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A Guidebook of Organic Reaction Mechanism by Peter Sykes - Pdf-Cdekey - KHMO2NR6J7SFLII3VTTYGEEFIY2R7372
A Guidebook of Organic Reaction Mechanism by Peter Sykes - Pdf-Cdekey - KHMO2NR6J7SFLII3VTTYGEEFIY2R7372
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Ambident nucleophiles, 97 BAc2 pathway, 239,384 Benzotriazoles, 148, 176 cyclopentadienyl anion, 275
Amides Baeyer-Villiger oxidation, 127 Benzyne, 175,251 deuterium exchange, 288
from Beckmann, 123 Barton reaction, 337 dimerisation, 176 displacement reactions, 287
Hofmann reaction, 49, 122 Base catalysis isolation, 175 ElcB elimination and, 248,285
hydrolysis, 239,245, 388 general, 75 mass spec., 176 electronic effects in, 272
reduction, 214 ion exchange resins, 226 structure, 175 enolate anions, 279,290,295
Amidines specific, 75 Biosynthetic pathways, 48 formation, 271
basicity, 69 Basicity Biphenylene, 176 in carbonation, 284
formation, 244 aromaticity and, 69,72 Bipolar non-protic solvents, 81,98,173, in Danens reaction, 290
Aminoazo comps, 148 Brensted and, 53 252 in decarboxylation, 285
Anionic polymerisation, 200,226 cation stability and, 67, 68, 72, 73 Biradicals, 315,331, 337 in Favorskii reaction, 294
Antarafacial shifts, 353 constant, 65 oxygen, 315,330 in halogenation of ketones, 295
Anthracene, 17 effect of solvent on, 66,67 stable, 338 in Kolbe-Schmidt reaction, 291
photodimer, 337 H-bonding in, 67 Bisulphite addition comps., 207, 213 in Michael reaction, 200
transannular peroxide, 331 inductive effect and, 22,66 Bond in Reimer-Tiemann reaction, 290
Anti-bonding orbitals, 6, 292 Lewis and, 54 angles, 4 intermediates, 41,200,229,295
Anti-knock agents, 305 multiply bonded N and, 72 energy, 9,304 in Wurtz reaction, 289
Anti-Markownikov addition, 317 nucleophilicity and, 96 heterolytic fission, 20,299 oxidation, 294,307
Anti-oxidants, 330 origin in organic comps., 66 homolytic fission, 20, 299 rearrangement, 292
Antiperiplanar conformation, 118,253 ortho effects in, 71 Bond-breaking solvation, 45
Arenium ions, 131 softness, 96 AH+ and, 38 stabilisation, 251,257,262,273,2%
Arenonium ions, 131 steric effects in, 70,71 Bond lengths, 7 steric effects in, 276
Arndt-Eistert reaction, 119 Basic strength hybridisation and, 7 tautomerism and, 277
Aromaticity, l 4 aliphatic amines, 66 Bonding orbitals, 6 trapping of, 286
cycloheptatrienyl cation, 18, 104, 106 amides, 68 Branching, 321 triphenylmethyl, 271,272
cyclopentadienyl anion, 18, 275 amidines, 69 Bredt's rule, 259 Carbenes, 21
cyclopropenyl cation, 18, 106 aromatic bases, 69 Bridged species, 105,118,129,335,377 dichlorocarbene, 4,50, 267,290
n.m.r. spectrum and, 18 catalysis and, 75 Bromodealkylation, 162 intermediates, 119,266
requirements for, 17 conjugate acids, 65 Bromonium ions, cyclic, 180 Carbinolamine intermediates, 50,219
Aromatic substitution, 41 AP and, 66 detection, 181 Carbocations, 21, 101-119
electrophilic, 130-167 guanidine, 68 isolation, 181 acyl, 102, 144,242,379
internal, 334, 381 heterocyclic bases, 72, 166 l-Bromotriptycene, 87 addition to 113, 188,225
C+ ,
nucleophilic, 167-177 t e t r a a k y h m m ~ ~hydroxides,
~m 67 Brensted allylic, 85, 105, 1%
radical, 331-335 Beckmann rearrangement, 123 acids, 53 benzylic, 84,91, 102, 105, 112,371
Arrhenius equation, 38 acid catalysis, 124 bases, 53 bridged, 105,118,129,377
Arrows ~,'80 in, 125 Butyl rubber, 189 cycloheptatrienyl, 18, 104, 106
curved, l9 intramolecularity, 126 cyclohexadienyl, 159
double-headed, 19 solvent polarity and, 126 cyclopropenyl, 18, 106
Arylation, 332 stereoselectivity, 124 decomposition, 102
