Practical organic chemistry 5ed vogel

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VOGEL's TEXTBOOK OF PRACTICAL ORGANIC CHEMISTRY FIFTH EDITION Revised by former and current members of The School of Chemistry, Thames Polytechnic, London Brian S Furniss Antony J Hannaford Peter W G Smith Austin R Tatchell ~ ~ ~ Longman Scientific & ~rechni nice1 Copublished in the United States with John Wiley & Sons, Inc., New York Longman Scientific & Technical Longman Group UK Limited Longman House, Burnt Mill, Harlow Essex CM20 2JE, England and Associated Companies throughout the world Copublished in the United States with John Wiley & Sons, lnc., 605 Third Avenue, New York, NY 10158 © Longman Group UK Limited 1989 All rights reserved; no part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without either the prior written permission of the Publishers, or a licence permitting restricted copying in the United Kingdom issued by the Copyright Licensing Agency Ltd, 33-34 Alfred Place, London, WCIE 7DP First published 1948 New Impression with minor corrections, October 1948 Second Edition 1951 New Impression with addition of Chapter XII on Semimicro Technique 1954 Third Edition 1956 New Impression with corrections and additions 1957 New Impressions 1959, 1961, 1962, 1964, 1965, 1967 Fourth Edition 1978 Reprinted, with minor corrections 1979, 1981, 1984, 1986, 1987, 1988 Fifth Edition 1989 British Library Cataloguing in Publication Data Vogel, Arthur Israel Vogel's textbook of practical organic chemistry 5th ed I Organic chemistry Laboratory techniques I Title I Furniss, B S (Brian Stanley), 1941 547 '0028 ISBN 0-582-46236-3 Library of Congress Cataloging-in-Publication Data Vogel, Arthur Israel Vogel's Textbook of practical organic chemistry - 5th ed / rev by Brian S Furniss [et al.] p cm Fourth ed published in 1978 under title: Vogel's Textbook of practical organic chemistry, including qualitative organic analysis Includes bibliographies and indexes ISBN 0-470-21414-7 Chemistry, Organic-Laboratory manuals Chemistry, Analytic-Qualitative I Furniss, Brian S (Brian Stanley), 194111 Vogel, Arthur Israel Vogel's Textbook of practical organic chemistry, including qualitative organic analysis Ill Title QD26I.V63 1989 547-dc19 88-36786 CIP Set in 10/11 pt Lasercomp Times New Roman Filmset by Eta Services (Typesetters) Ltd, Beccles, Suffolk Printed in Great Britain by The Bath Press CONTENTS CHAPTER ORGANIC SYNTHESIS 1.1 INTRODUCTION 1.2 STRUCTURE OF THE TARGET MOLECULE 1.3 REACTION MECHANISM AND THE METHODOLOGY OF SYNTHESIS 1.4 REACTION MECHANISM AND THE STRATEGY OF SYNTHESIS 1.5 CONCLUSION 10 17 23 REFERENCES 23 CHAPTER EXPERIMENTAL TECHNIOUES 26 2.1 GENERAL INSTRUCTIONS FOR SAFE WORKING IN ORGANIC CHEMICAL LABORATORIES 2.2 PLANNING OF EXPERIMENTS AND RECORDING OF RESULTS 2.3 HAZARDS IN ORGANIC CHEMISTRY LABORATORIES 2.3.1 Introduction 34 2.3.2 Explosion and fire hazards 35 2.3.3 Reactive inorganic reagents 42 2.3.4 Hazards due to toxic chemicals 44 2.3.5 Electrical safety 51 2.3.6 Ultraviolet radiation 52 APPARATUS AND REACTION PROCEDURES 2.4 INTERCHANGEABLE GROUND GLASS JOINTS 2.5 TYPES OF GROUND GLASS JOINTS 2.6 CARE AND MAINTENANCE OF GROUND GLASS JOINTS 2.7 APPARATUS WITH INTERCHANGEABLE GROUND GLASS JOINTS SUITABLE FOR GENERAL USE IN PREPARATIVE ORGANIC CHEMISTRY 2.8 OTHER TYPES OF INTERCHANGEABLE JOINTS AND STOPCOCKS 2.9 THE USE OF CORKS AND RUBBER STOPPERS 2.10 CUTTING AND BENDING OF GLASS TUBING 26 31 34 52 52 55 57 58 63 64 65 v CONTENTS 2.11 2.12 2.13 2.14 2.15 GENERAL LABORATORY APPARATUS COOLING OF REACTION MIXTURES HEATING OF REACTION MIXTURES MECHANICAL AGITATION TYPICAL GROUND GLASS JOINT ASSEMBLIES FOR STANDARD REACTION PROCEDURES 2.16 PRECAUTIONS FOR UNATTENDED REACTIONS 2.17 APPARATUS FOR SPECIAL REACTION TECHNIOUES 2.17.1 2.17.2 2.17.3 2.17.4 2.17.5 2.17.6 2.17.7 2.17.8 66 70 71 73 80 86 87 Catalytic hydrogenation 87 Reactions under pressure 97 Uncatalysed and catalysed vapour phase reactions 99 Ozonolysis 103 Organic photochemistry 106 Electrolytic (anodic) syntheses 115 Liquid ammonia techniques 116 Reactions involving air-sensitive compounds 120 ISOLATION AND PURIFICATION PROCESSES 2.18 GENERAL CONSIDERATIONS 2.19 FILTRATION TECHNIOUES 2.20 RECRYSTALLlSATlON TECHNIOUES 2.21 SUBLIMATION TECHNIOUES - FREEZE DRYING 2.22 SOLVENT EXTRACTION 2.23 DRYING OF L10UlDS OR OF SOLUTIONS OF ORGANIC COMPOUNDS IN ORGANIC SOLVENTS 2.24 DISTILLATION AT ATMOSPHERIC PRESSURE 2.25 STEAM DISTILLATION 2.26 FRACTIONAL DISTILLATION AT ATMOSPHERIC PRESSURE 2.27 DISTILLATION UNDER DIMINISHED PRESSURE ('VACUUM' DISTILLATION) 2.28 HIGH VACUUM DISTILLATION - MOLECULAR DISTILLATION 2.29 VACUUM PUMPS 2.30 MANOMETERS, VACUSTATS, VACUUM GAUGES AND MANOSTATS 2.31 CHROMATOGRAPHY 2.32 STORAGE OF SAMPLES 165 169 171 173 181 186 191 193 197 234 DETERMINATION OF PHYSICAL CONSTANTS 2.33 MELTING POINT - MIXED MELTING POINTS 2.34 DETERMINATION OF BOILING POINT 2.35 DETERMINATION OF MOLECULAR WEIGHT 2.36 DETERMINATION OF OPTICAL ROTATORY POWER 2.37 DETERMINATION OF REFRACTIVE INDEX 236 236 241 243 244 249 REFERENCES 250 vi 131 131 133 135 153 156 CONTENTS CHAPTER SPECTROSCOPIC METHODS AND THE INTERPRETATION OF SPECTRA 254 Introduction 254 The electromagnetic spectrum 255 3.1 INFRARED SPECTROSCOPY 256 Instrumental features of infrared spectrophotometers 258 Determination of infrared spectra 259 Sample preparation 260 Features of an infrared spectrum 268 Interpretation of an infrared spectrum 271 Characteristic group frequencies 273 3.2 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 316 Features of the nuclear magnetic resonance spectrum 319 The chemical shift 324 Spin-spin splitting 338 Protons attached to heteroatoms 348 Simplification of IH spectra 350 Interpretation of the p.m:r, spectrum 359 Further information from 13C-spectra 360 3.3 MASS SPECTROMETRY 361 The mass spectrum 362 Appearance of the mass spectrum 372 Interpretation of the mass spectrum 373 Mass spectra of classes of organic compounds 373 14 ULTRAVIOLET-VISIBLE SPECTROSCOPY Instrumental features of ultraviolet-visible spectrophotometers 384 Determination of ultraviolet-visible spectra 384 Laws of light absorption 