xúc tác chuyển pha phiên bản tiếng anh

Handbook of Phase Transfer Catalysis JOIN US ON THE INTERNET VIA WWW GOPHER FTP OR EMAil: WWW: GOPHER: FTP: EMAIL: http://www.thomson.com gopher.thomson.com ftp.thomson.com findit@kiosk.thomson.com A service of lOOP" Handbook of Phase Transfer Catalysis Edited by Y Sasson and R Neumann Casali Institute of Applied Chemistry The Hebrew University of Jerusalem Israel BLACKIE ACADEMIC & PROFESSIONAL An Imprint of Chapman & Hall London Weinheim New York Tokyo Melbourne Madras Published by Blackie Academic and Professional, an imprint of Chapman & HaD, 2-6 Boundary Row, London SE18HN, UK Chapman & Hall, Boundary Row, London SEI 8HN, UK Chapman & Hall GmbH, Pappelallee 3, 69469 Weinheim, Germany Chapman & Hall USA, liS Fifth Avenue, New York, NY 10003, USA Chapman & Hall Japan, ITP-Japan, Kyowa Building, 3F, 2-2-1 Hirakawacho, Chiyoda-ku, Tokyo 102, Japan DA Book (Aust.) Pty Ltd, 648 Whitehorse Road, Mitcham 3132, Victoria, Australia Chapman & Hall India, R Seshadri, 32 Second Main Road, CIT East, Madras 600 035, India First edition 1997 © 1997 Chapman & Hall Typeset in 10112pt Times by AFS Image Setters Ltd Glasgow ISBN-13:978-0-7514-0258-2 e-ISBN-13:978-94-009-0023-3 DOl: 10.1007/978-94-009-0023-3 Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the UK Copyright Designs and Patents Act, 1988, this publication may not be reproduced, stored, or transmitted, in any form or by any means, without the prior permission in writing of the publishers, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms oflicences issued by the appropriate Reproduction Rights Organization outside the UK Enquiries concerning reproduction outside the terms stated here should be sent to the publishers at the London address printed on this page The publisher makes no representation, express or implied, with regard to the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any errors or omissions that may be made A catalogue record for this book is available from the British Library Library of Congress Catalog Card Number: 96-71964 ~ Printed on acid-free paper, manufactured in accordance with ANSIINISO Z39 48-1992 (Permanence of Paper) Contents List of contributors Preface xi xiii Nucleophilic aliphatic and aromatic substitution in phase transfer catalysis: mechanism and synthetic applications I.A Esikova 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 Introduction General considerations 1.2.1 Reactions in liquid-liquid systems 1.2.2 The advantages of solid-liquid systems Reactivity of anions The role of water in solid-liquid substitution The omega phase Kinetics and mechanism ofPTC substitution Design of catalytic system The role of catalyst, solvent and other factors 1.6.1 Catalyst 1.6.2 Solvent 1.6.3 Stirring 1.6.4 Concentration of catalyst 1.6.5 Stability of catalyst Applications 1.7.1 Synthesis of fluorides 1.7.2 Synthesis of chlorides 1.7.3 Synthesis of bromides and iodides 1.7.4 Synthesis of thiocyanates 1.7.5 Synthesis of nitriles 1.7.6 Synthesis of azides 1.7.7 Synthesis of nitro compounds 1.7.8 Synthesis of thiols and sulfides 1.7.9 Trichloromethyl anion substitution 1.7.10 Hydrolysis and saponification I 7.11 Esterfication 1.7.12 PTC in carbohydrate chemistry 1.7.13 Aromatic nucleophilic substitution 1.7.14 PTC in polymer chemistry 1.7.15 Some industrial applications of PTC substitution Conclusion References Kinetic modelling of catalytic phase transfer systems M.