Aryne intermediates, 21, 174 Benzene Cadmium Alkyls, 238 ethyl, 83, 104,380
Associative process, 239, 241 aromaticity and, 14 Cannizzaro reaction, 47,216 formation, 101, 107, 120
Atactic polymers, 322 bond lengths, 15 intramolecular, 217 hydride shifts in, 108, 109
Atomic orbitals, 1, 342 charge cloud, 15, 130 isotopic labels in, 47,217 in E l pathway, 248,261
Aufbau principle, 3 delocalisation in, 14, 130 crossed, 216 in Friedel-Crafts, 108, 141, 145
Autoxidation, 306, 318,328 heat of hydrogenation, 16 Canonical structures, 19, 152 in S,1 pathway, 78, 81, 83,90,371
alkenes, 329 KekulC structures, 14, 194 Carbamic acids, 122 loss of H@, 107, 111
benzaldehyde, 306,330 m.0.s of, 14 Carbanions, 21,270-298 methyl, 83, 104,380
cumene, l28 n.m.r. signal, 18 acetylide anion, 223,272,289,294 2-methylpropyl, 78,83, 102, 104
ethers, 329 ozonolysis, 194 acidity and, 272,277 n.m.r. and, 102, 181,393
tetralin, 329 planarity, 14 addition to 200 phenonium, l05
Axial overlap, 6 stability, 15 addition to C=O, 221-236,284 phenyl, l69
h i d e s , 123, 194 Benzilic acid rearrangement, 232 alkylation of, 288 propyl, 83,104,107,109
Azoalkanes Benzoin condensation, 231 as nucleophiles, 288 rearrangement, 32,102,107,109-119
photolysis, 304 cyanide ion in, 231 configuration, 276 reduction, 306
thermolysis, 305 thiazolium ylids in, 232 cyclooctatetraenyl dianion, 275 solvation, 45
400 Index Index 401
Ambident nucleophiles, 97 BAc2 pathway, 239,384 Benzotriazoles, 148, 176 cyclopentadienyl anion, 275
Amides Baeyer-Villiger oxidation, 127 Benzyne, 175,251 deuterium exchange, 288
from Beckmann, 123 Barton reaction, 337 dimerisation, 176 displacement reactions, 287
Hofmann reaction, 49, 122 Base catalysis isolation, 175 ElcB elimination and, 248,285
hydrolysis, 239,245, 388 general, 75 mass spec., 176 electronic effects in, 272
reduction, 214 ion exchange resins, 226 structure, 175 enolate anions, 279,290,295
Amidines specific, 75 Biosynthetic pathways, 48 formation, 271
basicity, 69 Basicity Biphenylene, 176 in carbonation, 284
formation, 244 aromaticity and, 69,72 Bipolar non-protic solvents, 81,98,173, in Danens reaction, 290
Aminoazo comps, 148 Brensted and, 53 252 in decarboxylation, 285
Anionic polymerisation, 200,226 cation stability and, 67, 68, 72, 73 Biradicals, 315,331, 337 in Favorskii reaction, 294
Antarafacial shifts, 353 constant, 65 oxygen, 315,330 in halogenation of ketones, 295
Anthracene, 17 effect of solvent on, 66,67 stable, 338 in Kolbe-Schmidt reaction, 291
photodimer, 337 H-bonding in, 67 Bisulphite addition comps., 207, 213 in Michael reaction, 200
transannular peroxide, 331 inductive effect and, 22,66 Bond in Reimer-Tiemann reaction, 290
Anti-bonding orbitals, 6, 292 Lewis and, 54 angles, 4 intermediates, 41,200,229,295
Anti-knock agents, 305 multiply bonded N and, 72 energy, 9,304 in Wurtz reaction, 289
Anti-Markownikov addition, 317 nucleophilicity and, 96 heterolytic fission, 20,299 oxidation, 294,307
Anti-oxidants, 330 origin in organic comps., 66 homolytic fission, 20, 299 rearrangement, 292
Antiperiplanar conformation, 118,253 ortho effects in, 71 Bond-breaking solvation, 45
Arenium ions, 131 softness, 96 AH+ and, 38 stabilisation, 251,257,262,273,2%
Arenonium ions, 131 steric effects in, 70,71 Bond lengths, 7 steric effects in, 276
Arndt-Eistert reaction, 119 Basic strength hybridisation and, 7 tautomerism and, 277
Aromaticity, l 4 aliphatic amines, 66 Bonding orbitals, 6 trapping of, 286
cycloheptatrienyl cation, 18, 104, 106 amides, 68 Branching, 321 triphenylmethyl, 271,272