385 Solvents for ultraviolet spectroscopy 386 Solution preparation 386 Optical cells and their care 387 Features of an ultraviolet-visible spectrum 388 383 REFERENCES 393 CHAPTER SOLVENTS AND REAGENTS 395 4.1 THE PURIFICATION OF COMMON ORGANIC SOLVENTS 395 Saturated a1iphatic hydrocarbons 397 Aromatic hydrocarbons 398 Halogenated hydrocarbons 399 Aliphatic alcohols 400 Ethers 404 Ketones 407 Esters 409 VB COlTEITS Nitrogen-containing solvents 409 Sulphur-eontaining solvents 411 Phosphorus-containing solvents 412 4.2 THE PREPARATION AND PURIFICATION OF REAGENTS 413 REFERENCES 468 CHAPTER ALlPHATIC COMPOUNDS 470 5.1 ALKANES 470 Structure 470 Summary ofpreparative methods and of retrosynthetic strategies 471 Spectroscopic features 472 5.1.1 The catalytic hydrogenation and chemical reduction of alkenes 472 5.1.2 The hydrolysis of alkylmagnesium halides and the hydrogenolysis of alkyl halides and of alkyl methane- or toluene-p-sulphonates 474 5.1.3 The reduction of aldehydes and ketones 476 5.1.4 Coupling reactions (a) using organometallic compounds, and (b) at the anode 477 5.2 ALKENES 484 Structure 484 Summary ofpreparative methods and of retrosynthetic strategies 485 Spectroscopic features 486 5.2.1 1,2-Elimination processes (p-elimination) 486 5.2.2 The partial hydrogenation of alkynes 493 5.2.3 Wittig and related reactions 495 5.2.4 Selected rearrangements of alkynes to allenes 504 5.3 ALKYNES 507 Structure 507 Summary ofpreparative methods and of retrosynthetic strategies 508 Spectroscopic features 508 5.3.1 The dehydrogenation of vic- and gem-dihalides 509 5.3.2 The oxidation of dihydrazones of 1,2-diketones 512 5.3.3 Alkylation of a terminal alkyne 513 5.3.4 Coupling reactions leading to diynes 515 5.4 ALlPHATlC ALCOHOLS Structure 517 Summary ofpreparative methods and of retrosynthetic strategies 517 Spectroscopic features 519 5.4.1 The reduction of aldehydes, ketones and esters 519 5.4.2 The interaction of carbonyl-containing compounds with organometallic reagents 531 5.4.3 The hydroboration-oxidation of alkenes 542 5.4.4 The oxymercuration-demercuration of alkenes 545 5.4.5 The hydroxylation of alkenes 547 5.4.6 Methods for the protection of the hydroxyl group 550 Vlll 517 CO.TEITS 5.5 ALlPHATIC HALlDES 553 Structure 553 Summary ofpreparative methods and of retrosynthetic strategies 554 Spectroscopic features 554 5.5.1 Preparation of alkyl chlorides from alcohols 555 5.5.2 Preparation of alkyl bromides from alcohols 559 5.5.3 Preparation of alkyl iodides from alcohols 566 5.5.4 Displacement reactions involving a halogen atom 570 5.5.5 Displacement reactions involving a methanesulphonyloxy group 572 5.5.6 Displacement reactions involving the amino group 574 5.5.7 Addition of hydrogen halides or halogens to alkenes 574 5.5.8 The replacement of reactive allylic hydrogen atoms by bromine 577 5.6 ALlPHATIC ETHERS 579 Structure 579 Summary ofpreparative methods and of retrosynthetic strategies 580 Spectroscopic features 580 5.6.1 The formation of ethers from alcohols under acidic conditions 581 5.6.2 The interaction of an alcohol with a halogen compound under basic conditions 583 5.7 ALlPHATlC ALDEHYDES 585 Structure 585 Summary ofpreparative methods and of retrosynthetic strategies 585 Spectroscopic features 587 5.7.1 The controlled oxidation or dehydrogenation of primary alcohols 587 5.7.2 The oxidative cleavage of 1,2-diols 590 5.7.3 The ozonolysis of suitably substituted alkenes 592 5.7.4 The reduction of nitrites, carboxylic acids and carboxylic acid chlorides 594 5.7.5 Methods based upon alkyl halides 596 5.7.6 The hydrolysis and decarboxylation of ~,Il-epoxy esters (glycidic esters) 598 5.7.7 The oxidative hydrolysis of nitronate salts derived from primary nitroalkanes 599 5.7.8 Methods for the alkylation of the carbon chain 600 5.8 ALlPHATIC KETONES 604 Structure 604 Summary ofpreparative methods and of retrosynthetic strategies 605 Spectroscopic features 606 5.8.1 The oxidation of secondary alcohols 607 5.8.2 The hydration of alkynes 612 5.8.3 The thermal decarboxylation of acids over a metal oxide catalyst 612 5.8.4 The interaction of organometallic compounds with carboxylic acid chlorides and N,N-dimethylcarboxamides 616 ix CONTENTS 5.8.5 The hydrolysis and decarboxylation of Il-keto esters and the hydrolysis of IJ-diketones 619 5.8.6 The acid-catalysed rearrangement of 1,2-diols 623 5.8.7 The oxidative hydrolysis of nitronate salts from secondary nitroalkanes 623 5.8.8 Methods for the protection of the carbonyl group in aldehydes and ketones 623 5.9 DICARBONYL COMPOUNDS 626 Structure 626 5.9.1 1,2-Dicarbonyl compounds 627 5.9.2 1,3-Dicarbonyl compounds 632 5.9.3 1,4-Dicarbonyl compounds 635 5.10 CARBOHYDRATES Structure 637 5.10.1 Carbohydrate 5.10.2 Carbohydrate 5.10.3 Carbohydrate 5.10.4 Carbohydrate 5.10.5 Carbohydrate 637 interconversions interconversions interconversions interconversions interconversions 642 644 651 658 660 5.11 ALlPHATIC CARBOXYLIC ACIDS 664 Structure 664 Summary ofpreparative methods and of retrosynthetic strategies 664 Spectroscopic features 666 5.11.1 Oxidative methods 667 5.11.2 Hydrolysis of alkyl cyanides 671 5.11.3 Carboxylation of Grignard reagents 673 5.11.4 The Arndt-Eistert method 675 5.11.5 Electrolytic (anodic) coupling 677 5.11.6 Methods utilising diethyl malonate 680 5.11.7 The synthesis of optically active carboxylic acids 687 5.11.8 Methods for the protection of the carboxyl group 690 5.12 CARBOXYLIC ACID DERIVATIVES 691 Structure 691 Summary of retrosynthetic strategies 692 Spectroscopic features 692 5.12.1 Acyl halides 692 5.12.2 Acid anhydrides 693 5.12.3 Esters 695 5.12.4 Acid amides 708 5.13 ALlPHATlC NITRILES Summary ofpreparative methods and of retrosynthetic strategies 710 Spectroscopic features 711 5.13.1 Displacement with cyanide ion on an alkyl halide 711 5.13.2 Displacement with cyanide ion on an arylsulphonylhydrazone 712 5.13.3 Dehydration of amides and aldoximes 715 x 710 CUIIlEITS 5.13.4 Cyanoethylation procedures and the ee-afkylatien of nitriles 717 5.14 SUBSTITUTED CARBOXYLIC ACIDS AND THEIR DERIVATIVES 719 Structure 719 Spectroscopic features 720 5.14.1 Halogenoacids720 5.14.2 Hydroxy acids