Compendium of Organic Synthetic Methods Volume 2

Compendium of Organic Synthetic Methods Volume 2 IAN T. HARRISON and SHUYEN HARRISON SYNTEX RESEARCH PAL0 ALTO, CALIFO...

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Compendium of Organic Synthetic Methods Volume 2 IAN T. HARRISON

and SHUYEN HARRISON SYNTEX RESEARCH PAL0 ALTO, CALIFORNIA

A Wiley-lnterscience Publication JOHN WILEY & SONS, New York

Chichester

Brisbane

Toronto

ANOTETOTHEREADER

This book has been electronically reproduced from digital We arc information stored at John Wiley & Sons, Inc. pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.

Copyright @ 1974, by John Wiley &Sons, Inc. All rights reserved. Published simultaneously in Canada.

Reproduction or translation of any part of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner IS unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data:

Harrison, Ian T Compendium of organic synthetic methods.

1. Chemistry, Organic-Synthesis. Shuyen, joint author. 11. Title QD262.H32 547’.2 ISBN 0-471-35551-8

71-162800

I. Harrison,

PREFACE Compendiun? of Organic Synthetic Methods, Volume 2 presents the early 1971 to early 1974 crop of published functional group transformations, plus the gleanings from previous years. It is in part a supplement to Volume 7 and in addition contains a new chapter on the preparation of difunctional compounds. Previous reviewers and abstractors have tended to avoid difunctional compounds, having found the data particularly well concealed in the literature. Addition of this new chapter increases the complexity of the classification schemes, requiring more instruction in the use of the book. However, the system used is still simple enough that those who wish to just jump in will do well with no more guidance than that offered by the indexes. The task of abstracting the approx. 90 journals covered by Volume 7 and 2 of the Compendium becomes ever more difficult as chemical publications continue t o appear in increasing numbers. Within a few more years it will not be possible for a team of two to continue as sole abstractors, writers, artists, typists and proofreaders for the Compendium. Perhaps a fully organized abstracting service, responsive to the needs of the synthetic chemist, will someday be set up. It would help, of course, if chemists would learn to write orderly, concise papers that can actually be read rather than deciphered. Ian T. Harrison Shuyen Harrison Palo Alto, California May 1974

iii

CONTENTS AB B REVIAT10 NS INDEX, MONOFUNCTIONAL COMPOUNDS IN DEX, DI FUNCTIONAL COMPOUNDS HOW TO USE THE COMPENDIUM I NTRODUCT ION 1 PREPARATION OF ACETYLENES 2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES 3 PREPARATION OF ALCOHOLS AND PHENOLS 4 PREPARATION OF ALDEHYDES 5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS 6 PREPARATION OF AMIDES 7 PREPARATION OF AMINES 8 PREPARATION OF ESTERS 9 PREPARATION OF ETHERS AND EPOXIDES 10 PREPARATION OF HALIDES AND SULFONATES 11 PREPARATION OF HYDRIDES 12 PREPARATION OF KETONES 13 PREPARATION OF NITRILES 14 PREPARATION OF OLEFINS 15 PREPARATION OF DIFUNCTIONAL COMPOUNDS

V

vii ix xi xiii xv

1

7

28 53 70

82 92

108 127 136

146 155 185

193 214

ABBREVIATIONS Ac 9-BBN

acetyl 9-borabicyclo[3.3. llnonane butyl

DCC

dicyclohexplcarbodiimide

DDQ DMA DMF Et HMPA Me

2,3-dichloro-5,6-dicyanobenzoquinone d imethylaceta m ide di methy I f or ma m ide ethyl hexa met hy Ip h o sp ho ram ide ( hexa met hy I ph0spho r ic t r iamide) methyl methanesulfonyl N-bromoacetam ide N-bromosuccinimide N-c hIo r o w cc inim ide Raney nickel N-iodosucci ni m ide phenyl

Bu

Ms N BA NBS NCS Ni NIS Ph Pr PYr TH F TH P Ts

ProPYl pyridine tetrahyd rof u ran tetra hydropyra nyl p-toluenesulfonyl

vii

-.X

3

2

12 4

5 Miscellaneous compounds 15 5

Olefins 14

Nitriles

Ketones

Hydrides (RH)

Halides,sulfonates,sulfates 10

Ethers, epoxides

Esters

Amines

Amides

Alkyls, methylenes, aryls

Aldehydes 4

acid halides,anhydrides 1 Alcohols, phenols

Acetylenes

1 1 Carboxylicacids, 2

Sections-heavy type Pages-light type

29 23 30 24

23 13 24 15 25 16 26 18 27 20

16 7 17 8 18 10 19 11 20 12 21 13

45 45 46

4.4

41

37 32 38 32 39 34 40 36 41 38 42

31 28 32 29 33 30 34 31

58 65 59 66 60 66

64

54 61 55 61 56 63 57

46 53 47 53 48 55 49 57 50 59 51 59 52 60

76

74 79

72 77

69 73 70 73 71

71 65 72

64

62 70 63 71 84

88 89 89 90

88

85

81 85 82 86 83 87

79 84

77 82 78

99 98 100 99 101 101 102 101 103 102 104 103 105 104

114 118 115 119 116 121 117 122 118 124 119 124 120 125

117

106 108 107 108 108 113 109 115

96 95 97 112 96 117 113

91 92 92 92 93 92 94 94

INDEX, MONOFUNCTIONAL COMPOUNDS

152 146 153 146 154 148

156 149 142 157 141 149 158 150 129 144 159 131 141 150 130 145 160 132 141 151 131 146 132 142 132 162 132 152 163 153 134 149 133 144 135 150 165 135 145 154

137 136 123 138 127 137 124 130

166 155 167 156 168 157 169 159 170 160 171 161 172 161 173 162 174 162 175 163 176 167 177 168 178 174 179 175 180 178

199

200

Blanks in the table correspond to sections for which no additional examples were found in the literature.

Sect. Acetylenes 15A Carboxylic acids 30A Alcohols, phenols 45A Aldehydes 60A Amides 90A Amines 105A Esters 120A Ketones 180A Olefins 210A

1-1

186 187 187 202 188 199 203 200 204 200 190 205 188 201 191 206 189 204 192 207 189 204 193 190 209 208 195 210 191 211

184 186

182 185

196 193 197 194 198 195 199 197

67 90 105 126 181 211

47

5 26

Pg.

INDEX, DIFUNCTIONAL COMPOUNDS Sections-heavy Pages-light

302 218 303 220 304 222

313 241 314 246 315 248

type

type

323 276 324 333 284 317 325 287

225 256 298 322 336 346 358 382

309 320 330 339 347 354 360 365 369 372 228 260 302 324 337 348 362 384 394 405 231 269 311 327 340 352 372 387 400 414 428 311 322 332 341 349 356 362 367 371 374 376 377 231 270 312 328 340 353 374 388 400 417 430 432

Blanks in the table correspond to sections for which no examples were found in the literature.

xi

HOW TO USE THE COMPENDIUM Preparation of Monofunctional Monofunctional ComDounds

1

Compendi u m Volume 1

Protection of Monofunctional Compounds

1 I

page xi

1

-

1

Compendium Volume 2

rn

Section and page with examples

1 I

Section

and page

with examples

=t

Basic details

References

literature Original L

Index page ix

page xi

I)

Preparation of Difunctional Compounds

details

I$Authors

I

Further references

B Perform reaction

I

I

INTRODUCTION Relationship Between Volume 1 and Volume 2. Compendium of Organic Synthetic Methods, Volume 2, presents more than 1000 examples of published methods for the preparation of monofunctional compounds, updating the 3000 or so in Volume 1. I n addition Volume 2 presents a new chapter with about 1000 examples of the preparation of difunctional compounds. Methods for the protection of carboxylic acids, alcohols, phenols, aldehydes, amines, and ketones were included in Volume 1. I n Volume 2 protective methods for acetylenes, amides, esters, and olefins are also covered. The same systems of section and chapter numbering are used in the two volumes. Classification and Organization of Reactions Forming Monofunctional Compounds. Examples of published chemical transformations are classified according t o the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section reactions are listed in a somewhat arbitrary order, although an effort has been made t o put chain-lengthening processes before degradations. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation, which appears in both starting material and product, or increases or decreases i n the length of carbon chains: for example, the reactions t-BuOH + f-BuCOOH, PhCHzOH --z PhCOOH and PhCH = CHCHzOH -+ PhCH =CHCOOH would all be considered as preparations of carboxylic acids from alcohols. The terms hydrides, alkyls, and aryls classify compounds containing react. ing hydrogens, alkyl groups, and aryl groups, respectively: for example, RCHz-H-+ RCH,COOH (carboxylic acids from hydrides), RMe -+ RCOOH (carboxylic acids from alkyls), RPh -+ RCOOH (carboxylic acids from aryls). Note the distinction between R2C0 + R2CH2 (methylenes from ketones) and RCOR’ 3 RH (hydrides from ketones). The following examples illustrate the application of the classification scheme t o some potentially confusing cases: RCH = CHCOOH RCH =CH, ArH

(hydrides from carboxylic acids) (carboxylic acids from hydrides) (carboxylic acids from hydrides)

RCH = CH2 RCH = CHCOOH + ArCOOH

4

4

xv

INTRODUCTION

xvi

ArH + ArOAc RCHO -+ RH RCH = CHCHO + RCH = CH, RCHO + RCH, R2CH2 + R2CO RCH2COR+ R,CHCOR RCH 5: CH2+ RCH,CH, RBr+RC=CH+RC=CR ROH

+ RCOOH + RCOOR

(esters from hydrides) (hydrides from aldehydes) (hydrides from aldehydes) (alkyls from aldehydes) (ketones from methylenes) (ketones from ketones) (alkyls from olefins) (acetylenes from halides; also acety. lenes from acetylenes) (esters from alcohols: also esters from carboxylic acids)

Yields quoted are overall; they are reduced to allow for incomplete conversion and impurities in the product. Reactions not described in the given references, but required to complete a sequence, are indicated by a dashed arrow. Reactions are included even when full experimental details are lacking in the given reference. In some cases the quoted reaction is a minor part of a paper or may have been investigated from a purely mechanistic aspect. When several references are given, the first refers to the reaction illustrated: others give further examples, related reactions, or reviews.

How to Use the Book to Locate Examples of the Preparation or Protection of Monofunctional Compounds. Examples of the preparation of one functional group from another are located via the monofunctional index on p. ix. which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes: Section 2, acetylenes from carboxylic acids: and so forth. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of the index. Thus Section 1 gives examples of the reactions of acetylenes that form other acetylenes; Section 16, reactions of acetylenes that form carboxylic acids: and Section 31, reactions of acety. lenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, transposition are found in Sections 1, 17, 33, and so on, which lie close t o a diagonal of the index. These sections correspond to such topics as the prepara. tion of acetylenes from acetylenes, carboxylic acids from carboxylic acids, and alcohols and phenols from alcohols and phenols. Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Sec. tion 199 on olefins from aldehydes and Section 207 on olefins from ketones. Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and olefins are also indexed on p. ix.