cyclopentadienyl anion, 18, 275 amidines, 69 Bredt's rule, 259 Carbenes, 21
cyclopropenyl cation, 18, 106 aromatic bases, 69 Bridged species, 105,118,129,335,377 dichlorocarbene, 4,50, 267,290
n.m.r. spectrum and, 18 catalysis and, 75 Bromodealkylation, 162 intermediates, 119,266
requirements for, 17 conjugate acids, 65 Bromonium ions, cyclic, 180 Carbinolamine intermediates, 50,219
Aromatic substitution, 41 AP and, 66 detection, 181 Carbocations, 21, 101-119
electrophilic, 130-167 guanidine, 68 isolation, 181 acyl, 102, 144,242,379
internal, 334, 381 heterocyclic bases, 72, 166 l-Bromotriptycene, 87 addition to 113, 188,225
C+ ,
nucleophilic, 167-177 t e t r a a k y h m m ~ ~hydroxides,
~m 67 Brensted allylic, 85, 105, 1%
radical, 331-335 Beckmann rearrangement, 123 acids, 53 benzylic, 84,91, 102, 105, 112,371
Arrhenius equation, 38 acid catalysis, 124 bases, 53 bridged, 105,118,129,377
Arrows ~,'80 in, 125 Butyl rubber, 189 cycloheptatrienyl, 18, 104, 106
curved, l9 intramolecularity, 126 cyclohexadienyl, 159
double-headed, 19 solvent polarity and, 126 cyclopropenyl, 18, 106
Arylation, 332 stereoselectivity, 124 decomposition, 102
Aryne intermediates, 21, 174 Benzene Cadmium Alkyls, 238 ethyl, 83, 104,380
Associative process, 239, 241 aromaticity and, 14 Cannizzaro reaction, 47,216 formation, 101, 107, 120
Atactic polymers, 322 bond lengths, 15 intramolecular, 217 hydride shifts in, 108, 109
Atomic orbitals, 1, 342 charge cloud, 15, 130 isotopic labels in, 47,217 in E l pathway, 248,261
Aufbau principle, 3 delocalisation in, 14, 130 crossed, 216 in Friedel-Crafts, 108, 141, 145
Autoxidation, 306, 318,328 heat of hydrogenation, 16 Canonical structures, 19, 152 in S,1 pathway, 78, 81, 83,90,371
alkenes, 329 KekulC structures, 14, 194 Carbamic acids, 122 loss of H@, 107, 111
benzaldehyde, 306,330 m.0.s of, 14 Carbanions, 21,270-298 methyl, 83, 104,380
cumene, l28 n.m.r. signal, 18 acetylide anion, 223,272,289,294 2-methylpropyl, 78,83, 102, 104
ethers, 329 ozonolysis, 194 acidity and, 272,277 n.m.r. and, 102, 181,393
tetralin, 329 planarity, 14 addition to 200 phenonium, l05
Axial overlap, 6 stability, 15 addition to C=O, 221-236,284 phenyl, l69
h i d e s , 123, 194 Benzilic acid rearrangement, 232 alkylation of, 288 propyl, 83,104,107,109
Azoalkanes Benzoin condensation, 231 as nucleophiles, 288 rearrangement, 32,102,107,109-119
photolysis, 304 cyanide ion in, 231 configuration, 276 reduction, 306
thermolysis, 305 thiazolium ylids in, 232 cyclooctatetraenyl dianion, 275 solvation, 45
402 Index
Index 403
Carbocations (contd.) Chugaev reaction, 268
stabilisation, 21,84, 87, 104, 109,371, Cisoid conformation, 197,344, 350 Cyanides, addition to, 244 in a complexes, 132, 151, 164
382 Claisen ester condensation, 229 Cyanoethylation, 199 steric inhibition of, 26, 71, 172
stereochemistry of, 79, 84, 86, 104 Claisen rearrangement, 355 Cyanohydrins, 212 tropylium cation, 18, 104, 106
structure, 104 Claisen-Schmidt reaction, 226 Cyclic bromonium ions, 180 6 steric parameter, 386
triphenylmethyl, 84,87, 102, 103, 381 Clemmensen reduction, 146 Cycloadditions, 341, 348-352 AG, 34
tropylium, 104 Colour 2ne + 2ze, 348 AG+, 38, 152, 158, 342, 394
Carbon acids, 270 conjugation and, 13,331, 391 4ne + 2 n e , 348,349 AGe, 36,58,66,394
Carbonation, 284 Combustion, heat of, 12 symmetry allowed, 349 AH, 16,34
Carbon, electron-deficient migration to, Competition experiments, 157 symmetry forbidden, 348 bond energy and, 35
108 Complexes, dissociation, 27 Cycloheptatrienyl cation, 18, 104, 106 AH+, 38,239,241,342,394
Carbonyl group, 203-244 Concerted reactions, 341 Cyclohexadienyl cation, 159 h p , 58,66, 394
