Table Of ContentPhotochemistry
Volume 33
A Specialist Periodical Report
Photochemistry
Volume 33
A Review of the Literature Published between
July 2000 and June 2001
Senior Reporter
A. Gilbert, Department of Chemistry,
University of Reading, UK
Reporters
N.S. Allen, Manchester Metropolitan University, UK
A. Cox, University of Warwick, UK
I. Dunkin, University of Strathclyde, Glasgow, UK
A. Harriman, University of Newcastle upon Tyne, UK
W.M. Horspool, University of Dundee, UK
A.C. Pratt, Dublin City University, Ireland
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Contents
Chapter 1
Introduction and Review of the Year 1
By Andrew Gilbert
Part I Physical Aspects of Photochemistry 11
Photophysical Processes in Condensed Phases 13
By Anthony Harriman
1 Introduction 13
2 General Aspects of Photophysical Processes 13
3 Theoretical and Kinetic Considerations 16
4 Photophysical Processes in Liquid or Solid Media 18
4.1 Detection of Single Molecules 18
4.2 Radiative and Non-radiative Decay Processes 19
4.3 Amplitude or Torsional Motion 21
4.4 Light-induced Proton-transfer Reactions 23
4.5 Quenching of Excited States 24
4.5.1 Energy-transfer Reactions 25
4.5.2 Electron-transfer Reactions 25
4.6 Photophysics of Fullerenes 27
5 Applications of Photophysics 29
6 Advances in Instrument Design and Utilisation 29
6.1 Data Analysis 29
6.2 Instrumentation 30
7 References 31
Photochemistry, Volume 33
© The Royal Society of Chemistry, 2002
v
vi Contents
Part II Organic Aspects of Photochemistry 51
Chapter 1 Photolysis of Carbonyl Compounds 53
By William M. Horspool
1 Norrish Type I Reactions 53
2 Norrish Type II Reactions 55
2.1 1,5-Hydrogen Transfer 55
2.2 Other Hydrogen Transfers 58
3 Oxetane Formation 60
4 Miscellaneous Reactions 61
4.1 Decarbonylation and Decarboxylation 61
4.2 Reactions of Miscellaneous Haloketones and Acid
Chlorides 66
4.3 Other Processes 66
5 References 69
Chapter 2Enone Cycloadditions and Rearrangements: Photoreactions of
Dienones and Quinones 74
By William M. Horspool
1 Cycloaddition Reactions 74
1.1 Intermolecular Cycloaddition 74
1.1.1 Open-chain Systems 74
1.1.2 Additions to Cyclopentenones and Related
Systems 75
1.1.3 Additions to Cyclohexenones and Related
Systems 77
1.2 Intramolecular Additions 80
1.2.1 Intramolecular Additions to Cyclopentenones 81
1.2.2 Additions to Cyclohexenones and Related
Systems 81
2 Rearrangement Reactions 84
2.1 , -Unsaturated Systems 84
2.1.1 Isomerisation 84
2.1.2 Hydrogen Abstraction Reactions 86
2.1.3 Rearrangement Reactions 87
2.2 , -Unsaturated Systems 88
2.2.1 The Oxa Di- -methane Reaction and Related
Processes 88
2.2.2 Other Rearrangements 89
Contents vii
3 Photoreactions of Thymines and Related Compounds 91
3.1 Photoreactions of Pyridones 91
3.2 Photoreactions of Thymines etc. 91
3.3 Miscellaneous Processes 94
4 Photochemistry of Dienones 95
4.1 Cross-conjugated Dienones 95
4.2 Linearly Conjugated Dienones 96
5 1,2-, 1,3- and 1,4-Diketones 97
5.1 Reactions of 1,2-Diketones and Other 1,2-Dicarbonyl
Compounds 97
5.2 Reactions of 1,3-Diketones 98
5.3 Reactions of 1,4-Diketones 100
5.3.1 Phthalimides and Related Compounds 102
5.3.2 Fulgides and Fulgimides 106
6 Quinones 108
6.1 o-Quinones 108
6.2 p-Quinones 108
7 References 110
Chapter 3 Photochemistry of Alkenes, Alkynes and Related Compounds 119
By WilliamM. Horspool
1 Reactions of Alkenes 119
1.1 cis,trans-Isomerisation 119
1.1.1 Stilbenes and Related Compounds 119
1.1.2 The Dithienylethene System and Related
Compounds 122