-L Wang 2.1 2.2 Introduction Two-phase phase transfer catalytic reactions 2.2.1 Normal phase transfer catalysis (NPTC) 2.2.2 Reverse phase transfer catalysis (RPTC) 2.2.3 Inverse phase transfer catalysis (IPTC) I I I 14 15 17 19 19 20 20 20 21 22 22 23 24 24 24 25 25 25 26 26 29 30 31 32 36 36 36 36 79 79 CONTENTS VI 2.3 Three-phase phase transfer catalytic (TPPRC) reactions 2.3.1 Synthesis ofhexachlorocyclotriphosphazene by triphase catalysis 2.3.2 Dynamic model of triphase catalysis 2.3.3 A pseudo-steady-state hypothesis for triphase catalysis References Synthesis of quaternary ammonium salts Y Sasson 3.1 3.2 3.3 3.4 3.5 3.6 3.7 Introduction Direct quaternization Liquid-liquid anion exchange Solid-liquid anion exchange Anion exchange with polymeric ion-exchange resins Quat hydroxides via a two-stage anion exchange Transformation of the anion 3.7.1 Reaction with acids: neutralization of hydroxide 3.7.2 Decomposition of anions 3.8 Temperature-stable phase transfer catalysts 3.9 Catalyst recovery and recycle 3.10 Typical procedures 3.10.1 Tributylbenzylammonium cyanide 3.10.2 Tetrabutylammonium chloride (TBAC) 3.10.3 Synthesis oftetrahexylammonium formate (THAFor) 3.10.4 Tricaprylmethylammonium fluoride (Aliquat 336-F) 3.10.5 Preparation of tetra-n-octylammonium hydroxide (TOAH) and tetra-n-butylammonium hydroxide (TBAH) 3.10.6 N-(2-Ethylhexyl)-4-dimethylaminopyridinium chloride 3.10.7 (-)-Benzoquininium chloride 3.10.8 (+ )-N-(4- Trifluoromethyl)benzyldihydrocinchonium bromide 3.10.9 (-)-N-(9-Fluorenyl)quininium bromide 3.10.10 Tetra-n-butylammonium bibenzoate 3.10.11 Dihexyltetramethylguanidinium bromide References Phase transfer catalyzed reactions under basic conditions M Makosza and M Fedorynski 4.1 4.2 4.3 4.4 4.5 Introduction and mechanistic picture Applications of phase transfer catalysis in reactions of organic anions 4.2.1 Reactions of carbanions with alkylating agents 4.2.2 Generation and alkylation ofheteroanions 4.2.3 Reactions of carbanions at electrophilic Sp2 carbon 4.2.4 Reactions of carbanions with heteroatom electrophiles Generation and reactions of carbenes 4.3.1 Dihalocarbenes 4.3.2 Other carbenes f3-Elimination General conclusions Abbreviations References 93 95 100 103 107 111 III III 113 115 116 117 118 118 118 123 127 128 128 128 128 128 129 129 129 130 130 130 130 131 135 135 137 137 141 143 149 151 151 156 158 160 161 162 CONTENTS Application of phase transfer catalysis in the chemical industry vii 168 M Sharma 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 5.15 5.16 5.17 Phase transfer catalysis in industrial processes Evaluation and optimization PTC options Applications based on benzyl chloride Substituted benzyl chloride derivatives PTC in oxidation of toluene and its derivatives Application to pharmaceuticals N-Alkylation 5.6.1 5.6.2 Preparation of antitumor agents from estradiols by PTC 5.6.3 PTC method for production of lysergic acid-based drugs PTC with activated oxygen carrier PTC for oxidative decarboxylation Halogen exchange Application of PTC to dyes 5.10.1 Sulfite displacement reaction 5.10.2 Monsanto's environmentally safer route to aromatic amines Application of PTC to polymers 5.11.1 Nylon-8 5.11.2 Triaryl phosphates (TAPs) Application of PTC to agrochemicals Miscellaneous reactions 5.13.1 Alkyl halides from primary alcohols 5.13.2 Oximation 5.13.3 Ethoxylation of phenols 5.13.4 Converting liabilities into assets 5.13.5 CO absorption in salt hydrates Some examples of deuterium-labeled compounds (H-D