ORGANIC PHOTOCHEMISTRY: A Comprehensive Treatment2.2.5 Photoaddition 72 2.2.6 Photocycloaddition 75...
Transcript of ORGANIC PHOTOCHEMISTRY: A Comprehensive Treatment2.2.5 Photoaddition 72 2.2.6 Photocycloaddition 75...
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
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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