INTRODUCTION

xvii

The pairs of functional groups alcohol, ester: carboxylic acid, ester: amine, amide; carboxylic acid, amide can be interconverted by quite trivial reactions. When a member of these groups is the desired product or starting material, the other member should, of course, also be consulted i n the text. A few reactions already presented i n Volume 1 are given again in Volume 2 when significant new publications have appeared. In such cases the starting material and product are shown in a contracted form: for example, ROH instead of PhCH2CH20H. The original literature must be used t o determine the generality of reactions. A reaction given i n this book for a primary aliphatic substrate may also be applicable t o tertiary or aromatic compounds. The references usually yield a further set of references t o previous work. Subsequent publications can be found by consulting the Science Citation Index. Classification and Organization of Reactions forming Difunctional Compounds. This new chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, aldehyde, amide, amine, ester, ether, epoxide. halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-arninoalcohols, 1,3aminoalcohols and 1,4-aminoalcohols are included i n a single section. It is recommended that the following illustrative examples of the classification of difunctional compounds be scrutinized closely. Difunctional Product

Section Title

RC E C-C CR RCH(0H)COOH RCH(COOH)CH,COOMe RCH(0Ac)COOH RCH = CHOMe R CH (0Me) RCHF2 RCH (Br) C H?F RCH(OAc) CH,OH RCH(0H)COOMe RCOCOOEt RCOCH,OAc RCH = CHCH,COOMe RCH = CHOAC RCH(Br)COOEt RCH(Br)CH,OAc RCH = CHCHzCH= CH2

Acetylene-Acetylene Carboxylic Acid-Alcohol Carboxylic Acid-Ester Carboxylic Acid-Ester Ether-0 lef in Ether-Ether Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Ketone Ester-Ketone Ester-Olefi n Ester-Olefi n Ester-Halide Ester-Halide Olefi n-0 lef i n

,

xviii

INTRODUCTION

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol-Esterj contains examples of the preparation of hydroxyesters; Section 323 (Alcohol -Alcohol) contains examples of the preparation of diols. Some preparations of olefinic and acetylenic compounds from olefinic and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, RCH =CHBr + RCH = CHCOOH, Carboxylic acids from Halides (monofunctional sections) or Carboxylic acid-Olefin (difunctional sections). In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. Thus the reaction RCI + ROH can clearly be extended to the preparation of diols by using the corresponding dichloro compound as a starting material Such methods are not fully covered in the difunctional sections. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acid, ester; amine, amide; carboxylic acid, amide can be interconverted by quite trivial reactions. Compounds of the type RCH(OAc)CH,OAc (Ester-Ester) would thus be of interest to anyone preparing the dial RCH(OH)CH?OH (Alcohol-Alcohol).

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PR E PARATIO N

Chapter 1

OF

AC ETY LE N ES

Section 1

t-BUCECH

Section 2

FOOMe (CH2)4COOH

Section 3

Acetylenes from Acetylenes

00000000000000000000000000

1 Ph3B

BuLi

2 I2 Et2O

THF

*

83%

t-BUCECPh JACS (1973)

95 3080

Acetylenes from Carboxylic Acids

P 000

C8H17CEC(CH2)3COOH e l e c t r o l y s i s MeOH

COOMe I

*

( C H ~ ) ~ C - C C ~7H I JCS (1955) 2218

Acetylenes from Alcohols

P

No additional examples

1

24%

2 Section 4

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 8

Acetylenes from Aldehydes

000000000000000000000000

CfCH

or BuLi T e t r L e t t (1972) 3769

CH=CH2

Br2 cc14 2 NaNH2 NH3

Et20

CECH

*

J Med Chem (1972)

Section 5

Acetylenes from Alkyls, Methylenes and Aryls

00000000000000000000000000000000000000000000

No examples

Section 6

Acetylenes from Amides

0000000000000000000000

Yo examples

Section 7

Acetylenes from Arnines 0000000000000000000000

140 a d d i t i o n a l examples

Section 8

Acetylenes

%ram Esters

P

No a d d i t i o n a l examples

Me

2 1262

48%

SECTION 10 Section 9

ACETYLENES FROM HALIDES

3

Acetylenes from Ethers 0000000000000000000000

No examples

Section 10

Acetylenes from Halides

P

Examples o f the conversion o f dibromides into acetylenes are included in section 14 (Acetylenes from Olefins)

1 Mg E t 2 O THF

OMe

2 coc12 3 ClCH=CC12

8 bMe

55%

c-c Me6

Synthesis (1972) 38

1 Li

Me

THF

4 Base

RBr

NaCXH NH3

2 BuLi

0 R2C-CHBu I t

31 %

SECTION 134 R2CO

133

ETHERS AND EPOXIDES FROM OLEFINS 0

MeCHBr2 BuLi THF

I \

R2C-CHMe

+

2 3009

Tetrahedron (1972)

2 6109

(1971)

(t-Bu)zCO

1 PhSCH2Li THF t -

2 Me30 BF4 CH2C12

3 NaOH H20

Section 133

*

0

(~ - B u ) ~ C - C H ~ I \

JACS (1973)

2 3429

Ethers and Epoxides f r o m Nitriles 000000000000000000000000000000000

No examples

Section 134

Ethers and Epoxides from Olefins

00000000000000000000000000000000

0

OMe

Synthesis (1972) 483

JCS

(1971) 1174

42%


134

MezC=CH2

T1( OAC ) 3 HOAc H20 THF

0

I \

< 82%

MezC-CH2 J O C (1971)

(40 AgOAc

t-Bu

SECTION 134

36

1154

KOH

t-Bu

t-Bu T e t r a h e d r o n (1972)

2 3475

74% MeCN H20

0 T e t r Lett (1973) 4359

[Mo (02)20] *HMPA

*

0 I \ CgH13CHCHMe T e t r a h e d r o n (1970) 26- 37

0

m-Chl oroperbenzoi c a c i d

I !

t

C~H~~CHCHZ

4,4 ' - t h i o b i s - (6-t-butyl-3-methyl phenol) C1CH2CH2C1 (Applicable t o unreactive o l e f i n s )

Chem Comm (1972) 64

*e

EPOXIDES FROM MISCELLANEOUS COMPOUNDS

SECTION 135

m-Chloroperbenzoic acid NaHC03 CH2C12 H20 OAc

135

86%

OAc (Method f o r a c i d s e n s i t i v e compounds) J O C (1973)

Peracid

R2CzCR2

___t

2 2267

0 I \ RzC-CRz

p-Methoxycarbonylperbenzoic a c i d J O C

(1972)

37

4210

disuccinoyl peroxide S y n t h e s i s (1973) 156 o-Sulfoperbenzoic a c i d T e t r Lett (1971) 691 P r e p a r a t i o n o f RC002H from RCOCl + (EtO)zP(O)OAg J O C (1971) 36 2162

S e c t i o n 135

Epoxides from Miscellaneous Compounds

0000000000000000000000000000000000000

J O C (1968)

33 4045


Chapter 10

Section 136

PREPARATION OF HALIDES AND SULFONATES

Halides and Sulfonatss from Acetylenes 00000000000000000000000000000000000000


Section 137

Br2

RCOOH

00000000000000000000000000008

HgO CCl4 b

n

(CH2)7

Halides from Carboxylic Acids

C=CHCOONa

W

a

RBr

6r2 DMF

O r g Synth (1971) 106 J O C (1972) 31 669 664

n

(CH2)7

C=Ch’Br

u

45%

J O C (1965) 30 2208 JCS (1971) 2352

ocooH NCS Pb(OAc)4*

EMF HOAc

Synthesis (1973) 493 136

83%

RCOOH

I2

Pb(OAc)4

1 TlOEt

CgHigCOOH

2 Br2

Section 138

RI

pet

Org React (1972)

ether f

CCl4

2 279

89%

C9H19Br J O C (1969)

34

1172

Halides and Sulfonates from Alcohols 000000000000000000000000000000000000

Halides from a l c o h o l s . . Sulfonates from a l c o h o l s .

ROH

137

HALIDES AND SULFONATES FROM ALCOHOLS

SECTION 138

(Ph0)3P.MeI

. . . . . . . . . . . . . . . . . page ....................

RI

Org S y n t h (1971)

(PhO)QP*PhCH2C1 0

xo

ROH

Ph3P CCl4

DMF

RC1

137-139 140

44

70% 0

xo

JOC (1972)

37

2289

JOC (1972)

37

1466

138

8uOH

ROH

Ph3P *C12

BuCl

NBS Ph3P

+

[)CH20H

JACS (1964)

RBr

CH@ ;H2c5N-SMe2

Ph2CHOH

OF ORGANIC SYNTHETIC METHODS VOL 2

COMPENDIUM

2 342

-

C1

> 95%

Ph2CHC1

( S p e c i f i c f o r a l l y l i c and b e n z y l i c a l c o h o l s ) Tetr Lett (1972) 4339

.

Me2S B r 2

D

CH2Br

Chem Comm (1973) 212

T r i c h l o r o i socyanuric a c i d

*

CSHlloH

0°”

CHC13 NaOH H20 t

-

PhCHzNEt3 C1

*

JOC (1970) 2 3967 Chem Ind (1971) 1416

ocl Me

JACS (1971)

78%

44%

%H11 c1

i-Pr

i-Pr

Me

99%

964

Chem Corn (1970) 602 Carbohydrate Res (1971) Tetr Lett (1973) 3937

t

CH2C12

SECTION 138

93

1820

139

HALIDES AND SULFONATES FROM ALCOHOLS

SECTION 138

Me

83% Angew (1972) ( I n t e r n a t Ed

OCONHW

84 158

11 229)

NBS Pyr

42% (t38% di bromide)

Chem Comm (1971) 1112

i-PrOH

51-2 SO2

%N

38%

i-PrBr

S y n t h e s i s (1971) 639

CH20H

N'

Me

68%

Me Org Prep and Procedures (1970)

1. 189

NO2

Pr2C=CHCH20H

MsC1' LiCl

DMF

*

93%

Pr2C=CIICH$l T e t r a h e d r o n (1971) JOC (1971) 36 3044

21 5979


140

SECTION 141

100%

JCS (1953) 1225 Chem Ind (1971) 702

MsCl C F3

Et3N

92%

CF3 JOC (1970) 2 3195

Section 139

Halides and Sulfonates from Aldehydes

0000000000000000000000000000000000000


Section 140

Halides and Sulfonates from A l k y l s 0000000000000000000000000000000000

No a d d i t i o n a l examples For t h e conversion RH

Section 141

4

Rlial see s e c t i o n 146 (Halides from Hydrides)