and lactones 725 5.14.3 Keto acids and esters 735 5.14.4 Amino acids and peptides 746 5.15 NITROALKANES 763 Structure 763 Summary ofpreparative methods and of retrosynthetic strategies 764 Spectroscopic features 764 5.15.1 The displacement of a halogen by a nitrite ion in an alkyl halide 764 5.15.2 The oxidation of oximes and amines 765 5.15.3 C-Alkylation of nitroalkanes and other homologation procedures 768 5.16 ALlPHATlC AliNES 769 Structure 769 Summary ofpreparative methods and of retrosynthetic strategies 770 Spectroscopic features 771 5.16.1 The reduction of alkyl azides, alkyl cyanides and amides 771 5.16.2 The reduction of nitro compounds and oximes 774 5.16.3 The reductive alkylation of ammonia or amines 776 5.16.4 The alkylation of ammonia and its derivatives 779 5.16.5 Imine and enamine formation 782 5.16.6 Molecular rearrangements of the Hofmann type 783 5.16.7 Methods for the protection of the amino and imino groups 784 5.17 ALlPHATlC SULPHUR COMPOUNDS 786 Structure 786 Spectroscopic features 787 5.17.1 Thiols and thioacetals 787 5.17.2 Dialkyl sulphides (thioethers) and trialkylsulphonium salts 789 5.17.3 Sulphoxides and suiphones 791 5.17.4 O,S-Dialkyl dithiocarbonates (xanthate esters) 792 5.18 UNSATURATED COMPOUNDS 794 5.18.1 Unsaturated alcohols 794 5.18.2 Unsaturated carbonyl compounds 798 5.18.3 Unsaturated acids and esters 820 5.19 RESOLUTION OF RACEMATES 809 REFERENCES 816 xi IIDEX of nitroketones, 635, 637 of nitrosamines, 962, 1227 of organomercury intermediates, 545, 546 of oximes, 774, 775, 1147, 1151 of phthalimide, 1063, 1065 of quinones, 1221, 1261 of a stilbenequinone, 1021, 1025 of sugar dimers, 653, 657 of sulphonyl chlorides, 887,888 of sulphoxides, 1231 of toluene-p-sulphonylhydrazones, 477, 828, 832 of ex,p-unsaturated carbonyl compounds, 795 of xanthone, 1270 Rosenmund, 594, 1000, 1004 Wolff-Kishner, 476, 827,831 Reductive acetylation, 1022, 1026 Reductive alkylation, 776, 778, 901, 905 Reductive cleavage of disulphides, 790 Reductive cyclisation, acyloin formation, 1096,1103 Reductive deamination, 926, 943 Reductive dimerisation, 840, 843 Reductive hydrolysis of azlactones, 747,755 Re-face, 16 Reference works, 1404 Reflux ratio, 177 Reformatsky reaction, 727, 732 Refractive index, determination of, 249 Regioselectivity, 13 in acylation of ketones, 633 in additions to unsaturated acids, 721 in alkyl bromide formation from alcohols, 560 in in in in in in in in alkyl iodide formation from alcohols, 566 aromatic electrophilic substitution, 852 Baeyer-Villit1greaction, 728 Birch reducti s, 1114 epoxidation dienes, 1133 hydration of a ynes, 612 hydroboration of alkenes, 542, 588 oxymercuration-demercuration of alkenes, 546 in reduction of carbonyl compounds, 795 Reimer-Tiemann reaction, 991, 992, 997 Replacement reactions, see Displacement and Substitution reactions Report writing, 32 Resolution of racemates by fractional crystallisation, 809 by g.l.c., 810 by h.p.l.c., 810 of acids, 809 of aldehydes and ketones, 810 of amino acids, 811 of bases, 809 of 1,1'-bi-2-naphthol 836 principles, 7, 809 with (-)-brucine, 810, 813 with papain, 812, 815 with (+ j-tartaric acid, 812 Resorcinol: carboxylation of, 1068 formylation of, 995 in heterocyclic synthesis, 1193 reaction with diazonium salts, 950 RL of, 48 sulphonation/nitration of, 980 p-Resorcyaldehyde, see 2,4Dihydroxybenzaldehyde p-Resorcyclic acid, see 2,4-Dihydroxybenzoic acid Response factors, in g.l.c analysis, 225 Retrosynthetic analysis (see also individ ual functional groups, i.e Alkanes, Alkenes, Alkynes, etc) for 7-acetoxyheptanal, 478 for 2-amino-4-methylthiazole, 1152 for 2-aminothiazole, 1152 for barbituric acid, 1175 for benzimidazole, 1162 for benzofuran, 1157 for benzotriazole, 1162 for 4-benzylidene-2-methyloxazol-5-one, 1155 for 5-chloro-3-methylbenzothiophene, 1157 for 5-chloro-2-phenylindole, 1157 for coumalic acid, 1173 for coumarin, 1191 for cyclobutanecarboxylic acid, 1089 for cyclopropyl methyl ketone, 1088 for diethyl 2,6-dimethylpyridine-3,5dicarboxylate, 1165 for 3,5-diethoxycarbonyl-2,4-dimethylpyrrole, 1146 for (+ )-(7aS)-7,7a-dihydro-7a-methyl1,5(6H)-indanedione, 1094 for 1,2-dihydro-2-methylquinoline, 1182 for 5,5-dimethylcyclohexane-I,3-dione, 1097 for 2,5-dimethylfuran, 1146 for 3,5-dimethylpyrazole, 1146 for 2,5-dimethylpyrrole, 1146 for 2,4-dimethylthiazole, 1152 for 2,5-dimethylthiophene, 1146 for 1,2-diphenylaziridine, 1131 for 5,5-diphenylhydantoin, 1152 for 2-ethoxycarbonylcyclopentanone, 1095 for ethyl ex-[(p-benzyloxy)phenyl)-2-oxo-lazetidineacetate, 1138 for 5-ethyl-5-phenylbarbituric acid, 1175 for flavone, 1192 for hept-l-ene, 478 for indane-I,3-dione, 1095 for methylenecyclohexene, 496 for 4-methylcoumarin, 1191 for 3-methylcyclohex-2-enone, 1093 for 3-methylcyclopentane-I,2,4-trione, 1097 for 3-methylcyclopent-2-enone, 1092 for 6-methylisoquinoline, 1183 for 3-methyl-I-phenylpyrazol-5-one, 1146 for phenyloxirane, 1131 for 2-phenylquinoline-4-carboxylic acid, 1182 1501 INDEX Retrosynthetic analysis-cont for piperazine-2,5-dione, 1176 for quinolines, 1181 for quinoxalines, 1184 for tetraphenylcyclopentadienone, 1095 for 2,4,6-trimethylquinoline, 1182 for 2,4,6-triphenylpyrylium tetrafluoroborate, 1166 Retrosynthetic strategies, computer programs for, 18 ()(- and !1-D-Ribopyranose, 642 Rimini test, 1217 Ring closure reactions, see Cyclisation reactions Ring construction, in heterocyclic synthesis, 1145, 1181, 1191 Ring contraction reactions, 11 I1, 1113 Ring expansion reactions, 1111, 1112 Ring opening: of cyclic amides, 1176, 1180 of epoxides (oxiranes), 547, 795, 797 of lactones, 721, 724, 728,733, 1088 of tetrahydrofuran, 479, 559, 566 of tetrahydropyran, 492, 559, 566 RL, see Recommended limit value R/S, configuration, Robinson annelation reaction, 1094, 1100 Rosenmund reduction, 594, 1000, 1004 Rotary film evaporator, 186 Rubber bungs, boring of, 64 Rubrene, see 5,6,11,12Tetraphenylnaphthacene Saccharin, and halogenation of, 888 Safety: electrical safety, 51 explosion and fire hazards, 35 conduct of explosive or violent reactions, 42 dangerous operations laboratory, 41 explosive compounds, 36 fire hazards, 39 general aspects, 34 