1.2 Miscellaneous Reactions 127
1.2.1 Addition Reactions 128
1.2.2 Electron-transfer Processes 128
1.2.3 Other Processes 128
2 Reactions Involving Cyclopropane Rings 129
2.1 The Di- -methane Rearrangement and Related
Processes 129
2.1.1 The Aza-di- -methane Rearrangement and
Related Processes 132
2.2 Miscellaneous Reactions Involving Three-membered
Ring Compounds 132
3 Reactions of Dienes and Trienes 135
3.1 Vitamin D Analogues 139
viii Contents
4 (2 ; 2 )-Intramolecular Additions 139
5 Dimerisation and Intermolecular Additions 140
5.1 Dimerisation 141
6 Miscellaneous Reactions 141
6.1 Reactions Involving Cations and Radicals 141
6.2 Miscellaneous Rearrangements and Bond Fission
Processes 144
7 References 146
Chapter 4 Photochemistry of Aromatic Compounds 155
By Andrew Gilbert
1 Introduction 155
2 Isomerisation Reactions 155
3 Addition Reactions 156
4 Substitution Reactions 164
5 Cyclisation Reactions 168
6 Dimerisation Processes 178
7 Lateral Nuclear Shifts 181
8 Miscellaneous Photochemistry of Aromatic Systems 183
9 References 188
Chapter 5 Photo-reduction and -oxidation 194
By Alan Cox
1 Introduction 194
2 Reduction of the Carbonyl Group194
3 Reduction of Nitrogen-containing Compounds 201
4 Miscellaneous Reductions 205
5 Singlet Oxygen 212
Contents ix
6 Oxidation of Aliphatic Compounds 213
7 Oxidation of Aromatic Compounds 217
8 Oxidation of Nitrogen-containing Compounds 223
9 Miscellaneous Oxidations 232
10 References 232
Chapter 6 Photoreactions of Compounds Containing Heteroatoms Other
than Oxygen 242
By Albert C. Pratt
1 Introduction 242
2 Nitrogen-containing Compounds 242
2.1 E,Z-Isomerisations 242
2.2 Photocyclisations 244
2.3 Photoadditions 254
2.4 Other Processes 261
3 Sulfur-containing Compounds 275
4 Compounds Containing Other Heteroatoms 287
4.1 Silicon and Germanium 287
4.2 Phosphorus 290
4.3 Other Elements 292
5 References 294
Chapter 7 Photoelimination 307
By Ian R. Dunkin
1 Introduction 307
2 Elimination of Nitrogen from Azo Compounds and
Analogues 307
3 Elimination of Nitrogen from Diazo Compounds and
Diazirines 308
3.1 Generation of Alkyl, Alicyclic and Heterocyclic
Carbenes 308
3.2 Generation of Aryl and Heteroaryl Carbenes 311
3.3 Photolysis of Diazo Carbonyl Compounds and
Sulfur Analogues 313
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4 Elimination of Nitrogen from Azides 314
5 Photoelimination of CarbonMonoxide and Carbon
Dioxide 316
5.1 Photoelimination of CO from Organometallic
Compounds 318
6 Photoelimination of NO and NO2 321
7 Miscellaneous Photoeliminations and
Photofragmentations 322
7.1 Photoelimination from Hydrocarbons 322
7.2 Photoelimination from Organohalogen Compounds 322
7.3 Photofragmentations of Organosilicon and
Organogermanium Compounds 324
7.4 Photofragmentations of Organosulfur,
Organoselenium and Organotellurium Compounds 327
7.5 Photolysis of o-Nitrobenzyl Derivatives and Related
Compounds 327
7.6 Other Photofragmentations 329
8 References 330
Part III Polymer Photochemistry 337
By Norman S. Allen
1 Introduction 339
2 Photopolymerization 339
2.1 Photoinitiated Addition Polymerization 340
2.2 Photocrosslinking 345
2.3 Photografting 351
3 Luminescence and Optical Properties 352
4 Photodegradation and Photooxidation Processes in
Polymers 369
4.1 Polyolefins 369
4.2 Polystyrenes 370
4.3 Poly(acrylates) and Poly(alkyl acrylates) 370
4.4 Polyesters 371
4.5 Polyamides and Polyimides 371
4.6 Poly(alkyl and aromatic ethers) 371
4.7 Silicone Polymers 371
4.8 Polyurethanes and Rubbers 372