Halides and Sulfonates from Amides

0000000000000000000000000000 000000


Section 142

NHZ

Ha,',~d,e,s,of~",oZ~~;~

CgHgONO CIiBrg

53%

NO2

NO2

1 ClCOOEt CgHg

RNMe2

t

2 KOH propylene glycol

Section 143

141

HALIDES FROM HALIDES AND SULFONATES

SECTION 145

JCS

C

(1966) 1249

RC1 J Med Chem (1971)

5 982

Halides and Sulfonates from Esters 0000000000000000000000000000000000


Section 144

Halides from Ethers 0000000000000000000

PhgP-Brp R20

Section 145

PhCN

t

RBr

JOC

(1972)

37

626

Halides from Halides and Sulfonates 00000000000000000000000000000000000

S L~CHZS~~]

PhCH2CHzBr

2 Me1 DMF

*

Ph(CH2131 T e t r L e t t (1972) 2743

C 70%


142

SECTION 146

50%

ROMs

liar EtCOMe

RI

0'' 1 Li

Et20

T e t r a h e d r o n (1971)

ox

~

2 Xp pentane

ArBr

CuCl

OH

picoline

ArCl

JACS (1958)

80

1716

Halides from Hydrides

P

MeCHCHzC1 I

PhH

57% (X=Br) 692 (X.1)

T e t r a h e d r o n (1972) 28 4883 Ber (1971) 104 2412-

____j

Section 146

11 5987

BF3 P2O5

*

Me PhCHCHzC1 JACS (1948)

37% 1772

p HpH s HALIDES FROM HYDRIDES

SECTION 146

143

53%

J Pled Chem (1972) 15_ 1297

JACS (1958)

Me

4327

NBS H2SO4 H20

t

95%

Other Ar brominating agents: IBr Br2-SO2 Br2-AgzS04 T1 (OAc)3-Br2 Ar chlorinating agents: TiC14-CF3C002H Ar iodinating agents: T1 (OCOCF~)Q-KI 12-HI04

t-BuOC1

dibenzoyl peroxide

30

J O C (1965)

304

JACS (1938) 60 256 B u l l SOC Chim F r (1971) 1785

Rec Trav Chim (1960)

31 88

J O C (1972)

Can J Chem (1972)

2 1022 1233

93 4841 (1971) 2 94

JACS (1971)

Org Synth

OC’ Helv (1957)

40 130

77%


144

HO (CHz)&HzMe

( i - P r )2NC1 hv H2SO4 H20

*

SECTION 149

tiO(CH2)6FHMe

6040%

c1

JACS (1971) 93 438 Synthesis (1973) 1

FH3 t-BuCMe2

Br2 HgO CCl4

*

CH2Br t- Bu ;Me 2 Can J Chem (1972)

Section 147

32% 3109

Hal ides from Ketones 00000000000000000000


For the r e a c t i o n C=O + C(Hal12 see s e c t i o n 368 (Halide-Halide)

Section 148

Halides and Sulfonates from N i t r i l e s 000000000000000000000000000000000000

No examples

Section 149

Halides from Olefins 00000000000000000000

For t h e conversion of o l e f i n s t o d i h a l i d e s s e e s e c t i o n 368 (Halide-Halide) For a l l y l i c halogenation s e e s e c t i o n 146 (Halides from Hydrides)

SECTION 150

HALIDES FROM MISCELLANEOUS COMPOUNDS

NBA

145

(I -Br

HF

Bu3SnH


i-PrCH=CHMe

BuCHSCH~

S e c t i o n 150

CH24HCH2Cl MeCH=CHCl

C7H1gSH

1 9-BBN

2 By2

THF

CHzC12

1 B2Hg THF 2 CH2=CHCHzI

*

air

i-PrCHeFHMe Br 3 Organometallic Chem (1971)

74%

2 C51

BuCH2CH2I JACS (1971)

93 1508

H a l i d e s from M i s c e l l a n e o u s Compounds

2

H2 (500 p s i )

Rh-Al2O3

ClCOSCl

Ph3P

*

*

MeCHzCH2Cl JOC (1964) 9 194

C7H15c1 Chem Corn (1972) 773

42-58%


Chapter 11

PREPARATION OF HYD R I D ES

This chapter 1 ists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen, e.g. RCH2X + RCH2-H or R-H

Section 151

Hydrides from Acetylenes

O O O O O O O O O O O O O O O O O O O O O O ~ ~

No examples of the reaction R C 3 R + RH occur in the literature

Section 152

Hydrides from Carboxylic Acids 000000000000000000000000000000

This section lists examples of the decarboxylation o f acids, RCOOH

CCOOH

-

---f

RH

Soda-1 ime

230'

Ph

JCS (1962) 1445

JACS (1950)

Section 153

72 1849

Hydrides from Alcohols and Phenols

0000000000000000000000000000000000

This section lists examples o f the hydrogenolysis of alcohols and phenols, ROH + RIi 146

SECTION 153

HYDRIDES FROM ALCOHOLS AND PHENOLS PhgSiH CF3COOH

Et3COH

*

CH2C12 (3ry only)

JOC (1971)

( PhO) 3P * Me1

ClOH210H

Et3CH

HMPA

NaBH3CN

b

147

a 758

c1 OH22

78%

99%

Chem Corn (1971) 1097

-G d j

1 BuLi MeOCH2CH20Me 2 (Me2N)zPOCl 3 Li EtNH2 t-BuOH THF

JACS (1972)

OH

1 Li

89%

94

5098

NH3 THF

2 NH4C1

Tetr Lett (1971) 1853

OH

@ OH

PhNCO

OCONHPh

OCONHPh Chem Ind (1973) 187

70%


148

ArOH

?h N -N 1 ‘lgN-;;

K2C03 Me2CO

2 H2 Pd-C

SECTION 154

ArH 0rg Synth (1971)

82

-

@@OH

2 A

3 NaOH MeOH

JOC (1966)

Also via:

Halides and Sulfonates Ethers

Section 154

31 3980

Section 160 159

Hydrides from Aldehydes 00000000000000000000000

This s e c t i o n l i s t s examples o f the decarbonylation of aldehydes, RCHO 3 RH. For the conversion RCHO + RMe e t c . s e e s e c t i o n 64 (Alkyls from Aldehydes)

RCHO

C6Hl 3CH0

Pd-C

‘190’

hl/

RH

JOC

PhCH2SH PhCOMe

t

(1968)

33 923

CtiH14 JACS (1963)

85 4010

HYDRIDES FROM AMINES

SECTION 157

CHo

Fe(C0)5 Bu2CO

*

i-Pr

i-Pr

149

36%

Tetr Lett (1973) 447

Section 155

Hydrides from Alkyls, Meth,ylenes a n d Aryls 000000000000000000000000000000000000000000


Section 156

Hydrides from Amides

~ ~ ~ O C O C O O O O O O O O C ~ O ~ ~

-

This section l i s t s examples of the conversion RCONH2 -+ RH

t-BuCiCCONH2

Also via:

Section 157

NaNH2 NH3

t-BuCXH

JCS (1963) 4402

Carboxylic acids (Section 152)

Hydrides from Amines 00000000000000000000

This section l i s t s examples o f the conversion RNH2 -+ RH

66% JCS Perkin I (1973) 5 4 1


150

SECTION 159

gJNH2 +.a COOEt

i-PrCH2CH20NO hydroquinone

H2SO4 dioxane

COOEt

ArNH2

-

Section 158

COOEt

COOEt


+ -

ArM2

X

Y

ArH

Y=RhCl (PPh)3 J O C (1971) 36 1725 Bu3SnH T e t r a h e d r o n (1970)

4609

Hydrides from Esters 00000000000000000000

This section lists examples of the reaction RCOOR' + R'H PhCOOCHPh2

Bu202 Bu3SnH

*

Ph2CH2 T e t r L e t t (1968) 4351

Section 159 PhONe

Hydrides from Ethers

Ni MeOH

PhH

A u s t J Chem (1963)

16 20

62%

HYDRIDES FROM HALIDES AND SULFONATES

SECTION 160

151

Hydrides from Hal i d e s and Sulfonates

Section 160

000000000000000000000000000000000000

This s e c t i o n l i s t s t h e r e d u c t i o n o f h a l i d e s and s u l f o n a t e s RX

NaBH3CN HMPA

c12H25X

--f

RH

96% (X=I) 97% (X=Br) 78% (X=OTs )

c12H26

C h e m Corn (1971) 1097 J O C (1971) 1568 J A C S (1973) 95 6 1 3 1

a

C8H17x

Cu I- L i A1 H (OMe ) 3 THF

b

C8H18 J A C S (1973)

95 6452

98% (X=Br) 95% (X=OMs)

99% J A C S (1973)

PhCH=CHCH2Cl

NaH TsNHNH2

Me2SO

95

1669

HOAc

PhCHzCHCH2NHNHTs + PhCHzCH'CH2

60%

T e t r L e t t (1969) 8 7 1

99% J A C S (1973)

95 6452

152


SECTION 162

30% Tetr Lett (1973) 447

PhFHCH2Br Br

NaBH4 Me2SO

64%

PhCH2Me Tetr Lett (1969) 3495

JACS (1948) (1947)

Section 161

2 2517 2 2555

Hydrides from Hydrides

dOOOOOOOIIOOOOOOOODb000

No additional examles

Section 162

Hydrides from Ketones 000000000000000000000-

This section lists examples of the conversion R2CO ---t RH. For the conversion R CO --t R2CH2 or RzCHR' see section 72 (Alkyls and Methylenes from Ketones?