bond length, 11 stereoselectivity in, 341 Cyclohexadienyl radical, 331
characterisation, 219 symmetry allowed, 348 Cyclooctatetraene, 16
conjugated, 12,23,200,205,223 symmetry forbidden, 348, 357 dianion, 275
dipole, 23,203 Configuration, 38, 88 n.m.r. signal, 18 Desulphurisation, 212
hydrates, 207 apparent retention, 94 shape, l7 Deuterium
hydrogen bonding, 204,209 carbanions, 276 Cyclopentadiene exchange, 131,158,174,211,288
i.r. spectrum, 219 carbocations, 104 acidity, 275 kinetic isotope effect, 46, 136,139,288
nucleophilic addition, 31, 200, 203- determination of relative, 88, 90 in Diels-Alder, 197, 350 Diamagnetism, 308
244 inversion, 87, 90, 190 tricyclic dimer, 351 Diaryls, synthesis, 333
protection, 210,211 oximes, 124 Cyclopentadienyl anion, 18,275 Diazoamino cornps., 147
protonation, 103,204 racemisation, 89, 90, 326 Cyclopropanes rearrangement, 148
reactivity, 205 radicals, 309 from carbenes, 50,266 Diazo coupling, 26,28, 146
reduction, 212,214-219 retention, 93, 326 thermolysis, 337 amines, 26, 147
structure, 23,203 Conformation Cyclopropanone electron density in, 148
Carboxylic derivs., reactions, 236244 antiperiplanar, 118,253 hydration, 209 intramolecular, 148
acid hydrolysis, 240 intermediates, 294 kinetics, 147, 148
chair, 355
base hydrolysis, 238 Cyclopropenyl cation, 18, 106 p H and, 146
cisoid, 197, 344, 350
electronic effects in, 237 phenols, 147, 155
eclipsed, 7,254
Grignard reagents, 238 steric effects in, 27
staggered, 7,254
leaving groups and, 237 Diazoketones, rearrangement, 119
synperiplanar, 253,269
reduction, 215 Danens reaction, 290 Diazonium cations, 27, 119, 146
tram diaxial, 255
steric effects in, 238 Dealkylation, 143 akyl, 107, 120
transoid, 197, 350 aryl, 121, 146
tetrahedral intermediates in, 236 Debromination, 264
Conjugate
Catalysts Decarbonylation, 145, 335 coupling by, 27, 146
acids, 53, 65
acid, 42, 74 Decarboxylation, 271,285 decomposition, 104, 107, 120, 333
bases, 53
base, 75 carbanions in, 271,285 stability of, 120, 146
Conjugate addition, 201
cyanide ion, 231 Conjugated carbonyl cornps., 12, 23, cyclic T.S.s in, 286 nucleophilic substitution, 169, 306
heterogeneous, 143, 191,264 electronic effects on, 286 Diazotate anions, 146
200, 223
Lewis acid, 131, 189 Conjugated dienes, 11 trapping in, 286 Diazotisation
metal, 191 Conjugation, 11, 368 Dehydration aliphatic amines, 107, 119
nucleophilic, 99 Conrotation, 345 acid-catalysed, 103,220,225,247, 380 aromatic amines, 121, 146
reaction pathway and, 41 Coordination polymerisation, 322 base-catalysed, 225,262 Dichlorocarbenes, 4,50,267,290
thiazolium ylids, 232 Copolymerisation, 322 Delocalisation, 13 Dieckmann reaction, 230
Cationic polymerisation, 189 Cope reaction, 268 amidines, 69 Diels-Alder reaction, 175, 197, 340, 349
Cellulose oxidation, 37 Cope rearrangement, 354 benzene, 14,130 cyclopentadiene in, 197
Chain length, 314, 324 Cracking, 112, 305 canonical structures and, 19 electronic effects in. 198, 349
Chain reactions, 300, 314 Cram's rule, 235 carbanions, 21,23,229,274 endo v.exo addition, 350
Chain transfer agents, 321 Cross-linking, 323 carbocations, 21, 83, 84, 87, 104, 110 +
4 n e 2 n e , 349
Chair conformation, 355 Crossover experiments, 116, 122, 126 carbonyl a m p s . , 23,205 reversibility, 351
Charge transfer complexes, 131 carboxylate anions, 19,55,57 secondary orbital interaction, 350
Crowding, 8,110,162,165,183,206,235,
Chelation, 291 conditions necessary for, 18 stereoselectivity in, 198, 349
259, 261, 301, 311
Chirality, 87, 116,235,254, 278, 326 Cumene, phenol from, 128 dienes, 13, 194 steric effects in, 198,350
