Compendium of Organic Synthetic Methods [Vol 4]

511 Pages·1980·6.901 MB·English

by  L. Wade

Compendium of Organic
Synthetic Methods
Compendium of Organic
Synthetic Methods
Volume 4
LEROY WADE, Jr.
G.
DEPARTMENT CHEMISTRY
OF
COLORADO STATE UNIVERSITY
FORT COLLINS, COLORADO
A Wiley-lnterscience Publication
JOHN WILEY & SONS, New York Chichester Brisbane Toronto
Copyright 0 1980 by John Wiley 8 Sons, Inc.
All rights resewed. Published simultaneously in Canada.
part of this book may be reproduced by any means, nor
No
transmitted, nor translated into a machine language with-
out the written permission of the publisher.
Library Congress Catalog Card Number: 71-162800
of
ISBN 0-471-04923-9
Printed in the United States America.
of
10 9 8 7 6 5 4 3 2 1
CONTENTS
ABBREVIATIONS ix
INDEX, MONOFUNCTIONALC OMPOUNDS xi
INDEX, DIFUNCTIONAL COMPOUNDS xii
INTRODUCTION xiii
1 PREPARATION OF ACETYLENES 1
2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES,
AND ANHYDRIDES 9
3 PREPARATION OF ALCOHOLS AND PHENOLS 28
4 PREPARATION OF ALDEHYDES 73
5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS 102
6 PREPARATION OF AMIDES 135
7 PREPARATION OF AMINES 146
8 PREPARATION OF ESTERS 176
9 PREPARATION OF ETHERS AND EPOXIDES 198
10 PREPARATIONO F HALIDES AND SULFONATES 21 5
11 PREPARATIONO F HYDRIDES 235
12 PREPARATION OF KETONES 252
13 PREPARATION OF NITRILES 297
14 PREPARATION OF OLEFINS 309
15 PREPARATION OF DIFUNCTIONAL COMPOUNDS 340
PREFACE
By their compilation of Volumes 1 and 2 of this Compendium, Ian and
Shuyen Harrison filled one of the greatest needs of the synthetic community:
a method for rapidly retrieving needed information from the literature by
reaction type rather than by the author’s name or publicationd ate.
Compendium of Organic Synthetic Methods, Volume 4, presents the func-
tional group transformations and difunctional compound preparations of
1977, 1978, and 1979. We have attempted to follow as closely as possible
the classification schemes of the first three volumes; the experienced user of
the Compendium will require additional instructions on the use of this
no
volume.
Perhaps it is fitting here to echo the Harrisons’ request stated in Volume 2
of the Compendium: The synthetic literature would become more easily ac-
cessible and more useful if chemists could write well-organized, concise
papers with charts and diagrams that allow the reader to assess quickly and
easily the scope of the published research. In addition, the reporting of ac-
tual, isolated yields and detailed experimental conditions will save a great
deal of wasted effort on the part of other chemists hoping to apply the re-
ported reactions to their own synthetic problems.
I wish to express my gratitude to the many people who helped to bring this
book to completion: To Mrs. JoAnn Barley for her patience and dedication in
the typing of the camera-ready copy; to Roy Smith, James McKearin, and
Jon Lawson for proofreading the manuscript with great care and offering
hundreds of helpful suggestions; and to my wife Betsy for her patience and
moral support throughout the arduous preparation of this Compendium.
LEROYG . WADE,J R.
Fort Collins, Colorado
September, 1980
V
ABBREVIATIONS
An attempt has been made to use only abbreviations whose meaning will
be readily apparent to the reader. Some of those more commonly used are
the following:
Ac Acetyl
Am Amy1
Ar Awl
9-BBN 9-borabicyclo[3.3.1 Inonane
Bu Butyl
BZ Benzyl
CP Cyclopentadienyl
DBU 1,5-diazabicyclo[5.4.O]undecene-5
DCC Dicyclohexylcarbodiimide
DDQ 2,3-Dichloro-5,6-dicyanobenzoquinone
DEAD Diethyl azodicarboxylate
DIBAL (DIBAH) Diisobutylaluminum hydride
DMAD Dimethyl acetylenedicarboxylate
DME 1,P-Dimethoxyethane
DMF Dimethylformamide
DMSO Dimethyl sulfoxide
Et Ethyl
Hex Hexyl
HMPA, HMPT Hexamethylphosphoramide (hexamethylphosphoric triamide)
hv Irradiation with light
L Triphenylphosphinel igand (if not specified)
LAH Lithium aluminum hydride
LDA Lithium diisopropylarnide
MCPBA meta-C hloroperbenzoic acid
Me Methyl
MEM p-Methoxyethoxymethy I
Ms Methanesulfonyl
MVK Methyl vinyl ketone
NBS N-bromosuccinimide
Ni Raney nickel
@ Polymeric backbone
Ph Phenyl
PPA Polyphosphoric acid
X ABBREVIATIONS
PPE Polyphosphate ester
Pr Propyl
Py, Pyr Pyridine
Sia secondary-isoamyl
Tf Trifluoromethane sulfonate
TFA Trifluoroacetic acid
TFAA Trifluoroacetic anhydride
THF Tetrahydrofuran
THP Tetrahydrop yranyl
TMEDA Tetramethylethylenediamine
TMP 2,2,6,6-Tetramethylpiperidine
TMS Tri methylsiI y l
Ts p-Toluenesulfonyl
A Heat
Pg. 8 22 63 95 145 165 197 287 338
(PROTECTION] Sect. Acetylenes 15A Carboxylic acids 30A Alcohols, phenols 45A 60A Aldehydes Amides 90A Amines 105A 120A Esters Ketones 180A Olefins 210A Blanks in the table correspond to sections for no additional which examples were found in the literature.
6 9 8 4 9 7 0 0 2 3 3 3 4 4 5 7 7 1 8 5 9 6 0 7
90 919102 02020202 03030313
13 131323 23232323 23232323
181 297 184 298 186 301 187 303 188 303 190 303 191 305 192 306 193 306 194 307 195 307
166 252 167 253 168 257 169 264 170 266 172 268 173 269 174 270 175 271 176 274 177 275 179 282 180 284
152 235 153 236 155 239 157 239 158 241 159 242 160 243 163 250 165 251
136 21 5 137 217 138 217 139 221 140 222 142 223 144 225 145 226 146 227 147 230 149 231 150 233
3 8 4 3 8 5 9 6 0 6 2 8 4 9 5 4
12191220 122012201320 1320 13201321
7 6 8 2 9 6 1 8 2 9 3 9 4 1 5 1 6 2 7 4 9 6 0 7
070808 18181819191919 1929
111111 11111111111111 1111