SECTION 164

HYDRIDES FROM OLEFINS ‘OPh

153

t-BuOK H20

95%

____)

anisole

Ber (1971)

Section 163

Hydrides from Nitriles

0000000000000000000000

This section lists examples of the conversion RCN RCN

Fe(acac)3-Na

CgHg

w

-P

Li

RCN

EtNH2

Na NH3

Section 164

c12H26

RH

Hydrides from Olefins 000000000000000000000


RH

RH JACS (1971)

C12H25CN

104 2637

93 7113

46% (R=Ph) 100% (R’C8H17)

JACS (1969) 91 2059 Tetr Lett (1968) 1975

JOC (1972)

31 508

35%


154 Section 165

Hydrides from Miscellaneous Compounds

a

o

~

o

o

~

~

~

~

~

~

~

~

o

~

~

~

SECTION 165 ~

~

o

o

~

This sect ion lists examples of the rep1 acement of miscellaneous functional groups by hydrogen (RX + RH)

& -

NaBH4 hv

~

60% T e t r Lett (1971) 2197

-

KOH

“2

diethylene glycol

60%

Tetr Lett (1971) 3203

’” Me

Me

Ni

EtOH Me

Me

JOC (1966)

2 3980

70%

~

o

o

~


PREPARATION OF KETO N ES

Chapter 12

Ketones from A c e t y l e n e s

S e c t i o n 166

BuCXH

00000000000000000000006

1 RLi 2 (CgH17)3B

*

BuFHCOCBH17

hexane

Me

3 Me2S04 d i g l y m e 4 NaOH H202 H20

RCXR

1 BH 2 H202

NaOH


RCH2COR BH = BH2C1

BH = c a t e c h o l borane

1 NaNHNH2

85%

N2H4

2 H2SO4

Et20

*

JOC (1973)

JACS (1972)

PhCH2COC6H13 Ber (1966)

A c e t y l e n i c ketones 01 e f i n i c ketones

38 1617 94 4370

Section 309 374

155

99 1843

76%


156 Section 167 RCOCl

PhCOF

Ketones f r o m Acid Halides

aooooooooooooooo~ooooooo~

RiCuLi

RCOR'

BupCuLi

Et20

T e t r Lett (1971) 829 Synthesis (1972) 701

PhCOBu

94 5106

JACS (1972)

ME

Br(CH2)10COCl

SECTION 167

ide Br(CH2)10CObHEt

( t -BuOCu ;HE t ) L i

t

83%

T e t r L e t t (1973) 1815

C5H11 COCl

PhCH=CHCOCl

1 NapFe(CO)4

2 EtI

HMPA THF

Li [PhCOFe(C0)4]

h

C5H11 COEt JACS (1972)

2 1788

PhCH=CHCOPh

t

87%

22%

Synthesis (1971) 5 5

PhCH=CHCOCl

RhCl (CO) (PPh3)2 PhLi Et20 THF

t

PhCH=CHCOPh JACS (1973)

95 3040

85%

KETONES FROM ALCOHOLS AND PHENOLS

SECTION 168

~ 1 ~ 1cs2 3*

157

gCo@

NO2

50%

NO2

Organometallics in Chem Synth (1971) 1 1 5 1

Also v i a :

Olefinic ketones (Section 374)

Section 168

Ketones f r o m Alcohols and Phenols

D0D0000000000000000000000000000~0

23% JCS Perkin I (1972) 2100

0 OH

t-Bu

1 Me2SOnC12 2 Et3N

> 97%

t-Bu

Tetr Lett (1973) 919

91 % JACS (1972) 94 7586


158

Resin-CHzN=C=NPr-i Ph

H3P04 Me2SO C6Hg

b

SECTION 168 67%

Ph T e t r L e t t (1972) 3285

C U ~ O 250-300"

C5H11 !HOH Pr

(gas phase)

100%

C5H11F0 Pr

-+

T e t r Lett (1972) 257

68% Acta Chem Scand (1971)

Cr03-3,5-dimethyl pyrazole T e t r Lett (1973) 4499

R2CHOH

PhZCHOH

PhCHOH I

Me

RuO4

R2CO

*

Ph2C=NBr hv

C6H6

1125

T e t r Lett (1970) 4003

PhIC12 Pyr CHC13

-

25

Ph2CO

49% T e t r Lett (1973) 3635

PhTO

Me

94%

JOC (1970)

35

4245

SECTION 169

159

KETONES FROM ALDEHYDES

J O C (1973)

PhCHOH PhLHOH

HC(OEt)3

-

PhCHO;C,,oEt

BuLi

PhbHO

Et20

38

625

PhCH2

< 76%

I

PhCO

Aust J C h e m (1968)

21 2013

Me PhtOH

T1 (NO3)3

HOAc

w

PhCOH

PhCOMe

I

Me

JOC (1972)

Ye

63% 4204

Ye

PhCOCHCl

@JoH

37

@ocHcoph ___t

MeCO

K2C03

Me2CO

M~CO

JOC (1961) R e l a t e d methods:

S e c t i o n 169

26

4308

Aldehydes from A l c o h o l s and Phenols ( S e c t i o n 48)

Ketones f r o m Aldehydes

a o o D ~ ~ ~ o ~ ~ o o o o ~ o o ~ o ~ o o

P h C H 2 0 g CHO

CH3COEt NaOH MeOH

PhCH20

MeCO

320-350"

-

'+>CH=CHCOEt Cycl ohexene PhCti20QCH2CH2CO:TI Pd-C

THF

JOC (1972)

37

PhCH20 2204

< 30%

160

PhCHO

-


1 PhSH ZnC12 HOAc

PhC(SPh)2

2 NaH Me1 DMF

CH24HCHO

Me

HgCl2

-----+

PhCO

HgO (1971)

1 HCN

2s 961 36

3553

J Med Chem (1973)

CHz=CHCHCN I OCHMe

2 EtOCH.CH2

t

Me

JOC (1963)

-

bEt

SECTION 170

1 (i-Pr)2NLi

THF

*

la 749

CH2=CHCOC6H13

C6H13Br 3 H2SO4 MeOH 4 NaOH H20

N

75%

JACS (1971) 9 3 5286 Synthesis ( l v 3 ) 777

PhCHO --+ PhyHCN OH

- D i h y d r o p y r an

HC1

Et20

PhCHCN

1 NaH Me2SO

2 C7H15Br 3 HC1 H20

0 5


R e l a t e d methods: Also v i a :

Aldehydes from Aldehydes ( S e c t i o n 49)

O l e f i n i c Ketones ( S e c t i o n 374)

S e c t i o n 170

Ketones from A l k y l s and Methylenes

~ ~ ~ ~ ~ ~ O O O O O O O O ~ O O ~ O ~ O O O ~ O O O O O O O O O O

1 0

1 NBS h3

______f

2 Na2C03

H20


PhCOC7H15 56%

KETONES FROM AMINES

SECTION 172 02

PhBu-t

Co(OAc)2 HC1

HOAc

Section 171

PhCONEt2

b

PhCl

161

PhCOMe

23% Chem Comm (1971) 1166

Ketones from h i d e s 0000000000000000000

EtBr Li

THF

PhCOEt (One-step procedure)

(79%)


Section 172

t

-

PhNMe3 I

EtCHNH2

Ketones from Amines

0000000000000000000

1 MeCOCH2K K

2 CrO3 HzSO4

NH3

*

JACS (1972)

(V-CgHg) 2Mo (SMez)Br]+ PF6-

I

Me

P hCH2 COMe

H20

*

56%

94 683

EtCO I Me Chem Corn (1971) 1274

1

@CCtiO

C6H6

2 MeONa 3 (COOHI2 MeOH H20

Oo

JCS Perkin I (1972) 1652

86%


- -

162

COMPENDIUFI

No PhCHhs

1 TsCl

PhCHNH2

2 NaN02

Me

hY MeOH

{,e

HOAc

< 25%

PhCO Me

Rec Trav Chim (1971)

0

NH2

NHCH2C0Ph h r

MeOH

31 1254

Ketones f r o m E s t e r s

0000000000000000000

PrMgCl

HMPA

1 EtCHZMgCl

w

HMPA

+

2 Me1

t - Bu COPr

98%

t -BU COCHE t

81 %

I

Me

Tetrahedron (1973)

R2CHC)R

Ketones f r o m E t h e r s and Epoxides 00000000000000000000000000000000

t - B u t y l perbenzoate

t

R2COR

--+

R2CO

PhCO6

Synthesis (1972) 1

t -

(Me2CH)zO

40%

Tetr Lett (1968) 5357

L i C X N P h HMPA

PhCECCl

638 33

PhCXNMe2

) I

BuCECOEt

2%

PhCXNEt2

C6H6

BuBr

223

Angew (1964) (Internat Ed

16 537

1211

87%

3 506)

44%

t-BuCXNMe2 Angew (1964) 76 537 (Internat Ed 3 506 582) Ber (1970) 103 564

PhCfCNEt.2

86% Angew (1963) (Internat Ed

75 638 2 477)

224


Section 306

Acetylene

~

~

~

~

~

~

- Ester O

O

O

O

O

O

O

O

O

~

O

SECTION 306

~

Acetylenic esters C5H11 C X H

1BuLi THF

2 BF3

C5H11 CZCCHzCOOEt

3 N2CHCOOEt

C1 COOEt

MeCECH --+ MeCXLi

PhCXH

C(OEt)4

Can J Chem (1972)

71 %

JOC (1973) 38 3588 Annalen (1958) 614 37

* PhCECC(OEt)3

1 Ph3P=CHCOOEt CgH6

>

270"

2 1105

MeCSCCOOEt

ZnCl2

~ c o c l2

87%

--+

PhCXCOOEt

JACS (1958)

4607

()-

CXCOOEt

< 14%

70%

J Med Chem (1973) 16 72 Ber (1961)

94 3005-

Synth Corn (1972) 331

LiCHzCONMe2

COCHZCONMez Tetr Lett (1973) 1495

CECCOOMe

ACETYLENE

SECTION 307

CuCECCOOEt

- ETHER,

225

EPOXIDE

Pyr N

JCS

CgH17CfC(CH2)7COOH

C5H11 COCH2COOMe

COOH I (CH2)4COOMe

28%

JCS (1955) 2218

-

C5H11 CrCCOOMe

2 Tl(N03)3

Also via:

(1969) 2173

CgH17CEC(CH2)11COOMe

t

electrolysis

1 N2H4 MeOH

61%

Angew (1971) ( I n t e r n a t Ed

60 48)

-

90%

Acetylenic acids (Section 301)

Section 307

Acetylene

- Ether,

Epoxide

000000000000000000000000000

Acetylenic ethers and acetylenic epoxides Review: Ethynyl Ethers and Thioethers as Synthetic Intermediates

Advances i n Org Chem (1960) 2 117

CXH

1 BuLi

Et20

CXCH20Et

2 ClCH20Et Rec Trav Chim (1965) 84 31 Bull Soc C h i m Fr (196v4514

90%


226

EtCHzCHO

1 PhCH20H

HC1

MgS04

t

CsH6 2 Br2 C6Hg

EtyH-yHOCH2Ph

Br Br

1 PhNEt2

SECTION 308

EtCECOCHZPh

C6H6 2 NaNH2 Rec Trav Chim (1964)

EtBr

HCECOBu-t

LiNH2 NH3

Acetylene

Rec Trav Chim (1961) 80 810 JCS (1954) 1860 Org Prep and Procedures (1972)

4 89

0

11

BuC~CC-CH~ I Me

2 BrCH2COMe 3 KOH Et20

Section 308

a 301

EtCECOBu-t

t

1 EtMgBr

BuCXH

60%

40% Zh Obshch Khim (1960) (Chem Abs 2 499)

30 1194

- Halide

~ ~ ~ ~ ~ O O O O O O O O O O O O O O

-

Acetylenic ha1 i d e s

BuCXH

C5H11 C X H

1 NaNH2 NH3

2 I(CH2)4C1

1 KNH2 NH3

2 Clp Et20

53%

BuCX(CH2)4Cl JACS (1948) 2 1699 JCS (1950) 2100 J O C (1951) 16 1405

C5H11 CXC1 JACS (1937)

TsCl

1307

Annales de Chimie (1931)

16 309

SECTION 308

ACETYLENE BuMgCl

PhCXH

THF

S02C12

hexane

- HALIDE

227

PhCECCl

t

48% JCS

C

(1968) 1265

638 33

C l N E t 2 or NBS Annalen (1960) JACS (1961)

Br2

PhCXH

NaOH

PhC3CBr

____t

THF

H20

@

CECH

89% JCS (1963) 2295 Org S y n t h (1965)

1 HgCI2

CH=CHBr

4663

KI

45 86

NaOH

79%

E t O H H20 2 B r 2 CgHg JCS (1963) 2295

C5H11 CECH

1 EtMgBr

Et20

*

2 Br2

C5H11CtCBr JACS (1937)

BrCN

PrCICH

1 MeMgBr

2 12

Et20

t

70%

2

1307

Annales de Chimie (1926)

25

Annales d e Chimie (1926)

5

PrCXI

JACS (1933)

55

2150

5


228

SECTION 309

40% -

S e c t i o n 309

-

Acetylene

Can J Chem (1971)

49 403

- Ketone

OOOOOODOOOOOOOOOOOO

Acetyl e n i c ketones

BuCZCH

1 BuLi

Et20 pet e t h e r

UJ

t-BuCECH

PhCXH

1 EtMgBr

2 EtCH-y=NOH I Me C1

Et2O C&

A c O

PhCXH

Ye

t-BuCZCCCHEt II NOH

b

93 7320

Ye

---L.