exchange) Use ofPTC in named organic ractions 5.15.1 Aldol reaction 5.15.2 Michael reaction 5.15.3 Darzen reaction 5.15.4 Williamson ether synthesis 5.15.5 Wittig reaction 5.15.6 Horner-Emmons reaction 5.15.7 Reimer-Tiemann reaction 5.15.8 Hofmann rearrangement Separation and recovery of phase transfer catalyst 5.16.1 Extraction method 5.16.2 Distillation method Wastewater treatment References Phase transfer catalysis in polymer synthesis 168 168 169 171 172 173 173 175 176 177 178 180 182 183 183 183 185 185 187 190 190 190 191 191 192 192 193 193 193 193 194 194 194 194 194 195 195 196 196 197 200 L.H Tagle 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 Introduction Polyethers Polyesters Polycarbonates Polythiocarbonates Polythioethers, polysulfonates and polysulfones Copolymers Carbon-1:arbon chain polymers Miscellaneous polymers References 200 201 211 219 224 228 231 236 238 240 viii CONTENTS Phase transfer catalysis in carbohydrate chemistry R.Roy Introduction Non anomeric transformations 7.2.1 Introduction of protecting groups 7.2.2 Oxidation and reduction 7.2.3 C-C bond-forming reactions 7.3 Anomeric transformations 7.3.1 O-Glycosides 7.3.2 S-Glycosides 7.3.3 Others 7.4 N ucleosides 7.5 Carbohydrates as catalysts 7.6 Conclusions References 7.1 7.2 Phase transfer catalysis in heterocyclic chemistry E Diez-Barra and A de la Hoz 8.1 8.2 Introduction Synthesis of heterocyclic systems 8.2.1 Substitution at a saturated carbon atom 8.2.2 Addition to carbonyl carbons 8.2.3 Addition to activated double and triple bonds 8.2.4 Epoxidation addition of carbenes and nitrenes 8.2.5 Electrocyclic reactions 8.2.6 Cycloaddition reactions 8.2.7 Ring transformations 8.3 Reactivity of heterocyclic systems 8.3.1 Heterocycles as nucleophiles 8.3.2 Heterocycles as electrophiles 8.4 Heterocycles as phase transfer catalysts 8.4.1 Normal phase transfer agents 8.4.2 Chiral phase transfer agents 8.4.3 Inverse phase transfer catalysis (IPTC) 8.4.4 Electron transfer catalysis (ETC) References 244 244 245 245 253 255 258 261 263 264 265 268 271 272 276 276 276 276 278 281 283 285 286 286 287 287 296 299 299 301 307 308 309 Phase transfer catalysis in oxidation processes M Hronec 317 Introduction Reagents 9.2.1 Permanganate and chromate anions 9.2.2 Hypochlorite 9.2.3 Hydrogen peroxide 9.2.4 Molecular oxygen 9.2.5 Other oxidants 9.3 Synthetic utility 9.3.1 Oxidation of hydrocarbons 9.3.2 Oxidation of oxygen-containing compounds 9.3.3 Oxidation of nitrogen compounds 9.3.4 Oxidation of sulfur compounds 9.4 Future prospects References 317 318 318 318 319 319 320 321 321 325 327 328 329 330 9.1 9.2 CONTENTS 10 Organometallic reactions under phase transfer conditions I Arner Abbreviations 10.1 Introduction 10.2 Phosphorus donor-phase transfer agent hybrid ligands 10.3 Separate phase transfer agent and organometallic species 10.3.1 Stoichiometric reactions 10.3.2 Catalysed reactions 10.4 Conclusions References 11 Sonochemical and microwave activation in phase transfer catalysis A Loupy and 1.