Chloral hydrate, 208 Curtius rearrangement, 122 energy, 13, 16 symmetry control in, 348
Chromatography, 43, 258 Curved arrows, 19 guanidine, 68 trapping in, 175
hyperconjugation and, 25 zwitterion intermediate, 351
402 Index
Index 403
Carbocations (contd.) Chugaev reaction, 268
stabilisation, 21,84, 87, 104, 109,371, Cisoid conformation, 197,344, 350 Cyanides, addition to, 244 in a complexes, 132, 151, 164
382 Claisen ester condensation, 229 Cyanoethylation, 199 steric inhibition of, 26, 71, 172
stereochemistry of, 79, 84, 86, 104 Claisen rearrangement, 355 Cyanohydrins, 212 tropylium cation, 18, 104, 106
structure, 104 Claisen-Schmidt reaction, 226 Cyclic bromonium ions, 180 6 steric parameter, 386
triphenylmethyl, 84,87, 102, 103, 381 Clemmensen reduction, 146 Cycloadditions, 341, 348-352 AG, 34
tropylium, 104 Colour 2ne + 2ze, 348 AG+, 38, 152, 158, 342, 394
Carbon acids, 270 conjugation and, 13,331, 391 4ne + 2 n e , 348,349 AGe, 36,58,66,394
Carbonation, 284 Combustion, heat of, 12 symmetry allowed, 349 AH, 16,34
Carbon, electron-deficient migration to, Competition experiments, 157 symmetry forbidden, 348 bond energy and, 35
108 Complexes, dissociation, 27 Cycloheptatrienyl cation, 18, 104, 106 AH+, 38,239,241,342,394
Carbonyl group, 203-244 Concerted reactions, 341 Cyclohexadienyl cation, 159 h p , 58,66, 394
bond length, 11 stereoselectivity in, 341 Cyclohexadienyl radical, 331
characterisation, 219 symmetry allowed, 348 Cyclooctatetraene, 16
conjugated, 12,23,200,205,223 symmetry forbidden, 348, 357 dianion, 275
dipole, 23,203 Configuration, 38, 88 n.m.r. signal, 18 Desulphurisation, 212
hydrates, 207 apparent retention, 94 shape, l7 Deuterium
hydrogen bonding, 204,209 carbanions, 276 Cyclopentadiene exchange, 131,158,174,211,288
i.r. spectrum, 219 carbocations, 104 acidity, 275 kinetic isotope effect, 46, 136,139,288
nucleophilic addition, 31, 200, 203- determination of relative, 88, 90 in Diels-Alder, 197, 350 Diamagnetism, 308
244 inversion, 87, 90, 190 tricyclic dimer, 351 Diaryls, synthesis, 333
protection, 210,211 oximes, 124 Cyclopentadienyl anion, 18,275 Diazoamino cornps., 147
protonation, 103,204 racemisation, 89, 90, 326 Cyclopropanes rearrangement, 148
reactivity, 205 radicals, 309 from carbenes, 50,266 Diazo coupling, 26,28, 146
reduction, 212,214-219 retention, 93, 326 thermolysis, 337 amines, 26, 147
structure, 23,203 Conformation Cyclopropanone electron density in, 148
Carboxylic derivs., reactions, 236244 antiperiplanar, 118,253 hydration, 209 intramolecular, 148
acid hydrolysis, 240 intermediates, 294 kinetics, 147, 148
chair, 355
base hydrolysis, 238 Cyclopropenyl cation, 18, 106 p H and, 146
cisoid, 197, 344, 350
electronic effects in, 237 phenols, 147, 155
eclipsed, 7,254
Grignard reagents, 238 steric effects in, 27
staggered, 7,254
leaving groups and, 237 Diazoketones, rearrangement, 119
synperiplanar, 253,269
reduction, 215 Danens reaction, 290 Diazonium cations, 27, 119, 146
tram diaxial, 255
steric effects in, 238 Dealkylation, 143 akyl, 107, 120
transoid, 197, 350 aryl, 121, 146
tetrahedral intermediates in, 236 Debromination, 264
Conjugate
Catalysts Decarbonylation, 145, 335 coupling by, 27, 146
acids, 53, 65
acid, 42, 74 Decarboxylation, 271,285 decomposition, 104, 107, 120, 333
bases, 53
base, 75 carbanions in, 271,285 stability of, 120, 146
Conjugate addition, 201
cyanide ion, 231 Conjugated carbonyl cornps., 12, 23, cyclic T.S.s in, 286 nucleophilic substitution, 169, 306
heterogeneous, 143, 191,264 electronic effects on, 286 Diazotate anions, 146
200, 223