*

PhCOyMe2

H20

30%

CH2CH20H

JOC (1973)

38

2129

Tetrahedron (1969)

BuCH=CH2

1 B2Hg

THF

2 Me3SiCZCH 0

BuLi

*

25 3157

BUCH~CH~COCH~CH~YHM~

21 %

OH

/ \

3 CH2-CHMe

4 H202

NaOH

H20

Tetr Lett (1973) 2741

MeCH20H

h r,

AcO

I

b

O ...,$HHMe

JCS (1967) 2032

YEt 1 L i [ (CH2)30CHMe]2Cu 2 CHC12COOH

H20

-6

Et20

(CH2)30H

JOC (1972)

31 1947

40%

SECTION 331

CH2=CHCOMe

ALCOHOL

1H 6 c

- NITRILE

i-PrOH THF

F

2 H202 base

31 1

HO( CH2)6COMe Chem Corn (1969) 1009

JACS (1969) (1973)

91 3083

95 3251

Also via: Acyloxyketones (Section 360)

Section 331

Alcohol

- Nitrile

000000000000000000

a-Hydroxynitriles (cyanohydrins) and B-hydroxynitriles

KCN HOAc

P

CHC13 EtOH

Ms 0 NaCN, NaHS03 HCN, Et3N Et2AlCN Me2FCN OH

JCS

C

(1968) 2283

Org Synth (1941) C o l l Vol 1 336

JACS (1956)

2 4100

T e t r Lett (1966) 1913

JACS (1953)

2 650

31 2


ft

PrCHO

BrCHCN

Zn THF

*

SECTION 332

EI t PrCHCHCN OH

-

66%

Compt Rend C (1969) 269 861 Organometallics in Chem Synth (1970) 1 5 7

CH3CN BuLi

PhCHO

PhTHCH2CN

f

THF

OH

83% Ber (1968)

101 3113

OH

HCN

Et3A1

THF

JCS

Ph2CO

CH3CN NaNH2 NH3

b

Section 332

C

93% JOC (1968) 33 3402 Ber (1968) 101 3113

Cyanohydrin trimethylsilyl ethers Cyanohydrin e s t e r s

Alcohol

(1970) 2365

Ph2TCH2CN OH

Also via:

56%

HO"

Section 366 361

- Olefin

0000000000000000d

..................... page ..................... ...................

Allylic alcohols Homoallylic alcohols Other o l e f i n i c alcohols

-

C=C-C-OH, Allylic and benzylic hydroxylation (C=C-CH i n section 41 (Alcohols and Phenols from Hydrides)

313-316 316 317

etc.) is listed

SECTION 332

ALCOHOL

1 (i-Bu)eAlH

BuCXH

2 MeLi

heptane

*

EtpO

- OLEFIN

31 3

73% (R=H) 68% (R=Me)

BuCH=CH$HOH

R

3 RCHO

trans JACS (1967) 89 2754 5085 T e t r L e t t (1971) 4571

1 Ph3P=CHMe

CgH13CHO

THF

3 HCHO

H\ /

Me

/

c=c

73%

\

CgH13 CH20H Me

\

/

Me

c=c

H'

67%

'FHOH

C6H13

h

C

H

( COOEt)2

U

-

JACS (1970) 92 226 6636 (1972) 94 4013 T e t r L e t t (1970) 447

NaH L i A l H 4

62%

MeOCH2CH20Me

J O C (1967) Ber (1970)

0

I \

EtCH2CHCHPr

1 PhzSez-NaBHq 2 H202

H20

EtOH

*

2 113 103 3771 98%

EtCH=CHCHPr OH

J A C S (1973) 95 2697 T e t r Lett (1973) 1979

0

OH

LiNPr2 BuLi (i-Bu)pAlH Li3PO4 (180') o r t-BuOK

JOC (1971) (1969)

34 3583

1365

J O C (1971)

a 3266

JOC (1972) 31 2060 Ber (1960)

93 2712

S y n t h e s i s (1972) 194

314

COMPENDIUM

-.

1 PhSOCHzCH=CMe2 ( i - P r ) z N L i

C6H13I

i-BuBr


2 (Me0)3P

THF

MeOH

--+ i-BuCuaMgBt-2

SECTION 332

CgH13CH=CH$Me2

OH Tetr Lett (1973) 1385 1389 JOC (1973) 38 2245 Chem Corn (1972) 702

1 EtCFCH

Et\

/

/

c=c

H 66%

\

BrCH20CH2CH2C1 i-Bu CH20H 3 BuLi Tetr Lett (1973) 2407

o:e

NaCZCH NH3,

C'CH

H2

Pd-SrCOg

Me

JCS (1952) 1610 642 Org Synth (1955) Coll Vol 3 416 JACS (1954) 3 4482

MezC=CH( CH2)2COMe

CH2=CHMgBr

THF +

VH

Me2C=CH( CH2)2yCH=CH2

83%

Me

Advances in Org Chem (1960)

1 Ph3P=CH2 THF

0

CHCH20H

2 EtCHLi I Me

3 HCHO

Me 2 CO

BuCH=CHAl (Bu-i ) 2 Et20

1. 1

37%


>

Me2fCH=CHBu OH Tetr Lett (1971) 4571

42%

ALCOHOL

SECTION 332

- OLEFIN

31 5

i-Pr

3 H202 4 A Bull SOC Chim Fr (1971) 3978

2 MeONa

OH

3 Ag(NH3)2N03 4 HOAc H20

EtCH=CH2 --+

(EtCH$H2)3B

H20

JACS (1972) 94 4013

0 I\ CH2-CHCHCH2

air

t

C6H6

Et(CH2)3CH=CHCH20H

JACS (1971)

93 2792 OH

1 :CBr2

2 BuLi

1 HgS04 HCOOH

CH=C=CH Et20

2 Ba(OH)2 H2:

((CH2)6’

CH=CHhH ((CH216

Bull SOC Chim Fr (1964) 3273

1 LiAlH4

/2 CECCH20H

12

3 MeeCuLi 12 LI 2i A l H 4

MeONa

* A l C l 3*

&cH20H

&\ /

3 Me2CuLi

JACS (1967) 89 4245 (1968) 90 5618

H20H

(73%

31 6


SECTION 332

Zn Et20

CH212

t

93%

JOC (1971) 2 3515

0

N2H4

HOAc

EtOH

*

O

O

66%

H

JOC (1961) 26 3615 (1968) 33 3347

83% A1H3 Et2SiH, (Ph3P)3RhC1

C5H11 C X H

1 BuLi

THF

4 HOAc

5 I2

0

Chem Corn (1970) 213 JOC (1969) 2 2206

T e t r Lett (1972) 5035

BIJ

\

/

C5Hll

75%

c=c

34 % CHZFHEt OH T e t r Lett (1973) 2741

C ;;HCHZBr

(One-step procedure) JOC (1973) (1963)

38 326 28 3269

(CH2=CHCH2)2Cd Bull SOC Chim F r (1969) 4038 8-Methal l y l n i c k e l bromide JACS (1967) 89 2755

95%

SECTION 333

ALDEHYDE

- ALDEHYDE

31 7

52% JCS

BuBr

1 Mg

2

C

Na EtpO

EtzO

c1y)

Bu

CIAO)

(1968) 2448

BuCH=CH(CH2)30H trans

J Med Chem (1967) lo 533 (1971) 14 236

?Et 1 Li(CH2)30CHMe

-73%

2 SOC12 Pyr

3 HC1 H20 EtOH

Pr$=CH(CH2)2CHO

71 %

J O C (1972) 37 1947

1 Ph3P=CH(CH2)40Li

THF

*

Pr2C=CH(CH2)2CH=CH( CH2)40H

-72%

Tetrahedron (1971) 2 5979

A l s o via: Acetylenic alcohols (Section 302)

Section 333

Aldehyde

- Aldehyde

00000000000000000000

Dialdehydes PhCH2CH2CHO --+ PhCH2CH2CH(OEt)Z

1 2‘

COC12 HCONMe2 NaOH H7O -

* PhCHZCH(CH0)2

Coll Czech (1958) 23 452 Synthesis (1973) 604 T e t r Lett (1973) 3979

31 8


SECTION 333

JCS (1959) 2441 Advances in Carbohydrate Chem (1961)

2 105

HI04 Ber (1956)

2224 Org React (1944) 1. 341

Pb(OAc)4 JACS (1949)

oo

m

2 3310

82% T e t r L e t t (1973) 4599

1 03 E t O H 2 Zn

HOAc

H20

EtOH

'

E

C

H

JACS (1957)

97%

O

2 3165

~ a 1 0 4 ,os04 JOC (1956) 2 4 7 8 Ru04 JACS (1958) 6682

0 Annalen (1962)

659 20

Electrol v s i s

30% Bull SOC Chim F r (1970) 183

ALDEHYDE

SECTION 335 Section 334

Aldehyde

-hide

Aldehyde

- Amine

- AMINE

31 9

0 0 0 0 0 0 0 0 0 0 0 0 0 ~ 0 0 0

No examples

Section 335

00000000000000000

Aminoaldehydes

n

OuNH*HC1

Me2CHCHO

PhCHO --+

A

HCHO

e! NCH2CCHO L-/ tie

0

t

1 3

iCH=N

85%

JACS (1951) 13 685 (1948) 2 2592 Ber (1932) 65 378 Org React (1942) 1 3 0 3

LiCii’I)