potentially dangerous mixtures, 36 some specific dangers of explosives, 37 first-aid personnel, 35 general safety considerations, 26, 86 accident procedure, 29 after hours working, 29 glassware, 27, 30 personal protection, 26 precautions for unattended reactions, 86 storage of chemicals, 30 waste disposal, 30 hazards due to toxic chemicals, 44 carcinogenic substances, 48 dangerously toxic gases and liquids, 46 highly toxic solids, 46 other harmful substances, 47 substances with very harmful cumulative effects, 50 reactive inorganic reagents, 42 1502 halogens, 44 reactive halides, 44 strong acids, 43 strong bases, 43 ultraviolet radiation, 52 Salicylaldehyde, and m.s data of, 997 i.r absorptions of, 299 oxime from, 1049 Perkin reaction with, 1040 phenoxyacetic acid from, 1160 p.m.r absorptions of, 997 Salicylaldoxime, 1049 Salicylic acid: esterification of, 1078 rearrangement of, 1068 Salting out, 158 Samples, storage of, 234 Sandmeyer reaction, 923, 1063, 1081 disadvantages of, 924 Saytzeff rule, 487 Schiemann reaction, 925, 939 Schiff base, 782 Schiff's reagent, and test, 1219 Schmidt reaction, 784, 898 Schotten-Baumann benzoylation reaction, 917 of amines, 1274 of phenols, 1076, 1080, 1248 Sebacic acid, 679 acid chloride from, 676 esterification of, 700, 703 methyl hydrogen ester of, 703 Sebacoyl chloride, 676 reaction with diazomethane, 676 Selectivity, in reactions, 13 t-Selectride, see Lithium tri-sbutylborohydride Selenium: dehydrogenation agent, 840, 844 precautions in use of, 629, 844 RL of, 46 Salenium dioxide: oxidations with, 629 precautions in use of, 460, 629 purification procedure of, 460 Semicarbazones: characterisation of by hydrolysis, 1228 of aldehydes, 1258 of quinones, 1261 m-Serine, and t.l.c of, 755 Shakers, mechanical, 78 Sharpless epoxidation reaction, 1134, 1135 Shift reagents, 350 Sia,BH, see Disiamylborane Side-chains, oxidation of: in arenes, 1239 in aromatic ethers, 1256 in aromatic nitro compounds, 1282 in aryl halides, 1254 Si-face, 16 [3,3)-Sigmatropic shift, 796, 978 Silica gel, chromatographic grading of, 212 Silicon tetrachloride, hazards of, 44 Silver carbonate-on-Celite, and oxidation with,1024 Silver nitrite, 461 IIDEX Silver oxide, 677 reaction involving use of, 676 P-Silylalcohols, from carbonyl compounds, 498 elimination reaction of, 498 Silylating agents, 229, 461 e-Silylcarbanions 498 Silyl enol ethers, 801,803 reaction with nitro olefins, 635 Silyl esters, of carboxylic acids, 691 Silyl ethers, 552 Simmons-Smith reaction, 1107, 1108 Simon's test, 1217 Skraup's quinoline synthesis, 1181,1185 'Slit-sieve' funnel, 68 Smiles'test, 1212 Soda lime, ignition with, 1205, 1265, 1271 Sodamide, 462 destruction of residues of, 37 precautions in storage and use of, 37,43, 462, 885 reactions involving use of, 513, 541, 599, 885, 1171 Sodium: amalgam, 464 reactions involving use of, 741, 1039, 1270 granular, 'molecular', power or sand, 462 reactions involving use of, 628, 773, 1036 in liquid ammonia: for partial hydrogenation of alkynes, 494 in Birch reducton, 1115, 1116 organosodium reagent from, 1069 wire, 405 Sodium: destruction of residues of, 41 fusion with, 1205 precautions in use of, 462 Sodium acetate, anhydrous fused, 464 Sodium acetoxyborohydride, reduction of amides with, 774 Sodium acetylide, and reaction involving use of, 513, 541 Sodium anthraqinone-z-sulphonate, 867 conversion to alizarin, 972 Sodium azide, reactions involving use of, 772, 899 Sodium benzophenone ketyl, 407, 741 Sodium borohydride, 447 borane from, 543 chemoselectivity of, in reductions, 519, 697 estimation of, 448 other reactions involving use of, 474, 477, 494, 497, 523, 546, 602, 772, 774, 777 stabilised solution of, 92 Sodium bromate, oxidation with, 1046 Sodium p-brombenzenesulphonate, 875 Sodium N-clorotoluene-p-sulphonamide (see also Chloramine-T), 883 Sodium cyanamide, alkylation with, 780 Sodium cyanate, reaction involving use of, 964 Sodium cyanide: hazards in use of, 464 reactions involving use of, 712, 729, 1044, 1054 Sodium cyanoborohydride, 448 reaction involving use of, 795 Sodium dichromate, 425 reactions involving use of, 588, 609, 1057 Sodium dihydro-bis(2methoxyethoxy)aluminate [sodium bis(2methoxyethoxy)allumium hydride, 'Red AI': deprotection of allyl aryl ethers with, 989 reduction with, 775 Sodium disulphide, in situ preparation of, 913 Sodium dithionite, reductions with, 949, 952, 1026 Sodium ethoxide, 464 dry reagent, 634 ethanol solution of, 620 precautions in use of, 621 reactions involving use of, 620, 634, 636, 1102, 1104, 1105, 1113 Sodium fluoroborate, reaction involving use of,939 Sodium hydride: dispersion in oil, 449 precautions in use of, 449 reactions involving use of, 494, 497, 600, 769, 797, 806, 1110 Sodium hypobromite, reactions involving use of, 516,669,898 Sodium hypochlorite, 670 Sodium iodide, solution in acetone, 571, 1233 Sodium metaperiodate, 454 on silica gel, 455 example of use of, 592 reactions involving use of, 657, 792 Sodium naphthalene-z-sulphonate, 876 fusion with potassium hydroxide, 971 Sodium nitrite: diazotisation with, 921, 927 et seq., 1129, 1163 other reactions involving use of, 765, 978, 1151 Sodium paraperiodate, 454 Sodium per borate, reaction involving use of, 792 Sodium polysulphide, 895 Sodium sulphide, 790, 913, 1142 Sodium sulphite, reductions with, 960, 1143 Sodium toluene-p-sulphinate, 887 Sodium toluene-p-sulphonate, 874 Sodium trifluoroacetoxyborohydride, reduction of amides and nitriles, 774 Solubility of organic compounds, 1198 Solvents: auto-ignition of, 40 flash points, table of, 40 for i.r spectroscopy, 263 for n.m.r spectroscopy, 324 for u.v-visible spectroscopy, 386 purification procedures for, 395 413 removal of per oxides from, 396, 397,402, 404, 406 1503 INDEX Solvents-cont storage, recommended procedures for, 40 table of physical data, 1142 Solvent extraction, see Extraction Sommelet reaction, 999, 1002 Sonication, reactions involving use of, 727, 1107, 1108 Sorbic acid, 807 Soxhlet extraction apparatus, 164 Spatulas, 69 Spectacles, safety, 26 Spectra: interpretation of: i.r., 271 mass, 373 n.m.f.,359 u.v.