survey of, 212 Triazolines, oxidation of, 506 Triphenyl methane, C-alkylation of, 400 Tribromide ion, formation of in PTe, Tris(2,5-dioxaheptyl)amine [TDA-l], 256,532 157, 165 Trichloroacetate displacement, products, as high-temperature PTe catalyst, 287, 358 291 668 / Index

pennanganate oxidations with, 502 Vinyl monomers, PTe-polymerization of, separation of, by extraction, 293 481 Trithiocarbonate as a reducing agent, 570 Vinylation of polymer tenninal groups, Tungstate co-catalyst 489 in alkyne oxidations, 527 in epoxidation of olefins, 523 Wacker process, PTe modification of, in oxidation of aromatics, 527 540 in hydrogen peroxide oxidation, 529 Wastewater clean-up with hypochlorite, 515 Ultrasonic agitation in PTe reactions, Waste-treatment questions in PTe, 293 222,537 Water Urea derivatives, N-alkylation of, 408 C vs O-alkylation, effect on, 386 Ureas, alkylated, from cyanate reaction, fluoride displacements, effect on, 353 370 nitrite displacements, effect on, 367 Vanadium carbonyl anions, in PTe, 607 optimal concentrations of, 318 . Vapor phase PTe reactions, 21 solid-liquid PTe reactions, 110-119 alcohols with Hel or HBr, 185 trace level effects on s-I PTe, 114 alkylation of acetylacetone, 390 transfer to organic phase, 185 alkylation of diethyl malonate, 390 Weak- and strong acid-anions in PTe, alkylation of ethyl acetoacetate, 390 328-332 ambident ion selectivities in, 390 Williamson ether synthesis, 410-433 Variables in design of PTe systems, 266 polyethylene glycol catalysts for, 166 Vinyl benzyl chloride for insoluble PTe, in polyetherification, 459 493 Wolff-Kishner reductions using PTe, Vinyl bromides, carbonylation of, 600 572 Vinyl dibromides, hydrolysis to acids, 617 Xanthine, N-alkylation of, 403 Vinyl halides, in cyanide displacements, Xylylene dihalides in polymerizations, 346 455,457