‘s

t

2 Chloramine-T

c1

(46%

PhCHCHO I

v

Tetr Lett (1972) 2991

Me2C=CH2 --+ Me2CCH2NO t1

Me2CCHO I

Br

Me2NH H20

1 EtNH2

EtOH

2 NaN02 HC1

t

H20

Me2:CHO EtNH

Zh Obshch Khim (1960) 30 805 (Chem Abs 55 556)

32%

Me2tCHO NMe2 JACS (1948)

2 2592

320 Section 336

COMPENDIUM OF ORGANIC SYNThETIC METHODS VOL 2

SECTION 336

Altebdwi0; 5 s t e r 00

0

0

0000

Esters of hydroxyaldehydes and e s t e r s o f carboxyaldehydes C5H11 CH2CHO

Pb(OAc)4 BF3

+

C5H11 FHCHO

C6H6

OAc

T1 (OAc)3

-

MeZFCHO c1

MeONa

EtzO

DMF

AgOAc

RCH2CtiO --+ RFHCHO I

Bull SOC Chim Fr (1968) 4083 Synthesis (1973) 567

2 3359

J O C (1968)

RCHCHO OAc

Bull SOC Chim F r (1968) 4083

-

0 Me$-CHOMe

1 HOAc E t Z O

I \

2 Et3N

JACS (1957)

Ph CHCOC 1 I

OAc

L i A1 H4

t-BuOH

diglyme

MezCHCHO --+ MeZC=CHN

t

10%

2 3448

55%

Ph:HCHO

OAc

3

DAc I Me2CCHO

B u l l SOC Chim F r (1968) 4083

1 N2CHCOOEt CuCl

t

2 HC1

E t O H H20

MeZFCHO CH2COOEt

Synth Corn (1973)

2

255

SECTION 336

1 BuBr

ALDEHYDE

9 3 N'

CH2COOEt

2 HC1 H20 3 NaBH4 E t O H THF

t-BuOK

- ESTER

THF

*

Ye

CO

COOEt

pH 5-6

JOC (1973)

H2 (600 atmos)

67%

BuTHCHO

4 (COOH)2

CH?=CCOOMe

321

38

36

Ye

MeCCOOMe

b

94%

Brennst-Chem (1967) (Chem Abs 66 85430)

3 46

SOMe 1 CH2=CSMe L i N ( P r - i ) p

EtCH2COOMe

THF

t

2 HC104 MeCN H20

90%

E t FHCOOMe CH2CHO

Tetr Lett (1973) 4711 4715

MeCH=CHCOOMe

1 EtSCH2SOEt BuLi

THF

t

2 ~ ~ 1 0 4

MeFHCH2COOMe

CHO Tetr Lett (1973) 3271

r t o

1 HC(OEt)3 H2SO4 E t O H 2 TsOH

t

flCoEt 1 03 E t O H

(CH2)10

EH

w

2 H2 Pd-BaCO3

Annalen (1962)

JACS (1952)

Also v i a :

Carboxyaldehydes ( S e c t i o n 314)

656 97

If_ 5324

CI O O E t

(FH2)10 CHO


322 S e c t i o n 337

- Ether,

Aldehyde

SECTION 338

Epoxide

OOOOoOOOOOOOOOoOuOOoooooo

Aryloxyaldehydes, a1 koxyaldehydes and epoxyaldehydes

PhOH

1 EtONa

*

PhOCH2CHO

2 BrCHzCH(OEt)2 3 H2SO4

MeCH=CHCHO

H20

PrOH

NaOH

JCS (1937) 1057

45%

MeCHCH2CHO I

OPr

JCS (1952) 4083

350'

50%

( v a p o r phase)

PhCH=CHCHO

t-BuOOH

MeOH

CHO JACS (1960)

73%

PhCHCHCHO \ I

0

J O C (1960)

H202 JACS (1956)

S e c t i o n 338

Aldehyde

82 6419

25 275 78 3087

- Halide

000000000000000000

Hal o a l dehydes

t-BUCECH

Et2NC1

hv

H2SO4 H20

60%

t-BU$HCHO c1 J O C (1967)

32

3263

SECTION 338

O C H o

ALDEHYDE

- HALIDE

323

O H 0

B r 2 CHCl3+

80%

JCS (1949) 737

Br2, CaC03

2 456

JACS (1957)

IBr

Chem Corn (1968) 849

30 587

CuBr2 J O C (1965)

EtCH2CHO

CuC12 DMF

3448

EtCHCHO

tl

30 587 32 4008

J O C (1965) (1967)

S02c12

2 3448

JACS (1957) (1954)

76 2695

-1 6 Ye

Me

1 Br2

2 H20

R

JACS (1957)

C5H11CH2CHO

Ace0 KOAc

C5H11 CH=CHOAc

1 Br2

CCl4

2 MeOH 3 HC1

7s 1115

C5H11 FHCHO

h

Br

H20

Org S y n t h (1955) C o l l Vol 3 127

Iodoaldehydes

EtCH2CHO

--+ EtCH=CHOEt

JACS(1953)

N-Bromophthalirnide MeOH

t

?Me

2 3493

EtCHCHOEt I

Acid

---*EtCHCHO

Br

Tetr Lett (1972) 4055 Brz;, NaHC03, H20 JACS (1955) 6365

1

Br

35%

324

Ph2CO

COMPENDIUM 1 LiCHC12


THF

+

2 LiCl

I

r.7

1 B2Hg THF

2 CH2=FCHO

Aldehyde

Tetr Lett (1969) 2181 (1972) 4661 Annalen (1966) 691 33

MeCH2CHCH2FHCHO I

81 %

Br

Me

Br

S e c t i o n 339

74%

Ph2CCHO LI

-

MeCH=CHMe

SECTION 339

JACS (1968) 9 0 4 1 6 5

- Ketone

000000000000000000

K e t o a l dehydes

1 HC1

CoCHN2

COCHO

2 Piperidine 3 Hg(OAc)2 HOAc H20 Ber (1971) 104 2475 Helv ( 1 9 4 3 ) z 2050 Rec Trav Chim (1971) 90 429 PhCH2COCl

--+

PhCH2COCHN2

1 EtSCl

Et20

*

2 EtSNa 3 B r 2 HC1

H20

PhCH2CH2COC1

--+

PhCH2CH2COCHN2

PhCH2COCHO

HOAc Ber (1957) 90 1230

1 Ph3P

2 NaN02 HC1 H20 THF

PhCH2CH2COCHO

Ber (1963) 2259 (1959) 2 1345

SECTION 339

PhCOOEt

PrCOOEt

ALDEHYDE

-

Me2SO t BuOK

*

t-BuOH

MeSOCH2SMe BuLi

THF

- KETONE

325

1 HC1

PhCOCH2SOMe

H20

PhCOCHO 2 Cu(OAc)2 CHCl3 Org Synth (1968) 48 109

64-73%

J O C (1967) 32 2 7 8 6 J A C S (1966) 88 5498

PrCOTHSOMe SMe

Hydro1y s i s

PrCOCHO

Tetr L e t t (1973) 4707

@-

CHCl2COC1

Me

c;o;3+

JQJCOC'"

QOCHO

Me

85%

Me T e t r L e t t (1971) 199

SeO2

dioxane*

@JcoCHo

-71%

PhO

PhO@ J C O C H 3 COCHC12

f

1 MeONa

PhCOCH3 --+ PhCOCH2Br

Me2SO

2 HC1 HOAc H20 J Med Chem (1964) 1 2 5 5 Org Synth (1943) C o l l Vol 2 509 Org React (1949) 2 331

PhCOCHO

a-picoline-1-oxide

J A C S (1957)

(71%

2 6562

Yakugaku Zasshi (1964) sd, 287 (Chem A b s 61 638)

COMPElUDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

326

yH20H

1 6

94 %

BuCOCH~CHO

(47%

CHO I

Air

CU(OAC)~

MeOH

HO.,'

BuCHO

SECTION 339

JOC (1963) 2 2001 Annalen (1973) 2078

-

1 HS(CH2)$H

HC1

2 ClCH$H(OEt)2 3 HOAC THF

H20

Bu,C,CH~CHO --+

ss U T e t r L e t t (1972) 3735

Me2CHCHO

--+

u -

n 0

Me2C=CHN

PhCOCl

dioxane

Me2yCHO

H20 p H 8

BuCH2COCOOMe

61%

Organometallics in Chem Synth (1971) 1 2 4 9


364 0

Ph6tkHCOOEt

BF3 C6H6

PhCH2COCOOEt

1 ClS02NCO CH2C12

EtCXEt

*

2 MeOH

SECTION 360 80%

JACS (1958)

2 6386

58%

EtCOFHCOOMe Et

T e t r Lett (1970) 27

1 NZCHCOOEt

PhCOCl

2 Ph3P i-Pr20 3 MeOH H20 4 ZnC12 EtpO 5 Pyr

?Si (Me2)Bu-t Et3N THF

t-BuOH

b

2 HC1 H20

2 TsOH CgH6

1

Di ketene

-

EtCH2COCH2COOEt

EtCOCHZCOOEt

>

85%

60%

JACS (1944) 1286 (1959) 2907 JCS C (1971) 2821

MeCOCHZCOOEt Na CgH6

2 NH3 NH4C1 H20

96 1948

T e t r L e t t (1973) 1297

COOBU- t 1 EtOMg-iHCOOEt Et20

EtCOCl

45%

Ber (1963)

1 CH24OEt

EtCH2COCl

PhCOCl

PhCOCH2COOEt

b

PhCOCH2COOEt

50%

Org Synth (1943) Coll Vol 2 266 (1963) Coll Vol 4 415

MeCOCH2COOBu-t

Org Synth (1962) 42 28 g 225

MeCOCH2COF JOC (1961)

7540%

SECTION 360 Review:

ESTER

- KETONE

365

The Acetoacetic E s t e r Condensation Org React (1942) 1 2 6 6

CH3COOEt

Na 3

MeCOCHZCOOEt

Org Synth (1932) C o l l Vol 1 235 NaH B u l l SOC Chim F r (1954) 504

NaN(SiMe3)z

Me2CHCOOEt

1 PhgCNa

Et20

2 PhCOCl

Ba3N4

Angew (1963) (Internat Ed

793

2 617)

2 Naturforsch (1969)

2 937

Me

50-55%

PhCOLCOOEt

Me

L i t h i u m N-isopropylcyclohexylamide

Org Synth (1943) Coll Vol 2 268 Tetr Lett (1971) 2953

77% J O C (1956)

11 245

RX, K2CO3 Synthesis (1973) 316

Y - A l k y l a t i o n o f B-ketoesters

JACS (1970)

JOC (1972)

EtCOEt

N2CHCOOEt CHzC12

92 6702

31 3687

+-

Et3O BF4

*

EtCOFHEt COOEt JACS (1970)

