Fluorocarbon and Related Chemistry Vol. 2 A review of the literature published during 1971 and 1972

502 Pages·1974·21.116 MB·English

by  R E Banks, M G Barlow, Chemical Society

A Specialist Periodical Report
Fluorocarbon and Related
Chemistry
Volume 2
A Review of the Literature Published
during 1971 and 1972
Senior Reporters
R. E. Banks
M.G . Barlow
Reporters
J. M. Birchall
R. Fields
W. T. Flowers
D. R. Taylor
All ot Department of Ch,mistrj Universit of Manch ster Institute
of Science and Technology
0 Copyright 1974
The Chemical Society
Burlington House, London, W1 V OBN
ISBN :0 85186 514 3
Library of Congress Catalog Card No. 72-78530
Printed by Eyre & Spottiswoode Ltd, Thnet Press, Margale
Preface
This is the second volume in a series of biennial reviews concerned with the
chemistry of organic, organometallic, and organometalloidal compounds
of the fluorocarbon class and of their polfluorinated analogues. As in the
first volume (referred to throughout as Vol. l), compounds containing a low
proportion of C-F bonds are mentioned only when relevant to the main
theme.
The fluorocarbon literature boomed during the two-year period now
reviewed, so we have cause to congratulate ourselves on acquiring the
sterling services of our friends and colleagues Mike Birchall, Roy Fields,
Thain Flowers, and David Taylor as contributing authors. Without their aid
and the remarkable skill of our dedicated typist Mrs. Joan Colclough, it
would have taken us much longer to produce the typescript. We also greatly
appreciate the assistance given by Michael P. Amor, our proof-reader, and
David H. Whitehurst, our Departmental Librarian.
R.E.B.
September 1973 M.G.B.

Contents
Chapter 1 Saturated Fluorocarbons, FI uorocarb on Hy drides,
and Fluorocarbon Halides 1
By R. E. Banks
1 Fluorocarbons 1
2 Hydrides 10
3 Halides 21
4 Bibliography 34
Chapter 2 Per- and Poly-fluorinated Olefins, Dienes,
He terocum ulenes, and Acetylenes 37
By M. G. Barlow and D. R. Taylor
1 Olefins 37
Physical Aspects 37
Preparation 43
Ionic Reactions 51
Free-radical React ions 72
Cycloaddit ion Reactions 77
2 Valence-bond Isomers of Aromatic Compounds 84
3 1,SDienes 88
4 Allenes (1,2-Dienes) 94
5 Heterocumulenes (Ketens, Thioketens, etc.) 98
6 Acetylenes 106
7 Bibliography 121
Chapter 3 Aliphatic Per- and Poly-fluorinated Carbonyl and
Thiocarbonyl Compounds 12 4
By R. E. Banks
1 Carboxylic Acids and their Derivatives 12 4
Monocarboxylic Acids 124
Dicarboxylic Acids 138
2 Aldehydes 145
3 Ketones 148
4 Bibliography 165
vi Contents
Chapter 4 Per- and Poly-fluorinated Aliphatic Derivatives
of the Main-group Elements 178
By R. E. Banks
1 Group I 178
Lithium 178
2 Group I1 186
Magnesium 186
Calcium 188
Zinc 188
Cadmium 189
Mercury 189
3 Group 111 195
Boron 195
Aluminium 195
Indium 196
4 Group IV 196
Silicon 196
Germanium 202
Tin 203
5 Group V 204
Nitrogen 204
Amines, Imines, Cyanides, Isocyanides, and Isocyanates 204
Nitroxides, Hydroxylamines, and Nitroso- and Nitro-
compounds 223
Azides, Diazoalkanes, Diazirines, Azo- and Hydrazo-
compounds, and Azines 235
Phosphorus 244
Arsenic 252
Antimony 252
6 Group VI 252
Oxygen 252
Alcohols, Alkoxides, and Ethers 252
Perfluoroalkyl Hypohalites, Fluoroperoxides, Hydro-
peroxides, Peroxides, and Trioxides 262
Sulphur 269
Compounds containing Bivalent Sulphur 269
PerfluoroalkanesulphonicA cids and Related Compounds 276
Derivatives of Sulphur Tetra- and Hexa-fluoride 282
Selenium 284
7 Bibliography 284
Contents vii
Chapter 5 Per- and Poly-fluorinated Aliphatic Derivatives
of the Transition Elements 290
By R. Fields
1 Introduction 290
2 Groups III-V and the Lanthanides 290
3 Chromium, Molybdenum, and Tungsten 292
4 Manganese and Rhenium 297
5 Iron, Ruthenium, and Osmium 302
6 Cobalt, Rhodium, and Iridium 315
7 Nickel, Palladium, and Platinum 326
8 Copper, Silver, and Gold 344
Chapter 6 Per- and Poly-fluorinated Aromatic Compounds 350
By J. M. Birchall, M. G. Barlow, and W. 1. Flowers
1 Carbocyclic Compounds 350
The Introduction of Fluorine into Aromatic Rings 350
The Introduction of Fluorinated Side-chains 356
Arenes from Aliphatic and Alicyclic Precursors 359
Fluorocarbons, Fluorohydrocarbons, and Polyfluorohalo-
geno-compounds 36 1
Olefinic Compounds and Related Polymers 374
Alcohols, Phenols, and Ethers 377
Carbonyl Compounds 380
Carboxylic Acid Derivatives 391
Arynes and Derived Compounds 397
Derivatives of Nitrogen 407
Physical Measurements and Calculations 41 7
2 Derivatives of the Transition Metals 420
Tetrafluorobenzobarrelene 420
Titanium and Hafnium 421
Vanadium 421
Molybdenum and Tungsten 421
Iron and Ruthenium 422
Cobalt, Rhodium, and Iridium 422
Nickel, Palladium, and Platinum 424
Copper and Gold 425
3 Derivatives of the Main-group Elements 427
Lithium 427
Calcium, Magnesium, and Mercury 427
Boron, Thallium, and Indium 429
viii Contents
Silicon, Germanium, and Tin 430
Phosphorus, Arsenic, Antimony, and Bismuth 435
Sulphur and Selenium 436
4 Heterocyclic Compounds 439
Introduction of Fluorine 439
Reactions 443
Preparation of Polycyclic Compounds 45 1
Chapter 7 Progress in Nuclear Magnetic Resonance
Spectroscopy 456
By M. G. Barlow
1 Introduction 456
2 TemperaturedependentP henomena 458
3 Studies involving 13CN uclei 462
4 Chemically Induced Dynamic Nuclear Spin Polarization of
19F Nuclei 463
5 Through-space Coupling 465
6 Fluoroalkanes 466
7 Solvent Dependence 467
8 Aromatic Compounds 468
Appendix I 470
Appendix II 473
Author Index 475