3 6 48 6 0 7 4 8 5 9 6 0 6 2 8 3 0 4 1 5 1
94 94 9595959505 05060606
1 1 1 1 1 111 11111111
77 135 79 137 81 138 82 140 83 141 84 141 85 142 86 142 87 143 88 144 90 145

61 102 62 103 63104 64 105 66 106 68 107 69 107 70 109 71 113 72 115 74 118
7 3 86 9 2 0 3 1 4 2 4 3 6 4 6 5 7 6 0 7 0 9 2 0 4
4747485858585858585 959 59 69
31 28 32 28 34 29 36 36 37 37 38 38 39 39 40 44 41 46 42 48 44 59
16 9 17 9 18 12 19 13 23 15 25 19 26 19 27 20 29 21 30 22
1 1 4 3 8 5 0 5 2 6 4 7
1 1 1
I
Acetylenes Carboxylic acids, acid halides, anhydrides Alcohols, phenols Aldehydes Alkyls, methylenes, aryls Amides Amines Esters Ethers, epoxides alides,sulfonates,sulfates (RH) Hydrides Ketones Nitriles Oletins Miscellaneous compounds
H
E.
DIFUNCTIONAL COMPOUNDS
INDEX,
Sections-heavy type
Pages-light type
315 325
352 367
317 327
306
344 359 370 403 410 415
307 318 328 337
360 372 391
344
309 320 339
330
345 361 375 392 412 420 440 465
448
310 331 340 355 361 370 373
347 381 394 413 429 456 474
362 382 395 407 413 430 441 457 475 490 493
348
Blanks in the table correspond to sections for which no examples were found in
the literature.
xii