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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
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