Lewis acid, 131, 189 Conjugated dienes, 11 trapping in, 286 Diazotisation
metal, 191 Conjugation, 11, 368 Dehydration aliphatic amines, 107, 119
nucleophilic, 99 Conrotation, 345 acid-catalysed, 103,220,225,247, 380 aromatic amines, 121, 146
reaction pathway and, 41 Coordination polymerisation, 322 base-catalysed, 225,262 Dichlorocarbenes, 4,50,267,290
thiazolium ylids, 232 Copolymerisation, 322 Delocalisation, 13 Dieckmann reaction, 230
Cationic polymerisation, 189 Cope reaction, 268 amidines, 69 Diels-Alder reaction, 175, 197, 340, 349
Cellulose oxidation, 37 Cope rearrangement, 354 benzene, 14,130 cyclopentadiene in, 197
Chain length, 314, 324 Cracking, 112, 305 canonical structures and, 19 electronic effects in. 198, 349
Chain reactions, 300, 314 Cram's rule, 235 carbanions, 21,23,229,274 endo v.exo addition, 350
Chain transfer agents, 321 Cross-linking, 323 carbocations, 21, 83, 84, 87, 104, 110 +
4 n e 2 n e , 349
Chair conformation, 355 Crossover experiments, 116, 122, 126 carbonyl a m p s . , 23,205 reversibility, 351
Charge transfer complexes, 131 carboxylate anions, 19,55,57 secondary orbital interaction, 350
Crowding, 8,110,162,165,183,206,235,
Chelation, 291 conditions necessary for, 18 stereoselectivity in, 198, 349
259, 261, 301, 311
Chirality, 87, 116,235,254, 278, 326 Cumene, phenol from, 128 dienes, 13, 194 steric effects in, 198,350
Chloral hydrate, 208 Curtius rearrangement, 122 energy, 13, 16 symmetry control in, 348
Chromatography, 43, 258 Curved arrows, 19 guanidine, 68 trapping in, 175
hyperconjugation and, 25 zwitterion intermediate, 351
404
Dienes, 11
Index
E,, 38
Ecli~sedconformation., 7.254
~ l e ~ t r o c ~ creactions,
lic
Electrolytic oxidation, 307
Electrolytic reduction, 3CV
Electromeric effect, 24
Electron configuration, 3
Electron density, 21,26, 29,393
Electron-donating groups, 23,26
addition to
-
341, 344-348
and, 183
addition to C=O and, 205,206
aromatic substitution and, 153, 158
pinacol change and, 115
Electronegativity, 21,22,95
Electrons, lone pair, 10, 72
Electron spin, paired, 2, 308
Electron-withdrawing groups, 23
acidity and, 59,61,62,272
Electrophilic addition to
194
bromine, 51, 179
temperature and, 36
Index
Enolisation, 201,219,225,280,297,356
Enthalpy, 34
of activation, 38
Entropy, 34
cyclisation and, 36
energy partition and, 35
hydrogen bonding and, 36
of activation, 39,79
rotational, 36
Dienes, 11
Index
E,, 38
Ecli~sedconformation., 7.254
~ l e ~ t r o c ~ creactions,
lic
Electrolytic oxidation, 307
Electrolytic reduction, 3CV
Electromeric effect, 24
Electron configuration, 3
Electron density, 21,26, 29,393
Electron-donating groups, 23,26
addition to
-
341, 344-348
and, 183
addition to C=O and, 205,206
aromatic substitution and, 153, 158
pinacol change and, 115
Electronegativity, 21,22,95
Electrons, lone pair, 10, 72
Electron spin, paired, 2, 308
Electron-withdrawing groups, 23
acidity and, 59,61,62,272
Electrophilic addition to
194
bromine, 51, 179
temperature and, 36
Index
Enolisation, 201,219,225,280,297,356
Enthalpy, 34
of activation, 38
Entropy, 34
cyclisation and, 36
energy partition and, 35
hydrogen bonding and, 36
of activation, 39,79
rotational, 36
Esterification (contd.) with cyclic anhydrides, 146 downward deviations in, 380 esters, 238, 374
AAc2 pathway, 241,384 Frontier orbital approach, 344 solvent effects and, 388 halides, 77
AA,l pathway, 241,380 f,, 156, 159,333 steric effects and, 361,383 Hydroperoxides
acid-catalysed, 240, 378 upward deviations in, 375 formation, 328
acyl-oxygen fission, 88,240,242 Gatterman-Koch reaction, 145 uses of, 374 in autoxidation, 328