-visible, 388 Spectroscopic methods, 254 Spectroscopy, collections of data, 394 Spin decoupling, 357 Spin-spin interactions: first order, 340 more complex, 342 Spin-spin splitting, 338 Spin-spin systems, 343 aromatic compounds, 344 table of, 1432 Spinning band fractionating columns, 180 Stationary phases: for alcohols, 544 for alicyclic hydrocarbons, 1116 for alkanes, 474 for alkenes, 491, 493, 494 for alkyl halides, 570 for alkynes, 506, 517 for alkynols, 517 for benzyl alcohol/benzaldehyde mixtures, 1030 for bromoacetylenes, 517 for cyclic esters, 1114 for cyclopropane esters, 1111 for dienes, 507 for furan derivatives, 1149 for polycyclic aromatic hydrocarbons, 847 for resolution of racemates, 812 for tricyclic hydrocarbons, 1108 Steam distillation, 171 examples involving use of, 977, 993 Stephen reaction, 594, 595 Stereochemistry of pericyclic reactions, 1117 Stereoelectronic requirements of a reaction, 14 Stereoisomers from a dehydrohalogenation reaction, 488 Stereoselectivity, 14 examples illustrating operation of, 520, 523 Stereospecificity, 14 examles illustrating operation of, 494, 542, 547,672,728, 1117, 1137 Stirrers, 76 Hershberg, 76 mercury-sealed, 77 precision ground, 77 Vibro-mixer, 77 Sitrring: electric motors for, 76 magnetic, 78 1504 mechanical, 73 Stobbe condensation, 739, 744 Stopcock, 'Rotaflo', 63 Storage of chemicals, 30 Strecker synthesis, 747, 753 Styphnates, of arenes, 1240 Styrene: epoxidaton of, 1135 oxymercuration/demercuration of, 547 p.m.r, spectrum of, 347 Styrene oxide, see 1,2-Epoxyethylbenzene Suberic acid, 672 Sublimation: technique of, 153 under reduced pressure, 154 Substitution reactions (see also Displacement reactions) aliphatic nucleophilic: examples illustrating operation of, 555, 560, 570, 583, 635, 680,688, 711 aromatic electrophilic: examples illustrating operation of, 851, 860, 865, 873, 877, 908,975,991,1006,1071 aromatic nucleophilic (addition-elimination, and elimination-addition): examples illustrating operation of, 880, 900, 959, 970 SNI,555 SN2,560 SNi', 505 Succinamide, 709 Succinic acid: anhydride from, 695 diphenylpolyenes from, 1042 Succinic anhydride, 695 acylation with, 1015 Succinimide, reaction with sulphur monochloride, 1130 Succinimide-N-sulphenyl chloride, and addition to cyclooctene, 1130 Sulphanilamide (paminobenzenesulphonamide), 883 Sulphanilic acid, 912 diazonium salt from, in synthesis, 950, 951 Sulphapyridine (2-[Paminobenzenesulphonamido]pyridine), 884 Sulphates, organic: group frequencies (i.r.) of, 316 correlation table, 1422 dialkyl, hydrolysis of, 1232 of alkanolamines, 1128 Sulphides (thioethers): characteristic chemical properties of, 1231 dialkyl, 1160 m.s data of, 377 table of physical constants of, 1395 Sulphinic acids, characteristic chemical/ spectroscoic properties of, 1212 Sulpholane: physical properties of, and purification procedures for, 412 Sulphonacetamides, from sulphonamides, 1285, 1286 Sulphonamides: arylsulphonamides, 879 INDEX retrosynthetic strategies for, 872 structure of, 872 characterisation by hydrolysis, 1228, 1230 derivatives of, 1286 from arenes, 1238 from aromatic ethers, 1256 from aryl halides, 1254 from sulphonic acids, 1284 spectroscopic features, 873 group frequencies (i r.), 316 correlation table, 1422 table of, and derivatives of, 1392 Sulphonanilides, from sulphonic acids, 1284 Sulphonates: alkyl sulphonates, hydrolysis of, 1232 arylsulphonates retrosynthetic strategies for, 872 structure of, 872 spectroscopic features: summary of, 873 group frequencies (i.r.), 316 correlation tables, 1422 Sulphonation: of aromatic amines, 908, 912 of aromatic compounds, 874, 875 of aromatic hydrocarbons, 873, 874 of nitrobenzene, 909, 914 of phenol, 975, 981 of resorcinol, 975, 980 Sulphones, 791, 1231 group frequencies (i.r.) of, 316 correlation table, 1422 table of physical constants of, 1395 Sulphonic acids: arylsulphonic acids: retrosynthetic strategies for, 872 structure of, 872 characteristic chemical properties, 1212 derivatives of, 1284 spectroscopic features: summaries of, 873, 1212 group frequencies (i.r.), 316 correlation table, 1422 table of, and derivatives of: aliphatic, 1390 aromatic, 1388 Sulphonium salts, 790 Sulphonyl chlorides: arylsulphonyl chlorides, 877 retrosynthetic strategies for, 872 structure of, 872 from sulphonic acids, 1284 group frequencies (i.r.) of, 316 correlation table, 1422 reduction products from, 887 Sulphoxides, 791, 1231 group frequencies (i.r.) of, 316 correlation table, 1422 table of physical constants of, 1395 Sulphur, as dehydrogenation catalyst, 839 detection of, 1207 Sulphur compounds, organic: group frequencies (i.r.) of, 314 correlation table, 1422 table of physical constants, 1395 Sulphur dioxide, 465 Sulphuric acid, 465 hazards in use, 43 preparation of 70%,918 Sulphuryl chloride, 465 reactions involving use of, 758, 864 Superhydride, see Lithium triethylborohydride Suprafacial, 1118 Swern oxidation, 608, 608 Symmetry elements, Synthesis: methodology and strategy of, 10 Synthons (see also retrosynthetic strategies of individual functional types), 19 of reversed polarity, 21 tables of common examples, 1447-50 Syringes, types of, and handling of, 122 Tables of derivatives, index to, 1298 Target molecule, structural assessment of, (+)-Tartaric acid, configuration of, esterification of, 591 pyruvic acid from, 740 use as resolving agent, 809 meso- Tartaric acid, configuration of, TBSH, see 2,4,6-Triisopropylbenzenesulphonyl hydrazide Terephthalic acid, 1058 Tetrabromoethane, TL V of, 47 Tetrabutylammonium borohydride, 520 Tetrabutylammonium fluoride, in deprotection of silyl-ethers, 553 Tetrabutylammonium hydrogen sulphate, as phase transfer catalyst, 584, 588, 656, 1132 Tetrabutylammonium iodide, as phase transfer catalyst, 806, 1132 3,3',5,5' -Tetra-t-butyldiphenoquinone, 1024 sym.