86%

92 5767

366

COMPENDIUM


A

Morpholine

S E C T I O N 360

- 0' C1 COOEt

90%

228

:H~OAC

co

CrO3

AcO~H

HOAc

LHOCOPh CH20Ac Aust J Chem (1971)

0"

SECTION 360

YOoMe (CH2 )4CHzCH2COMe

*

MeONa MeOH

?H20Ac CHOH I AcOCH


24

1219

Morphol i n e ____t

T1 (OAc)3 JOC (1968) Dibenzoyl peroxide JOC (1963)

OAc

1 m-Chl oroperbenzoic acid 2 HC1

CHC13

*

Et20 JOC (1967)

(1962)

33 3359 g 581

aAc 2 3934

2 2131

Chem Pharm Bull (1972)

JCS (1955) Synthesis JCS (1961) Chem Corn

4426 (1973) 567 4472 (1970) 406

2 2156 61 %

SECTION 360

ESTER

1 NH20H.HCl 2 Ac20

+

- KETONE

NaHC03 MeOH

Et2O

371

6 1

40-51 %

Ac

-

3 Me30 BF4 CH2C12 Et3N Acid H2°

JOC (1969)

@-

34 1430

C8Hl7

+-

EK,

Me4N OAc Me2C0

0

A

c

O

a

j

0 JOC (1961) 26 4563 JCS (1961) 2725 Tetrahedron (1963)

CgH13CH=CH2

Mn(0Ac)g Me2CO HOAc

*

CgH13FHCH2CH2COMe

KMnO4 Ac20

24 %

OAc JACS (1971)

CgH17CH=CH2

19 8 6 1

93 524

38%

C~H~~COCH~OAC JACS (1971)

Acta

93 3303

Chem Scand (1960)

14 1445


372

SECTION 361

Tetrahedron (1967) 2 2453 Bull SOC Chim Fr (1960) 1079

Also via:

Section 320 330

Ketoacids Hydroxyketones

Section 361

- Nitrile

Ester

aooooo0oo000~0~0

a , ,6 and higher cyanoesters.

PrCHO

Review:

CN tH2COOEt

He

Pd-C

HOAc

Esters o f cyanohydrins

FN

*

PrCH2CHCOOEt

94-96%

Org synth (195s) c o i l v o i 3 385

The Alkylation o f Esters and Nitriles Org React (1957) 9 107

FN

i-PrBr

QcHZBr

BuCHCOOEt

F"

EtONa

*

EtOH

BuCCOOEt I i-Pr

.

1 Mg

87% Org React (1957) 9 161 Tetr Lett (1972) 1279

Ye

QCH2i;,~COOEt

2 Me2C=yCOOEt

OMe

CN

OMe

JOC (1972) 37 825

SECTION 361

C

C

ESTER

e

- NITRILE

373

1 HCN MeOH

Me

2 Br2 NaHC03 CH2C12 H20 3 (Me0)zCO MeOLi MeOCH2CHzOMe JACS (1971)

PhCH2CN

CO(0Et)p to1 uene

PhCH=C(COOEt)2

NH2.HCl

-

EtONa

KCN H20

PhCHCN iOOEt

< 25%

93 4318

70-78% Org Synth (1963) C o l l Vol 4 461 JACS (1971) 2 4237

PhcHCH2COOEt

Pb(0Ac)q. CH2C12

EtOH

a:: COOEt

"HCOOMe

cN

Org Synth (1963) Coll Vol 4 804 (1955) C o l l Vol 3 377 J Med Chem (1972) 15 1297

COOEt

25%

C C N J O C (1971)

5 3668

OAc

J O C (1959) (1949)

24

1650

14 1013


374

O0Also v i a :

OCOPh 80% Compt Rend (1971)

Ester

272 1554

Section 331 321

Hydroxyni tri l e s Cyanoacids

Section 362

SECTION 362

- Olefin

000000000000000

. . . . . . . . . . . . . . . . . . . . . page 374-379 ....................... 379 ....................... 380 ..................... 380 .......................... 380-381

aB-Olefinic esters BY-Olefinic e s t e r s YG-Olefinic e s t e r s Other o l e f i n i c e s t e r s Enol Esters

For a l l y l i c a c e t o x y l a t i o n see s e c t i o n 116 vol 1 and 2 (Esters from Hydrides)

C5H11 CH2CECH

CgH1gCH2;HCOOH Me

NBS

NaOAc

HOAC

H20

C5H11CH2COCHBr2

1 Br2

PBr3

2 MeOH

Et3N

MeOH

C5H11CH=CHCOOMe cis

46%

Proc Chem SOC (1964) 148

-

Br Quinoline CgH1gCH2iCOOMe

Me

CgH1gCH=FCOOMe Me

Org Synth (1963) C o l l Vol 4 608 616

PhCHO

CH3COOEt EtOH

EtONa +

PhCH=CHCOOEt

68-74%

Org Synth (1932) Coll Vol 1 2 5 2

SECTION 362 8uCHO

PhCHO

ESTER

COOH CH2COOEt Pyr

*

p i peridi ne

1

375

Bu CH=CHCOOEt

78%

JACS (1948)

SCN bH2COOEt KF Et2O

*

2 NaOH EtOH

70 2601

PhCH=CHCOOEt Bull Chem SOCJap (1971)

-

CHO (iH2)3CHO

- OLEFIN

Ph-jP=CHCOOMe

44 1357

CHO (kH2)3CH=CHCOOMe

Me Ph3P=bCOOEt (Et0)2POCH2COOEt, NaH 8rCH2COOEt, (Me2N)3P, MeONa CH2=CHCOOEt, Ph3P

Annalen (1962) 658 91 Ore React (1965) 14 270

JACS (1972)

94 4298

2 1040 682 58 (1968) 90 1647

JOC (1971)

Annalen (1965)

JACS T e t r L e t t (1964) 1653

OiLi Pr-i

PrCHCH2COOMe it

1

THF

2 Me2S2

PrF=CHCOOMe

t

3 NaIO4 MeOH H20 4 120"

CgH1 gCH2CH2COOEt

1

R2NLi THF

2 PhSeCl

72%

Et

JACS (1973)

f

3 MeC002H EtOAc

2 6840

CgH1 gCH=CHCODEt JACS (1973)

95 6137

ocH2

376


SECTION 362

B u ~ P ~ H C O O E ~(JCH=CHCOOEt ~

89 5850 93 1693

JACS (1967) (1971)

CgH13I

PrCH2Br

CH2 ( COOMe) 2

NaH THF

CijH13CH(COOMe)2

--+ P r C H = P P h 3

-

CijH13iCDOMe Me2NH. HC1 CH2 2 Me1 3 75" Synth C o r n (1973) 3 359

I MebHCOOEt

1 HCHO Me2NH

I

Me

Ber (1970)

PhI

CH2=CHCOOMe

Pr3N

N-methylpyrrol i d o n e

CH2Br

1 MeCOCH2COOMe

CH=CMe2

NaH BuLi TH; 2 CH2=COAc TsOH I Me

Review:

P d ( OAc ) 2

T h e Wittig R e a c t i o n

*

103 685

81 %

PhCH=CHCODMe JOC (1972)

OAc YH$H&=CHCOOMe CH=CMe2

55%

PrCH=CCOOEt

C6H6

37

MepCuLi

-

1

Et20

2 Acid

*

16 1

i-PrCH$OCH=CHMe JCS

1 Li CH&=N

421

4 (1970)

1469

50%

Ph$=CHCOMe Angew (1968) 8 ( I n t e r n a t Ed I 7 )

aNuo -

0'

n

Morpholine*

i-PrCH2CHO

Ber (1962)

-86% CHCH2Pr-i

95 1493

1 Zn Me2SO C& Br

2 MeCHO

*

57%

0 ; H M e

JACS (1967)

0

1 CS2 4-methyl-2,6di-t-butylphenol

BuLi

2 Me1

5727

LiCuMe2

* C( SMe 12

T e t r L e t t (1973) 3817

Org Synth (1955) C o l l Vol 3 22 JACS (1953) 2 4740

422

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 NHBu Ph2POCH=CPh

Ph2CO

______+.

NaH THF

Ph2C.CHCOPh

SECTION 374 62%

T e t r L e t t (1971) 14 1 1419 J O C (1971) 36 2892

3 NaOH JACS (1973)

95 289

Ye

BrCHCOOEt

--------+

J O C (1971)

0

36

3232

0

0

DMF Dehydrohalogenation with:

CaC03, DMA L i B r , Li2CO3, Me2SO LiBr, Li2C03, DMF LiC1, DMF HMPA Coll idine PhNEt2

J O C (1972)

37

268

JCS (1961) 2532

JCS Perkin I (1972) 50 Tetrahedron (1973) J O C (1972) 2 2436

29 2575

T e t r Lett (1968) 2105 JCS (1961) 1583

I z v (1953) 889 (Chem Abs 49 1082)

Pyr Helv (1942) 5 821 NH2NHCONH2 JACS (1952) 483 JCS (1961) 2532

NH2NHCOOEt JCS (1959) 1691 continued

SECTION 374

KETONE

- OLEFIN

423

2 3951

2,4-Dinitrophenylhydrazine JACS (1952)

- +

(1950)

2290

(Fle0)ZPOz NMe4 B u l l SOC Chim F r (1971) 2962 2551 JACS (1960)

,Ac20

aoAc . a:e

HC104,

1 MeLi

Me

\I

LiN(Pr-i)Z 2 MegSiCl

130

*

2 61-2 3 LiBr Li2CO3

,3::iMe3

;;;i

0

~

M 0e

3 LiBr Li2CO3

EtCH=CH2

MeCH=CH2

1 B2H6

THF

2 HCXCOMe 3 Air

1 MeCOCl

J O C (1973)

72%

EtCH2CHzCH=CHCOMe JACS (1970)

AlCl3 CHzC12

2 Quinol ine

38 2576

*

9 3503

I>leCH=CHCOMe

Org Synth (1971) MeCOOH, (CF3CO)zO JCS (1953) 3628

51 115

*Q


424

1 EtONO

EtOH

2 HC1 3 NH20HaHCl 4 (COOH)2

C5H11CXCH20Me

SECTION 374

-

60%

Pyr

H20

1 BuLi

JACS (1951) 73 5856 NOF JOC (1968) 2 3699

Me2NCH2Cti2NMe2

*

2 Me2S04 3 BuLi

C5H11:=CHCOMe Me

4 Me1

5 Acid

T e t r L e t t (1973) 2585

C0CH2CH2C00H

Pb(OAc)4 Pyr

CU(OAC)~

*

C6H6

COCH=CH2 i-pr@JMe

31%

Synthesis (1973) 541 J O C (1968) 2 2008

1 HCHO Me2NH HC1

+

dioxane

C6H13COF=CH2

2 Me1

3 DMF 75'

Me T e t r L e t t (1973) 5037

T e t r L e t t (1973) 2071

Via en01 e t h e r

Chem Corn (1973) 907

52%

SECTION 374

KETONE

0

- OLEFIN

425

0 1 LiA1H4

Et20

62-75%

2 H2SO4

OEt

Org Synth (1973) Coll Vol 5 294

1 TsNHNH2

0

H2SO4 MeOH

52%

2 K2CO3 H20 JOC (1973)

38 3637

75%

JOC (1973) 38 3658

CH2CH2COOEt Piperidine 0 TSOH CgH6

0

CH2CH2COOEt 1 Hp P t MeOH 0 2 KOH E t O H

Ber (1964)