alkyl-oxygen fission, 240 Gegen ions, 91 Hammond's principle, 137 rearrangement, l28
isotope labels in, 88,241 General acid catalysis, 74,208,209,220, Hard bases, 96 Hydroxamic acids, Lossen degradation,
steric effects in, 242 297 Heat of combustion, 12 123
Esters General base catalysis, 75, 208 Heat of hydration, 97 Hydroxylation, 189
acyloin condensation, 218 Gibbs free energy, G, 34 Heat of hydrogenation, 12,16 Hyperconjugation, 25
Claisen condensation, 229 1,2-Glycols benzene, l 6 alkene stability and, 26
hydrolysis, 238-244,365,367,378, c k , 189 cyclohexene, l 6 aromatic substitution and, 153
384 rearrangement, l l 3 cyclooctatetraene, 16 carbocation stability and, 83
reduction, 215 tram, 190 cyclooctene, 16 Hypochlorites, alkyl, 327
E, solvent parameter, 391 Gomberg reaction, 333 dienes, 16, 194 Hiickel's rule, 17, 106
Ethanoate anion, 19 Grignard reagents Heat of reaction, 34 Hund's rule, 3,275
Excited state addition to 6 C + 0 , 201 Heisenberg principle, 2
carbon, 4 addition to C%N, 244 Hemi-acetals, 209 Imino-ethers, 245
dienes, 13 addition to 6 0 , 2 2 1 , 2 3 5 , 2 3 8 Heterolysis, 20, 129, 178,299 Inductive effect, 21
Exclusion principle, 2 structure, 221 Hexacene, 331 acidity and, 273
Exo addition, 350 Ground state Hofmann basicity and, 66
Exocyclic methylenes, 234 carbon, 3 elimination, 256 electronegativity and, 22
dienes, 13 reaction of amides, 49, 122 electrophilic substitution and, 152,
Fats, rancidity, 328 halogenobenzenes, 156 HOMO, 344 156,160
Favorskii rearrangement, 294 Grunwald-Winstein equation, 389 Homolysis, 20,129, 179,299 Inductomeric effect, 24
Fenton's reagent, 306 compound parameter, m, in, 390 Hybridisation, 4 Insertion reactions, 50,266,267
Ferrocene, 275 derivation of, 389 Hydration Intermediates
Field effects, 22, 152, 364 diagnostic use of, 391 C=C, 42,187 bridged, 105,118,129,335,377
Flash photolysis, 304 limitations of, 391 C==O. 207 catalysts and, 42
Fluorination, 121, 140, 170,315,326 solvent parameter, Y, in, 389 heat of, 97 criteria for, 49
Free energy, Gibbs, 34 standard reaction for, 389 Hydride transfer, 108,109,214,215,216 cyclic, 180,189,227
change and K, 35,359 standard solvent for, 389 Hvdroboration, 187 isolation, 48, 136, 142, 171,290
of activation, 38, 359 Gutta percha, 323 ~ i d r o ~ abstiaction,
en 309,316,321 models for T.S., 41, 51,78,137, 151
standard, 35 Hydrogenation spectroswpic detection, 50, 144, 171,
Freezing point depression Half-life, 301 *C, 191 181,219,237
benzoic acid, 242 Haloform reaction, 237, 296 M,191 study of, 49
ketones, 103 Halogenation C==O, 214 tetrahedral, 236
mesitoic acid, 243 alkanes, 300, 323 heat of, 16 trapping, 50, 175,286, 356
nitric acid, 134 alkenes, 179,186,313 homogeneous catalysis in, 192 Wheland, 41,131,151
Friedel-Crafts reaction benzene, 138,316 stereoselectivity in, 191 Intermolecular rearrangements, 143,
acylation, 143 ketones, 295 Hydrogen bonding 149,278
acylium ions in, 144 Hammett equation, 362 acidity and, 63,64 Intimate ion pairs, 91,249,291
alkylation, 141 additional parameters, 374, 388, 395 C==O and, 204,209,286 Intramolecular rearrangements, 116,
carbocations in, 108, 141, 145 derivation of, 362 intermolecular, 36,282 122, 126, 127, 128,217,232,279,
dealkylation in, 143 deviations from, 375 intramolecular, 36,208,281 355
formylation, 145 empirical nature of, 395 solvation and, 57,67,252,282 Inversion
intermediates in, 141, 144 implications of, 394 Hydrogen peroxide in SN1, 90
intramolecular, 243 reaction pathway, and, 375 Fenton's reagent, 306 in SN2,88,89, 190
Lewis acids in, 108, 141, 144 solvent effects and, 388 hydroxylation of *C, 189 Iodoform, 297