-L Luche 11.1 Introduction 11.2 Sonochemistry 11.2.1 Principles of sonochemical reactivity 11.2.2 Synthetic applications in phase transfer processes 11.2.3 Conclusion 11.3 Microwave chemistry 11.3.1 Principles of microwave activation 11.3.2 Synthetic applications in phase transfer processes 11.3.3 Conclusion References 12 Analytical applications of phase transfer catalysis C de Ruiter and H Lingernan 12.1 12.2 12.3 12.4 12.5 13 Introduction Analytical applications of liquid-liquid PTC Analytical applications of solid-liquid PTC Analytical applications of micellar PTC Conclusions References Triphase catalysis M Tornoi 13.1 Introduction 13.2 General methods for preparation oftriphase catalysts 13.3 Fundamental process of triphase catalysis 13.4 Effect of reaction conditions 13.5 Structure/properties and activity of triphase catalysts 13.5.1 Catalyst particle size 13.5.2 Active site structure and chemical structure of the polymer support 13.5.3 Cross-linking level 13.5.4 Catalyst loading level (ring substitution) 13.5.5 Space-chain effect 13.5.6 Morphology of polymer support 13.6 Problems with the practical use oftriphase catalysts 13.6.1 Stability of triphase catalysts 13.6.2 Synthetic applications 13.6.3 Chemical engineering oftriphase catalysis 13.7 Conclusion References IX 336 336 336 337 340 340 344 366 366 369 369 369 370 373 385 385 386 390 400 401 405 405 406 414 418 421 421 424 424 424 427 430 433 433 434 440 440 445 448 453 453 454 457 458 458 CONTENTS x 14 Chiral phase transfer catalysis T Shioiri 462 462 462 463 463 471 476 476 477 478 14.1 Introduction 14.2 Chiral phase transfer catalysts 14.3 Asymmetric phase transfer reactions 14.3.1 Carbon-{;arbon bond formation 14.3.2 Oxidation 14.3.3 Reduction 14.3.4 Carbon-nitrogen bond formation 14.4 Conclusion References 15 Chemical modification of polymers via phase transfer catalysis T Nishikubo 480 15.1 Introduction 15.2 Progress in chemical modification of polymers from the classical method to phase transfer catalysis 15.3 Chemical modification of polymers with pendant haloalkyl groups using phase transfer catalysis 15.3.1 Substitution reactions ofpoly[(chloromethyl)styrene] using phase transfer catalysis 15.3.2 Substitution reactions of other polymers containing pendant haloalkyl and haloaryl groups using phase transfer catalysis 15.3.3 Elimination reactions of polymers containing pendant haloalkyl groups using phase transfer catalysis 15.4 Synthesis of functional polymers by reactions of polymers containing pendant haloalkyl groups using phase transfer catalysis 15.5 Limitations of chemical modification of polymers using phase transfer catalysis 15.6 Chemical modification of polymers with pendant cyclic ether groups using new activity of phase transfer catalysts 15.7 Conclusion References 16 Phase transfer catalysis of uncharged species Y Sasson and R Neumann 16.1 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 Introduction Water Hydrogen halides Hydrogen cyanide Hypochlorite Hydrogen peroxide and alkyl hydroperoxides Metals and metal salts Carboxylic acids and alcohols Carbon acids 16.10 Ammonia and amines 16.11 Ammonium polyhalide complexes 16.12 Inverse phase transfer catalysis References Index 480 482 484 484 491 496 498 503 504 506 507 510 510 510 512 515 515 518 524 528 531 532 533 535 538 547 ... modelling of catalytic phase transfer systems M.-L Wang 2.1 2.2 Introduction Two-phase phase transfer catalytic reactions 2.2.1 Normal phase transfer catalysis (NPTC) 2.2.2 Reverse phase transfer catalysis... 2.3.1 Synthesis ofhexachlorocyclotriphosphazene by triphase catalysis 2.3.2 Dynamic model of triphase catalysis 2.3.3 A pseudo-steady-state hypothesis for triphase catalysis References Synthesis... Heterocycles as electrophiles 8.4 Heterocycles as phase transfer catalysts 8.4.1 Normal phase transfer agents 8.4.2 Chiral phase transfer agents 8.4.3 Inverse phase transfer catalysis (IPTC) 8.4.4 Electron