organic photochemistry: a comprehensive treatment2.2.5 photoaddition 72 2.2.6 photocycloaddition 75...

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ORGANI C PHOTOCHEMISTRY : A Comprehensive Treatmen t Dr WILLIAM _HORSPOO L Department of Chemistry, University of Dunde e Professor DIEGO ARMESTO

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ORGANICPHOTOCHEMISTRY:A Comprehensive Treatment

Dr WILLIAM _HORSPOO LDepartment of Chemistry, University of Dundee

Professor DIEGO ARMESTO

Preface

xii i

1. Introduction

11 .1 General principles

11 .2 Electronically excited states and transitions

31 .2 .1 Orbital types

31 .2 .2 Molecular orbitals

41 .2 .3 Multiplicity and lifetime

61 .2 .4 Radiative and non-radiative processes

71 .3 Quenching and sensitization

81 .3 .1 Triplet-state sensitization

1 01 .4 Photochemical reactions

1 21 .4 .1 Kinetic versus thermodynamic control

1 21 .4 .2 Photostationary states

1 41 .4 .3 Photochemical versus thermal reactants

1 5References

1 7

2. Hydrocarbon systems

-

1 92.1 Alkenes

1 92 .1 .1 Spectra of alkenes and dienes

2 12 .1 .2 Excited-state geometry of alkenes

2 12 .1 .3 Direct irradiation. Singlet-state reactivity of alkenes

2 12 .1 .4 Photoreactions of dienes and trienes

3 72 .2 Aromatic compounds

5 22 .2 .1 Spectra and excited states

5 22 .2 .2 Photoisomerization

55

2 .2 .3 Photochemical ring-opening

642 .2 .4 Photosubstitution

6 52 .2 .5 Photoaddition

722 .2 .6 Photocycloaddition

7 52 .2 .7 Photocyclization

9 12 .2 .8 Lateral-nuclear photorearrangements

10 82 .3 Alkanes

11 32 .3 .1 Excited states and spectra

11 32 .3 .2 Photochemistry of alkanes

1142 .4 Photo-oxidation of alkenes and dienes

11 82 .4 .1 Reactions with alkenes

11 92 .4.2 1,2-Addition

12 12 .4 .3 Reaction with dienes

12 2References

12 5

3. Oxygen-containing compounds

14 23 .1 Absorption spectra of alcohols, ethers and peroxides

14 23 .1 .1 Alcohols

14 23 .1 .2 Ethers

14 33 .1 .3 Peroxides

14 33 .2 Photochemical reactions

14 33 .2 .1 Alcohols

14 33 .2 .2 Ethers

14 53 .2 .3 Peroxides

15 63 .3 Carbonyl compounds

16 03 .3 .1 Spectra and excited states

1603 .3 .2 Norrish Type I fragmentation reactions

16 23 .3 .3 a-Fission of ß,y-unsaturated compounds

18 13 .3 .4 The photo-Fries reaction

1843 .3 .5 1,2-Migration in ß,y-unsaturated ketones

18 53 .3 .6 ß-cleavage

18 93 .3 .7 Hydrogen abstraction reactions

19 13 .3 .8 Cycloaddition reactions of carbonyl compounds

21 33 .3 .9 Enone and dienone rearrangements

2263 .3 .10 Cross-conjugated dienone rearrangements

24 13 .3 .11 Linearly conjugated dienone rearrangements

2483 .3 .12 Quinones

252References

262

4. Sulphur-containing compounds

28 24 .1 Absorption spectra of thiols, sulphides and disulphides

28 24 .1 .1 Thiols

2824 .1 .2 Sulphides

28 34 .1 .3 Disulphides

28 34 .2 Photochemistry of thiols, sulphides and disulphides

28 34 .2 .1 Thiols

28 34 .2 .2 Sulphides

2844 .2.3 Disulphides

28 64 .3 Photochemistry of compounds with sulphur halogen bonds 28 6

4 .3 .1 Alkyl sulphenyl halides

28 64 .3 .2 Aryl sulphenyl halides

28 84 .3 .3 Sulphonyl halides

28 94 .4 Photochemistry of compounds with sulphur-nitrogen bonds 29 1

4 .4.1 Sulphenamides

29 14.4.2 Isothiazolonones

2924 .4.3 Sulphonamides

2944.5 Photochemistry of compounds with sulphur-oxygen bonds 30 1

4 .5 .1 Sulphenates

30 14 .5 .2 Rearrangement of sulphoxides

3044 .5 .3 Photochemistry of sulphonates

3064.6 Sulphones and sultones

31 34.6.1 Spectroscopic data of sulphones and sultones

31 34 .6.2 Photochemistry of sulphones and sultones

31 34 .7 Thiocarbonyl compounds

3224.7 .1 Spectra of thiocarbonyl compounds

32 34.7 .2 Cleavage reactions

32 34.7.3 Hydrogen abstraction reactions

3264 .7 .4 Cycloaddition reactions

33 14.8 Photochemistry of thiophenes and related aromati c

compounds

3344.8 .1 Thiophenes

3344.8 .2 Isothiazoles

33 64.8 .3 Benzoisothiazoles

33 84.8 .4 1,2,3-Thiadiazoles

339References

34 1

5. Nitrogen-containing compounds

35 35 .1 Absorption spectra of imines and related compounds

35 35 .2 Photochemical reactivity of imines and related compounds

354

5 .2 .1 Reactions analogous to alkenes

35 55 .2.2 Reactions analogous to carbonyl compounds

3745 .2 .3 Miscellaneous reactions of the C=N double bond

37 85 .3 Photochemistry of enamides

3905.4 Nitriles

3925.5 Photochemistry of the N==N system and related

compounds

39 65 .5 .1 Absorption spectra of azo compounds, diaz o

compounds, diazonium salts and azides

39 65 .5 .2 Photochemistry of azo compounds

39 65 .5 .3 Diazo compounds

40 15 .5 .4 Diazonium salts

40 35 .5 .5 Azides

40 55 .6 The N=0 group and related compounds

40 85 .6 .1 Nitrites

40 85 .6 .2 Nitro compounds

41 15 .7 Oximes, oxaziridines, nitrones and heterocyclic N-oxides

41 75 .8 Aromatic heterocyclic compounds

424References

43 3

6. Halogen-containing compounds

44 36 .1 Alkyl halides

44 36 .1 .1 Spectroscopic data

44 36 .1 .2 Photochemical reactions of alkyl halides

4446.2 Vinyl halides

4486 .2 .1 Photochemical reactions of vinyl halides

4496.3 Aryl halides

4576 .3 .1 Spectroscopic properties

4576 .3 .2 Photochemistry of aryl halides

45 76 .4 Hypohalites

47 16.4.1 Spectra

47 16 .4.2 Photochemistry

47 16 .5 Photoreactions of halogens and hydrogen halides

4746.5 .1 Halogens

4746 .5 .2 Hydrogen halides

476References

477

7. Experimental techniques

48 47.1 Hazards

4857 .2 Mercury vapour lamp

485

7.2 .1 Low-pressure or resonance lamps

48 67.2 .2 Medium-pressure lamps

48 77.2 .3 High-pressure lamps

48 97 .3 Lamps in conjuction with filters

48 97.3 .1 Glass filters

48 97.3 .2 Solution filters

49 07 .4 Preparative photochemical reactors

49 17 .4.1 Immersion-well apparatus

49 17 .4.2 External irradiation

4937 .4.3 Reactors for quantitative work

4947 .4.4 Thin-film reactors

4977 .5 Actinometry

4987 .6 Purity of gases and solvents

50 1References

50 3

Index

504