-Tetrachloroethane, physical properties of, 1442 TLV of,47 Tetrachloromethane, see Carbon tetrachloride Tetracyclone, see Tetraphenylcyclopentadienone Tetradecane-S, lO-dione, 618 Tetradecane-I-thioI, 789 Tetradecanoic acid, see Myristic acid Tetradecan-l-ol, alkyl bromide from, 564 Tetraethylammonium cyanide, use as phase transfer catalyst, 712 Tetraethyl propane-l , I,3,3-tetracarboxylate, 685 1,2,3,4-Tetrahydrocarbazole, 1161 cis-I ,4,4a,9a-Tetrahydro-2,3-dimethyl-9,1 0anthraquinone, 1120 cis-I ,2,3,6-Tetrahydro-4,5-dimethylphthalic anhydride, 1120 Tetrahydrofuran: dihalides from, 563, 565 peroxides in, hazards from, 406, 552 physical properties, 1442 purification procedures for, 406 1505 INDEX (+ )-(3aS,7aS)-3a,4,7,7a-Tetrahydro-3a- hydroxy-7a-methyl-I,5(6H)-indanedione, and dehydration of, 1100 i.r and p.m.r absorptions of, 1100 Tetrahydropyran: diacetoxypentane from, 492 dihalides from, 563, 565, 568 Tetrahydropyranyl ethers, 551 hazards in reaction with, 552 Tetrahydrothiophene-I, l-dioxide (sulpholane), purification procedures for, 412 Tetralin, purification procedure for, 398 (X- Tetralone, 1015 reaction with Grignard reagents, 841 cis,trans,cis-3,3,8,8- Tetramethoxytricyclo[5.3.0.0'·O)decane, 1123 3,3' ,5,5'-Tetramethyl-4,4'-dihydroxystilbene, and p.m.r absorptions of, 1025 3,3' ,5,5'-Tetramethyldiphenoquinone, 1025 Tetramethylene glycol, see Butane-l,4-diol Tetramethylsilane, in n.m.r spectroscopy, 320 3,3',5,5'-Tetramethylstilbenequinone, and reduction of, 1025 Tetraphenylcyclopentadienone, 1101 Diels-Alder reaction with, 1121 3,4,5,6-Tetraphenyldihydrophthalic anhydride, 1121 5,6, 11,12-Tetraphenylnaphthacene, 844 Teuber reaction, 1020 Thallium salts, RL of, 46 Theoretical plate, 175 height equivalent of (HETP), 176 Thermally allowed reactions, 1118 Thermodynamic vs kinetic control, 12 examples illustrating operation of, 496, 574, 643, 874, 1007, 1112 Thermometers, calibration of, 238 Thexylborane (thexyl-BH,), 542 THF, see Tetrahydrofuran Thiele, acetylation, of quinones, 1021, 1261 Thiirane, and its derivatives, 1128 Thioacetals, 787 Thioacetamide, carcinogenicity of, 50 Thiocarbanilide, and phenyl isothiocyanate from, 966 Thiocyanates, table of physical constants of, 1395 Thioethers, see Sulphides Thiols, 787 characteristic chemical properties of, 1214 derivatives of, 1238 spectroscopic features: fragmentation (m.s.), 377 group frequencies (i.r.), 314 correlation table, 1422 table of, and derivatives of, 1387 Thionyl chloride: purification procedures for, 466 reactions involving use of, 559, 692, 705, 716, 723, 844, 911 Thiophene: acylation of, 1014 1506 detection of, in benzene, 398 formylation of, 996 Thiophene-2-aldehyde, see 2-Formylthiophene Thiophenols, hazards in use of, 888 Thiourea: carcinogenicity of, 50 decomposition of ozonides with, 104, 592 in heterocyclic synthesis, 1152 precautions in use of, 788 reaction with alkyl and aralkyl halides, 789 Thioureas, table of physical constants of, 1396 Thorium carbonate-pumice, 614 THP-ethers, see Tetrahydropyranyl ethers D- Threose, 640 Threshold limit value (TLV), 45 (S)-( - )-N-Tigloylproline, 730 bromolactonisation of, 731 i.r and p.m.r absorptions of, 730 Tigloyl chloride, and reaction with (S)-proline, 730 Tin, reactions involving use of, 892, 896, 1023 Tin(n) chloride: anhydrous, 465 reactions involving use of, 595, 949 Tinuv) chloride, reaction involving use of, 993 Tishchenko reaction, 520 Titaniumuu) chloride: precautions in use of, 637 reactions involving use of, 600, 636 Titaniumuv) chloride: hazards of, 44 reactions involving use of, 783, 803, 997, 1189 Titaniumnv) isopropoxide, use in asymmetric epoxidation, 1133 TMBS-ethers, see t-Butyldimethylsilyl ethers TMS-ethers, see Trimethylsilyl ethers Tobias acid, see 2-naphthylamine-I-sulphonic acid Tollen's test, 1219 p-Tolualdehyde: Cannizzaro reaction with, 1031 Doebner/Knoevenagel reaction with, 1041 in heterocyclic synthesis, 1189 a-Toluamide, 1080 Toluene: acylation of, 1012 aroylation of, 1027 chlorosulphonation of, 877 I3C-n.m.r spectrum of, 322 physical properties of, 1442 p.m.r spectrum of, 321 purification procedures for, 398 side-chain halogenation of, 864 sulphonation of, 874 Toluene-p-sulphinic acid, and sodium salt, 888 Toluene-a-sulphonamide, and i.r and p.m.r absorptions of, 880 m.s data of, 880 oxidation of, 881 Toluene-p-sulphonamide, and p.m.r absorptions of, 880 halogenation of, 882 i.r spectrum of, 317 m.s, data of, 882 INDEX Toluene-p-sulphonamides, from amines, 1275 Toluene-p-sulphonates: of amino acids, 1280 of monosaccharides, 659 of phenols, 1248 Toluene-p-sulphonic acid, and i.r absorptions of, 875 Toluene-o(and p)-sulphonyl chlorides, 877 amide from o-isomer, 880 amide from p-isomer, 882 esters from p-isomer, 661, 886 i.r and p.m.r absorptions of and m.s data of, 878 purification of p-isomer, 466 reduction of p-isomer, 887 separation of olp mixture, 878 Toluene-p-sulphonylhydrazones: of carbonyl compounds, 477 reduction of, 476, 477, 828, 832 o-Toluic acid, m.s data and p.m.r absorptions of, 1063 p-Toluic acid, and p.m.r absorptions of, 1064, 1069 p-Toluidides: from carboxylic acids, 1262 from esters, 1268 o-Toluidine: diazonium salt from, in synthesis, 933, 935, 937 formylation of, 1158 iodination of, 910 RL of, 48 m-Toluidine, RL of, 48 p-Toluidine: acetylation of, 944 Bucherer reaction with, 901 N-chlorination of, 915 diazonium salt from, in synthesis, 928, 931, 934, 938, 940 in heterocyclic synthesis, 1188 oxidation of, 858 RL of, 48 substituted ureas from, 965 P: Toluidine salts, of sulphonic acids, 1286 o-Tolunitrile, and i.r and p.m.r absorptions of,939 hydrolysis of, 1063 oxidation of, 1080 p-Tolunitrile, and i.r and p.m.r absorptions of,938 hydrolysis, 1064 o-(p-Toluoyl)benzoic acid, and cyclisation of, 1027 2-p- Tolylamino-5-naphthol-7-sulphonic acid, 901 4-(p- Tofylaminojpent-S-en-z-one, and cyclisation of, 1188 m-Tolylboronic acid, and oxidation of, 973 anhydride from, 974 p-Tolyl cyanide, see p-Tolunitrile p- Tolylsodium, and carboxylation of, 1069 alkylation of, 829 p-Tolylurea, 965 Tosyl chloride, see Toluene-p-sulphonyl chloride Toxic chemicals, ingestion, inhalation, and absorption of, 44 Toxic vapours, detection of, 45 Transesterification, 1268 Transetherification, 796 Transmetalation, 1067 Traps: gas absorption, 85 for oil pumps, 192 1,2,4-Triacetoxybenzene, 1026 1,1,1-Triacetoxy-2, l-benzoxiodol-3(3H)-one (periodinane), 588, 869, 871 Trialkynylalane, 513 2,4,6-Tribromacetanilide, 909 2,4,6-Tribromoaniline: and acetylation of, 909 diazonium salt from, in synthesis, 943 m.s data