1 NBS

C1

2 PhS-

,

91 1723

Cyclohexene,

0

3 m-Chl oroperbenzoi c

acid

0

Chem Corn (1974) 21

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 2

426

1 BuLi

hexane

C6H13,

*

CgH13CECH

2 (C6H13)$ diglyme 3 BrCH2COMe 4 HOAc

Ph Ph3P=C=COLi

EtCH2COPr

H

/

SECTION 374

/C6H13

c=c

\

75%

CH2COMe

T e t r L e t t (1973) 4491

52%

EtCH=CCHzCOPh I

Pr T e t r L e t t (1972) 933

1 t-BuOK

t-BUOH

2 HOAc

0

T e t r L e t t (1962) 669 S t e r o i d s (1964) 3 183

Via enol t r i c h l o r o a c e t a t e Tetrahedron (1969)

Me$HCH=CHCOMe

hv Et2O

25 1717

Me2C=CHCH$OMe

75%

T e t r L e t t (1964) 1203 JCS C (1966) 571

70% T e t r L e t t (1971) 3101

PhCOOH

C1 MgCH=CH2

THF

PhCOCH2CH2CH=CH2

84% Synthesis (1970) 189

SECTION 374

- OLEFIN

KETONE

427

PhOCti2CH=CH2

0J-(

a

Ph3P

--+

Pd ( O A C ) 2

70%

CH 2 CHzCH2

C6Hg

T e t r L e t t (1973) 121

Br

--+

@c0cH3

Br

0

COCH2Br ?r-Methallylnickel bromide

@JOCH2CHH 2[;i2

*

DMF

JACS (1967)

Br 2755

- OPh 1 HCOOEt

0 CHOCH$=CH2 he

MeONa 2 CH24CH20H Me

62%

2 K2CO3 CH2C=CH2 Me

35 570

J O C (1970)

Me

OH MezbCH=CHZ

I

CH2=COMe H3PO4

*

Me2C=CHCH2CHZCOMe

94%

Helv (1967) 2091 2095 T e t r L e t t (1969) 3243 JACS (1973) 95 553

TH

EtCCH=CH2 1

Me

Diketene MeONa

MeCOCH2CO? EtCCH=CH2 i

Me

A1 ( O P r - i ) 3

Etv=CHCH$H2COMe Me

Tetrahedron (1969)

CH2=CCH2C1 tie

MeCOCH2COMe K2CO3

EtOH

5 1667

CH2=yCH2CH2COMe Ne Org Synth (1973) C o l l Vol 5 767


428

Hp Pd-CaC03

MeCECCHzCH2COMe

SECTION 375

MeCH=CHCH2CHpCOMe

EtOAc

78%

JCS (1951) 2445 JACS (1972) 94 507

0

0

THF EtpO

JACS (1972) 94 7823 Can J Chem (1970) 48 1626 Helv (1971) 54 1 9 3 r Org React (1972) 19 1

(i-Bu)pAlCH=CHR Tetr Lett (1972) 4083 Me

M

-

t

O?, Oto I Ph3PCHz(CH2)2CMe I I

e

w

Also v i a :

Section 375

NaH MeZSO

Acetylenic ketones 6-Hydroxyketones

Nitrile

LI

Ye

/\IC=CH(CH2)2COMe Me

I

I

JCS P e r k i n I (1972) 2653

Section 309 330

- Nitrile

oOOODOOoOoODOOOOo

D i n i triles

75%

SECTION 375

NITRILE

CH2'C(CN)2

C12CHCHC12

A l C13

PhCH2CN NaCN

MeOH H2O

0

429

CHzCH(CN)2 Me

-

PhCHO

- NITRILE

JACS (1954)

76 1076

JACS (1958)

1752

Ph$H-$HPh CN CN

CN CN

NaCN

-40% Org Synth (1963) C o l l Vol 4 273 274 66 JACS (1965) 4403

PhCH2CN

CHz=CHCN EtONa

Ph$HCN CH2CHzCN

+

20-30% JACS (1943) 65 437 Org React (1949) 79

+-

MeCH=CHCN

Me$(CH2)zCOOH CN

Electrolysis Et4N OTs

f

DMF

MeCHCH2CN

Compt Rend

Electrolysis Na2CO3

MeOH

Me2F(CH2)4yMe2 CN CN

C

(1967)

265

751

Bull SOC Chim F r (1970) 183 Z Naturforsch (1947) & 185

60%

430

COMPENDIUM

S e c t i o n 376

OF

ORGANIC SYNTHETIC METHODS VOL 2

SECTION 376

-Olefin

Nitrile

00000000000000000

a#, By, and h i g h e r o l e f i n i c n i t r i l e s

1 (i-Bu)zAlH

BuCZCH

hexane ~

2 MeLi

Et20

BuCH=CHCN

87%

J A C S (1968)

3

COOH ~ .

3 7139

.

CH2CN

NH40Ac 74-78% Org Synth (1973) Coll Vol 5 585 JCS P e r k i n I (1973) 2241 J A C S (1949) 2 3562

+

Ph3PCH2CN C1

42%

MeCN Ber (1970) + (Ph3P)zCHCN 2Br, NaOH J O C (1971)

NH2 NCS

NaN02 HC1 Me2 3 2 CH2=CHCN CuC12

H20

3 Et3N

PhH

CHz=CHCN HOAc

103 2077

a 2026

NCSo c H = C H C N

JCS Perkin I (1973) 2241 Org React (1960) 11. 189

Pd( O A C ) ~ w

PhCH=CHCN Tetrahedron (1969)

2 4819

60%

SECTION 376

NITRILE

- OLEFIN

431

J O C (1972) 2 2201 T e t r a h e d r o n (1968) 24 3127 Can J Chem (1969) 41 3266

(Et0)2POCH2CN

NaH

v

b

MeOCH2CH2014e

J O C (1971) (1965)

Ph2CO

1 CH3CN B u L i

THF

hexane

36

30

1024 505

PhZC=CHCN

+

2 H3PO4 H20

75%

58%

J O C (1968) 33 3402 Angew (1972) 767 ( I n t e r n a t Ed 722)

11

i

PhCHZCN

-

HCHO PhCH2NMe3 OH

t

EtOH

I

CN JACS (1950)

EtCHO

CHpCHCN

Ph3P

t-BUOH

86%

PhCzCH2

2 5645

EtCH=CHCH2CN

44%

T e t r L e t t (1967) 2401 (1964) 1653

tOOH

1 CH2CN NH40Ac

76-91 %

2 165-175"

Org Synth (1963) Coll Vol 4 234 (1973) C o l l Vol 5 585

V i a enamine

Chem Pharm B u l l (1973)

21

1601


432

+

-

H C X H PhCHzNEt3 C1

EtCHCN I Ph

NaOH Me2SO

SECTION 377

CH=CHz Et!CN Ph

80%

Tetr Lett (1966) 5489

1

0

NHZOH-HCl Pyr

64%

2 TsCl JOC (1970) Coll

s 186

21 1961 1965 Czech (1962) 21 377

(1962)

Also via: Acetylenic nitriles (Section 310)

- Olefin 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . 1,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . 1,5-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . Other dienes . . . . . . . . . . . . . . . . . . . . . . . . . Section 377

EtCXEt

Olefin

0000000000000000

1 B2Hg THF

2‘ I2 NaOH

page 432-435 435-436 436-437 437

Et EtCH=C-b=CHEt cisEt trans

68% JACS (1968) 90 6243 JOC (1973) c 1 6 1 7

Me

BuCgCH

--+

BuCSCC1

1

i -PriBH2

Me

2 PrCZCH 3 MeONa 4 i-PrCOOH

BuCH=CHCH=CHPr trans trans Chem Corn (1973) 606

45%

SECTION 377

- OLEFIN

1 D i cyclohexyl borane THF

BuCXCXBU

BuCECH

OLEFIN

2 HOAc 3 H202 NaOH H20

1 (i-Bu)zAlH hexane

*

CuCl THF 3 H2SO4 H20 2

t

433

BuCH=CHCH=CHBu c i s cis

JACS (1970)

79%

92 4068 73%

BuCH=CHCH=CHBu trans trans

JACS (1970) 92 6678 Annalen (1960) 629 222

42% JACS (1953)

S;H3 MeTOH MeCOH I

CH3

HBr H20

Org Synth (1955) Coll Vol 3 312 123

MeZSO 160' JOC (1964)

+

PhCHO

MeC=CH2 MeC=CH2

75 384

-

PhCH=CHCH2PPh3 C1 EtOLi EtOH

NH2

1 NaN02

*

PhCH=CHCH=CHPh

40%


HC1 H20

2 CH2=CHCH=CH2 CuCl NaOAc Me2CO H20 3 KOH MeOH

CH=CHCH=CH2

57-62%

Org Synth (1963) Col.1 Vol 4 727 Org React (1960) 11 189

434


1 Mg

PrBr

THF

+

SECTION 377

PrCH2CH=CHCH=CH2

2 CH2=CHCH=CHCH2Br

Bull SOC Chim Fr (1964) 2485

Me

J

CH~=CHCH~PO:~ N I Me BuLi

THF

CHCH=CH2 t

2 H20

JOC (1969)

3 110-120"

2 3053

1 B r 2 CH2C12 2 LiCl HMPA

Li2CO3 JACS (1972) 2 2155


1 NBS b e n r o y l p e r o x i d e

+

CC14 2 t-BuOK

CECCH20THP

THF

59%

LiA,H4 THF

CHCH=CH2 52%

Acta

Mee , b e H

>

Me

Me

94 7118

JACS (1972)

Chem Scand (1972) 26 2540

Na2N203 HC1

H20

H JACS (1966)

MeCH=CHCH=CHMe

cis

88 1335

trans 2858

OLEFIN

SECTION 377

0 c H 2 N E l e 2 1 Me1 hexane+

- OLEFIN t

435

-

-

O - [ P Z N M e 3 OH

180'

2 Ag20 H20 J O C (1972)

*

1 TsNHNH2

2 MeLi

Et20 C&

-3

2 2201

90 4762

OAc I

Bu20 Ac 0

PhCH=CHBr

Compendium of Organic Synthetic Methods Volume 2

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods