Saturated Heterocyclic Chemistry (v. 3)

316 Pages·1975·15.31 MB·English

by  G. Pattenden

A Specialist Periodical Report
Saturated Heterocyclic Chemistry
Volume 3
A Review of the Literature Published
during 1973
Sen io r Reporter
M. F. Ansell, Queen Mary College, London
Reporters
D. J. Maitland, University of Bradford
J. M. Mellor, University of Southampton
A. E. A. Porter, University of Stirling
B. Walker, Queen’s University, Belfast
0 Copyright I975
The Chemical Society
Burlington House, London, W IV OBN.
ISBN: 0 85186 562 3
Library of Congress Catalog Card No. 72-83454
Printed in Northern Ireland at The Universities Press, Belfast
Fore word
The third volume of this Specialist Periodical Report reviews developments
in the field of Saturated Heterocyclic Chemistry for the period January-
December 1973. The format of the Report follows that of Volume 2,
except for the omission of the chapter on Medium-sized Rings. It is intended
to remedy this unfortunate omission by including a two-year Report (1973
and 1974) in Volume 4.
The production of this volume is due to the skill and patience with which
the contributors have compiled their Reports and the expert assistance of
the Chemical Society Editorial Staff. I express to all of them my sincere
thanks.
April 1975 M. F. Ansell

Cont ents
Chapter I Three-membered Rings 1
By D. /. Maitland
1 Introduction 1
2 Oxirans 1
Formation 1
Direct Insertion 1
Oxygen atom insertion 1
Carbon atom insertion 12
Cyclization of Halohydrin 16
Darzens Reaction 19
Met al-cata 1 y sed Epoxidati on 22
Miscellaneous 24
Reactions 28
Ring-opening 28
Electrophilic 28
Nucleophilic 32
Dipolar cycloaddition 40
Rearrangement 41
Ring Retention 45
Miscellaneous 46
3 Aziridines 49
Format ion 49
Direct Insertion of Nitrogen or Carbon Atoms 49
Cyclizati on 51
Ring Contraction 59
Formation via Azirines 60
React ions 62
Ring-o pening 62
Electrophilic and nucleophilic 62
Dipolar cycloaddition 65
Rearrangement 69
Ring Retention 70
4 Thiirans 73
Formation 73
Carbon Atom Insertion 73
Sulphur Atom Insertion 77
Cyclization 77
Miscellaneous 77
Episulphoxides 79
V
vi Contents
Reactions 80
Ring-opening 80
Desulphurization 81
Ring Expansion 82
5 Rings containing More than One Heteroatom 82
Formation 82
Diaziridines 82
Oxaziridines 84
Azaphosphiridines 84
Thiadiaziridine 1,l-Dioxides 85
React ions 85
Diaziridines 85
Oxaziridines 87
Thiadiaziridine 1,l-Dioxides 90
Chapter 2 Four-membered Rings 92
By B. 1. Walker
1 Introduction 92
2 Physical Methods 92
Magnetic Resonance 92
Miscellaneous 94
3 Formation 94
Oxetans 94
Cyclization 94
+
[2 21 Cycloaddition 96
Miscellaneous 99
Azetidines 100
Cyclizati on 100
+
12 21 Cycloaddition 103
Ring Contraction 112
Miscellaneous 113
Rings containing More than One Heteroatom 117
Cyclization 117
+
[2 21 Cycloaddition 118
Miscellaneous 121
4 Reactions 122
Oxetans 122
Ring-o pening 122
Rearrangement 125
Miscellaneous 126
Azet idines 127
Ring-opening 127
Rearrangement 128
Miscellaneous 131
Con tents vii
Rings containing More than one Heteroatom 136
Ring-opening 136
Chapter 3 Five- and Six-membered Rings and
Related Fused Systems 138
By A. E. A. Porter
1 Introduction 138
2 Conformational Analysis of Reduced Heterocycles 138
General 138
Oxygen-containing Rings 139
Nitrogen-containing Rings 144
Phosphorus-containing Rings 151
Sulphur-containing Rings 154
3 Cycloaddition Reactions 158
+
[3 21 Cycloaddition 158
General 158
Ni trones 159
Nitrile Imines 161
Nitrile Oxides 161
Nitrile Ylides 163
Azides and Diazoalkanes 165
Miscellaneous 166
+
[4 21 Cycloaddition 166
Oxygen-containing Rings 16 6
Nitrogen-containing Rings 168
Rings containing both Oxygen and Nitrogen 169
4 General Chemistry of Saturated Heterocycles 170
Oxygen containing Rings 170
Tetrahydrofurans 170
Dihy drofurans 172
Lactones 174
Miscellaneous Furanoid Derivatives 176
1, ZDioxolans 177
1,3-Dioxolans 177
Ozonides 179
Tet rahy dropy rans 180
Di hydropyrans 181
Dihydropyrones 183
Fused Pyrans 184
1, ZDioxans 184
lY3-Dioxans 185
1,4-Dioxans 185
Miscellaneous 185
viii Contents
Nitrogen-containing Rings 186
Pyrrolidines 186
Pyrrolidones 189
Dihy dropy rroles 190
Pyrazolines 19 4
Imidazolines 197
Triazolines 200
Tetrazolines 202
Piperidines 202
Piperidones 204
Tetr ahy dropyridines 205
Dihy dropyridines 207
Quinoline Derivatives 208
Isoquinoline Derivatives 209
Aza-steroids 210
Fused Systems 21 1
Hexahy dropyridazines 212
Tetrahyd r opyridazines 212
Dihy dropyridazines 213
Cinnoline Derivatives 213
Phthalazine Derivatives 214
Pyrimidine Derivatives 214
Piperazines 216
Dihydropy razines 217
Piperazinediones 21 8
Fused Pyrazines 221
1,2,4-Triazines 222
1,3,5-Triazines 223
Condensed Triazines 223
Tet r azines 224
Fused Tetrazines 226
Rings containing both Oxygen and Nitrogen 226
Isoxazole Derivatives 226
Oxazole Derivatives 229
Fused Oxazoles 236
Dioxazoles 236
Oxadiazoles 237
1,2-Oxazines 238
1,3-0xazines 239
Fused 1,3-Oxazines 241
1,4-0xazines 242
Dioxazines 243
Oxadiazines 244
Miscellaneous Fused Systems 245