for, 909 p.m.r absorptions of, 909 1,3,5-Tribromobenzene, 943 1,2,3-Tribromopropane, 577 Tributyl borate, reaction involving use of, 973 Tributyltin hydride, 450, 1125 reaction involving use of, 731, 1124 Tributyltin chloride, reduction of, 1125 Trichloroethanol, 523 Trichloromethane, see Chloroform Trichloromethylsilane-iodine, deprotection of methyl ethers with, 550 eis,trans.cis-Tricyclo[ 5.3.0.02.6)decane-3,8dione,l124 cis,trans,cis- T ricyclo[5.3.0.02.6)decane-3,10dione, 1123 Tricyclohexylphosphine, carbon disulphide complex of, 1104 Triethanolamine, physical properties, 1444 Triethoxymethane, see Triethyl orthoformate Triethylamine, physical properties of, 1442 Triethylbenzylammonium, chloride, use as phase transfer catalyst, 598, 1110 Triethyl orthoformate, and p.m.r absorptions of,707 reaction with Grignard reagents, 597 Triethyl orthopropanoate, oxazoline from, 689 Triethyl phosphate, N-alkylation with, 905 Triethyl phosphite, alkyl phosphonate from, 496 Triethyl phosphonoacetate, reaction with cyclohexanone, 806 Trifluoroacetic acid, physical properties of, 1442 reactions involving use of, 734, 772 Trifluoroacetic anhydride, peracid from, 766, 858 Triglyme, see Triethylene glycol dimethyl ether 2,4,6-Trihydroxyacetophenone, 1017 1,2,3-Trihydroxybenzene, see Pyrogallol; 1,3,5see Phloroglucinol (2R,3R)-2,3,4- Trihydroxybutanal (0erythrose), 640 (2S,3R)-2,3,4- Trihydroxybutanal (n-threose), 640 1507 INDEX 2,4,6-Trihydroxyisobutyrophenone, 1011 2',4',6'-Trihydroxy-2-methylbutanophenone, 1012 2,4,6-Trihydroxyvalerophenone, 1012 3,4,5-Triiodobenzoic acid, 931 3,4,5-Triiodobenzoyl chloride, 1244 2,4,6-Triisopropylbenzene, chlorosulphonation of, 878 2,4,6-Triisopropylbenzenesulphonyl chloride, 878 reaction with hydrazine, 881 2,4,6-Triisopropylbenzenesulphonyl hydrazide, 881 storage precautions, and purification of, 882 Trimethylacetic acid, see 2,2Dimethylpropanoic acid Trimethylamine N-oxide, oxidant for organoboranes, 542 2,4,6-Trimethylbenzaldehyde, m.s data and p.m.r absorptions of, 994 1,3,5-Trimethylbenzene, see Mesitylene Trimethylchlorosilane (chlorotrimethylsilane), RL of, 87 3,3,5-Trimethylcyclohexanone: reaction with Grignard reagents, 538 reaction with ylides, 499 Trimethylene dibromide, see 1,3Dibromopropane Trimethylene glycol, see Propane-I ,3-diol 3,3,5-Trimethyl-l-methylenecyclohexane, and g.l.c of, 499 Trimethyloxosulphonium iodide, methylide from, 797, 1110 2,4,6-Trimethylphenol, oxidation of, 1025 Trimethyl phosphate, N-alkylation with, 905 Trimethyl phosphite, reaction involving use of, 1189 0-[ I,2,2-Trimethylpropyl)Smethyldithiocarbonate, 794 pyrolysis of, 493 2,4,6-Trimethylquinoline, and g.l.c of, 1188 Trimethylsilylaton: reagents for, 229 of carbohydrates, and g.l.c of, 231, 1247 of ketones, 801 Trimethylsilyl ethers, 552 N- Trimethylsilylimidazole (TMSI), 229 1-Trimethylsilyloxycyclohexene, 803 Trimethylsulphonium iodide, ylide from, in synthesis, 790, 1132 Trimethylsulphoxonium iodide, 1111 ylide from, in synthesis, 797, 1110 (- )-2,7,7-Triomethyltricyclo[4.I 1.0H)octane, and p.m.r and 13C_n.m.r absorptions of, 1109 1,3,5-Trinitrobenzene, adducts with arenes, 1240 2,4,7-Trinitro-9-fluorenone, adducts with arenes, 1240 2,4,6-Trinitrophenol (picric acid), 976 hazards of, 48 2,4,6-Trinitroresorcinol (styphnic acid), 1240 1508 Trioctyloxyboroxine, 596 Triphenylchloromethane (triphenylmethyl chloride), carbanion from, 741 Triphenylethylene, 845 photochemical cyclisation/dehydrogenation, 846 Triphenylmethane, 834 Triphenylmethanol, 540 Triphenylmethyl halides, 466 Triphenylmethylphosphonium bromide, 498 ylide from, in synthesis, 499 Triphenylmethylsodium, 741 Claisen ester condensation with, 741 determination of, 742 Triphenylphosphine, aliphatic halide formation with, 556 reaction with alkyl halides, 498 reaction with bromine, 897 reaction with methyl bromide, 498 1,I,3-Triphenylprop-z-yn-l-ol and rubrene from, 844 2,4,6-Triphenylpyrylium tetrafluoroborate, 1169 reaction with benzylamine, 1170 Triton (benzyltrimethylammonium hydroxide), 1101 Tropinone, 17 DL- Tryptophan, 756 i.-Tryptophan, i.r spectrum of, 312 Tyrosine, removal from cystine, 761 Ullmann reaction, 835, 837 Ultrasonic baths: use in activation of metal surfaces, 727, 1107, 1108 use in cleaning glassware, 29 use in stopper loosening, 58 Ultraviolet and visible spectra: determination of,384 cells for, 387 electronic transitions in, 385 energy relationships in, 384 solution preparation and solvents for, 386 Ultraviolet radiation, hazards of, 52 Ultraviolet-visible spectroscopy (see also Absorption maxima (u.v.-visible)), 383-98 auxochrome, 388 bibliography, 394 chromophore, 388 electronic transitions in, 388 electron transfer (ET) bands, 390 molar absorptivity, 385 rules for diene and enone absorption, 390, 391 table of solvent correction values, 391 Umpolung, see Synthons, of reversed polarity Undecane, 477, 483 Unecane-l-thiol,789 Undecan-S-one, 614 Undecan-S-one toluene-p-sulphonylhydrazone, reduction of, 477 \lOEI Undec-IO-enoic acid: bromination of, 510 hydrobromination of, 576 Undecylenic acid (see also Undec-IO-enoic acid), 510 Undec-IO-ynoic acid, 510 hydration of, 612 Unsaturated compounds, see functional type, i.e Alkenes; Alkynes: Aldehydes, unsaturated analogues, etc Unsaturation, tests for, 1226 Uramil (Aminobarbituric acid), 1177 Urea: in heterocyclic synthesis, 1151, 1175, 1176,1177 substituted ureas from, 965 Vacustat, 194 Vacuum gauges, 193 Valeraldehyde (pentanal), 590 Valeric acid (see also Pentanoic acid), 671, 683 acid chloride from, 693 Valeronitrile, 714 hydrolysis of, 671 Valeryl chloride (see also Pentanoyl chloride), 693 acylation with, 1012 DL-Valine, 752 i.r spectrum of, 311 Vanadium(v) oxide (vanadium pentoxide): reaction involving use of, 1026 RL of, 46 Vanillin, O-alkylation of, 987 Vapour phase reactions and apparatus assemblies, 99-103 preparations involving use of, 492, 613, 614, 694,1122 Veratraldehyde, 987 Veratraldoxime, and dehydration, 1084 Veratronitrile, 1084 Vibro-mixer, 77 Vilsmeier reaction, 991, 992, 996 Vinylacetic acid, 673 esters from, 705 Vinylacetyl chloride, 705 Vinylbenzene, see Styrene Vinyl bromide, Grignard reagent from, 539 Vinyl chloride, carcinogenicity of, 50 l-Vinylcyclobutanol, and i.r and p.m.r absorptions of, 539 Vinyl halides, structural features, 553 Vinylic alcohols, structural features, 517 Wadsworth-Emrnons reaction, see HornerEmmons reaction Water, physical properties of, 1442 Wheaton-Hickman flask, 189 Willgerodt reaction, 1052, 1054 Williamson ether synthesis, 583, 584, 789, 984 PTC conditions for, 584, 988 Willstatter 'filtration nail', 146 Wittig reaction, 495 8, 796 Wittig-Horner reaction, 497 Wohl-Ziegler reaction, 577 Wohler's synthesis of urea, 963 Wolff rearrangement, 676, 676 Wolff-Kishner reduction, 476, 827,831 Woodward-Hoffman Rules, 1118 Wurtz reaction, 478, 479 Wurtz-Fittig reaction, 826, 829 Xanthate esters, 792 Xanthhydrol, 1270 Xanthrone, reduction of, 1270 Xanthylamides, of primary amides, 1270 N-Xanthylsulphonamides, from primary sulphonamides, 1289 o-Xylene: Birch reduction of, 1115 i.r spectrum of, 281 mass spectrum of, 364 p-Xylene: oxidation of, 1058 sulphonation of, 877 Xylenes (o,p,m): physical properties of, 1442 purification procedures for, 399 spectroscopic comparison of isomers, 825 p-Xylene-2-sulphonic acid (2,4dimethylbenzenesulphonic acid), 877 Xylidines, RL of, 48 e-n-Xylofuranose, 642 1,2-0-cyclohexylidene-, 657 P-D-Xylofuranose, 642 Yields, calculation of: g.l.c., 34 optical,34 percentage, 33 theoretical, 33 Ylides: of phosphorus, 495, 498 of sulphur, 496, 499, 790, 1089, 1131 Zeolites (molecular sieves), 396 Zemplen's method of deacylation, 644 Zinc: amalgamated, 467 reactions involving the use of, 476, 830, 843 powder or turnings, 467 activation of, 467, 727 reactions involving use of, 732, 893, 9558 Zinc chloride, reactions involving the use of, Zinc-copper couple, 467 activation of, by sonication, 1108 reactions involving the use of, 505, 1107, 1108 Zinc cyanide, 467 use in formylation reactions, 994 Zirconium-alizarin red S test paper, 1210 Zwitterionic structures: of animo acids, 746 i.r absorptions of, 308 of benzenediazonium-2-carboxylate, 833 of sulphanilic acid, 908 1509 REFERENCE DATA SPECTROSCOPY Page ref 270 271 Infrared absorption correlation chart Interpretation of infrared spectra Correlation tables for infrared spectroscopy 1421 I H chemical shift correlation chart 13C chemical shift correlation chart Common spin-spin splitting patterns Interpretation of proton magnetic resonance spectra Information from carbon-13 nuclear magnetic resonance spectra Correlation tables for nuclear magnetic resonance spectroscopy Solvents for nuclear magnetic resonance spectroscopy 325 326 341 359 329 1423 1431 Woodward-Fieser rules for ultraviolet-visible spectroscopy Ultraviolet-visible absorption of aromatic systems Solvent corrections in ultraviolet-visible spectroscopy Interpretation of mass spectra Data tables for mass spectrometry 390 390 391 373 1435 SOLVENTS Purification of solvents Table of properties of solvents Flash points of common solvents Drying agents for organic solvents and solutions Solvents for recrystallisation Solubility characteristics of organic compounds 395 1442 40 165 137 1198 SAFETY Recommended limit (RL) and control limit (CL) values of some common chemicals Carcinogenicity of groups of compounds and of specific substances Substances with very harmful cumulative effects Hazard symbols 44 48 50 1446 1511 PRACTICAL ORGANiC CHEMISTRY GENERAL Detection of elements Index to preparation and physical constants of derivatives of organic compounds The separation of mixtures of compounds Table of atomic weights 1512 1204 1236 1287 1494 ABBREVIATIONS NOMENCLATURE R Me or CH Et or C 2H Pr or C 3H Pr i or (CH 3hCHBu or C 4H g Bui or (CH3)2CH·CH2But or (CH 3hCBus or CH 3'CH 2'CH(CH 3)-Sia or (CH 3hCH'CH(CH3)Thex or (CH 3hCH'C(CH3hPh or C 6H alkyl n methyl s ethyl t n-propyl i isopropyl (I-methylethyl) n-butyl isobutyl t-butyl (I,I-dimethylethyl) s-butyl (I-methylpropyl) s-isoamyl (1,2-dimethylpropyI) t-hexyl (I, I,2-trimethylpropyl) phenyl Ac or Me'COBz or Ph·COBn or Ph'CH 2Boc or Me3C'O'COCbz or Ph·CH 2·O·COMEM or Me·O·CH 2·CH 2·O·CH2Ms or Me'S02Ts or p-Me'C 6H 4'S02 - acetyl benzoyl benzyl t-butoxycarbonyl benzyloxycarbonyl 2-methoxyethoxymethyl methanesulphonyl (mesyI) toluene-p-sulphonyl (tosyI) THPor tetrahydropyranyl D "0 straight-chain secondary tertiary iso REAGENTS AND SOLVENTS AIBN 9-BBN BDSC BTMSA DBU DCC DDQ DEG DET DIBAL DME IX,IX'-azo bisisobu tyronitrile 9-borabicyclo[3.3.1]nonane t-bu tyldimethyIchlorosilane N.O-bis(trimethylsilyl)acetamide I,8-diazabicyclo[5.4.0]undec-7 -ene dicyclohex ylcarbodiimide 2.3-dichloro-5.6-dicyano-l,4-benzoquinone diethylene glycol diethyl tartrate diisobutylaluminium hydride 1,2-dimethoxyethane (glyme) 1513 PRACTICAL ORGANIC CHEMISTRY DMF DMSO DNFB DSS EAA HMDS HMPA LAH LDA MCPBA MEK MVK NBS NCS PCC PDC PEG PPA PPTSA Py SBH TEG TFA THF TMEDA TMCS TMS 1514 dimethylforrnamide dimethyl sulphoxide 2,4-dinitrofluorobenzene sodium 3-(trimethylsilyl)-I-propanesulphonate ethyl acetoacetate hexamethyldisilazane [bis(trimethylsiIyl)amine] N,N,N',N',N",N"-hexamethylphosphotriamide lithium aluminium hydride lithium isopropylamide m-chloroperbenzoic acid ethyl methyl ketone methyl vinyl ketone N -bromos uccinimide N -chloros uccinamide pyridinium chlorochromate pyridinium dichromate polyethylene glycol poly phosphoric acid pyridinium toluene-p-sulphonate pyridine sodium borohydride triethylene glycol trifluoroacetic acid tetrahydrofuran N,N,N',N'-tetramethylethylenediamine chlorotrimethylsilane tetramethylsiIane ... Textbook of practical organic chemistry, including qualitative organic analysis Includes bibliographies and indexes ISBN 0-4 7 0-2 141 4-7 Chemistry, Organic- Laboratory manuals Chemistry, Analytic-Qualitative... Data Vogel, Arthur Israel Vogel' s textbook of practical organic chemistry 5th ed I Organic chemistry Laboratory techniques I Title I Furniss, B S (Brian Stanley), 1941 547 '0028 ISBN 0-5 8 2-4 623 6-3 ... Cataloging-in-Publication Data Vogel, Arthur Israel Vogel' s Textbook of practical organic chemistry - 5th ed / rev by Brian S Furniss [et al.] p cm Fourth ed published in 1978 under title: Vogel' s
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