polarised complexes in, 108, 141,144 spectroscopic correlations, 392 oxidation of ketones, 127 Iodonium ions, cyclic, 186
polyalkylation, 143 standard reaction for, 362,395 Hydrogen shifts Ionisation
rearrangements in, 108, 142, 143, 163 steric effects and, 361,383 1,3-photochemical, 354 AG* and, 58
solvent and, 143, 144 thermodynamic implications of, 394 1,s-thermal, 353 solvent and, 56,102, 388
thermodynamic control in, 163 Hammett plots, 359 1,7-photochemical, 354 temperature and, 64
with alcohols, 142 change in rate-limiting step and, 383 1,7-thermal, 354 Ion pairs, 20,45,57,64,79,102,136,
with alkenes, 142 change in reaction pathway and, 378 Hydrolysis, 141
406 Index Index 407
Esterification (contd.) with cyclic anhydrides, 146 downward deviations in, 380 esters, 238, 374
AAc2 pathway, 241,384 Frontier orbital approach, 344 solvent effects and, 388 halides, 77
AA,l pathway, 241,380 f,, 156, 159,333 steric effects and, 361,383 Hydroperoxides
acid-catalysed, 240, 378 upward deviations in, 375 formation, 328
acyl-oxygen fission, 88,240,242 Gatterman-Koch reaction, 145 uses of, 374 in autoxidation, 328
alkyl-oxygen fission, 240 Gegen ions, 91 Hammond's principle, 137 rearrangement, l28
isotope labels in, 88,241 General acid catalysis, 74,208,209,220, Hard bases, 96 Hydroxamic acids, Lossen degradation,
steric effects in, 242 297 Heat of combustion, 12 123
Esters General base catalysis, 75, 208 Heat of hydration, 97 Hydroxylation, 189
acyloin condensation, 218 Gibbs free energy, G, 34 Heat of hydrogenation, 12,16 Hyperconjugation, 25
Claisen condensation, 229 1,2-Glycols benzene, l 6 alkene stability and, 26
hydrolysis, 238-244,365,367,378, c k , 189 cyclohexene, l 6 aromatic substitution and, 153
384 rearrangement, l l 3 cyclooctatetraene, 16 carbocation stability and, 83
reduction, 215 tram, 190 cyclooctene, 16 Hypochlorites, alkyl, 327
E, solvent parameter, 391 Gomberg reaction, 333 dienes, 16, 194 Hiickel's rule, 17, 106
Ethanoate anion, 19 Grignard reagents Heat of reaction, 34 Hund's rule, 3,275
Excited state addition to 6 C + 0 , 201 Heisenberg principle, 2
carbon, 4 addition to C%N, 244 Hemi-acetals, 209 Imino-ethers, 245
dienes, 13 addition to 6 0 , 2 2 1 , 2 3 5 , 2 3 8 Heterolysis, 20, 129, 178,299 Inductive effect, 21
Exclusion principle, 2 structure, 221 Hexacene, 331 acidity and, 273
Exo addition, 350 Ground state Hofmann basicity and, 66
Exocyclic methylenes, 234 carbon, 3 elimination, 256 electronegativity and, 22
dienes, 13 reaction of amides, 49, 122 electrophilic substitution and, 152,
Fats, rancidity, 328 halogenobenzenes, 156 HOMO, 344 156,160
Favorskii rearrangement, 294 Grunwald-Winstein equation, 389 Homolysis, 20,129, 179,299 Inductomeric effect, 24
Fenton's reagent, 306 compound parameter, m, in, 390 Hybridisation, 4 Insertion reactions, 50,266,267
Ferrocene, 275 derivation of, 389 Hydration Intermediates
Field effects, 22, 152, 364 diagnostic use of, 391 C=C, 42,187 bridged, 105,118,129,335,377
Flash photolysis, 304 limitations of, 391 C==O. 207 catalysts and, 42
Fluorination, 121, 140, 170,315,326 solvent parameter, Y, in, 389 heat of, 97 criteria for, 49
Free energy, Gibbs, 34 standard reaction for, 389 Hydride transfer, 108,109,214,215,216 cyclic, 180,189,227
change and K, 35,359 standard solvent for, 389 Hvdroboration, 187 isolation, 48, 136, 142, 171,290
of activation, 38, 359 Gutta percha, 323 ~ i d r o ~ abstiaction,
en 309,316,321 models for T.S., 41, 51,78,137, 151
standard, 35 Hydrogenation spectroswpic detection, 50, 144, 171,
Freezing point depression Half-life, 301 *C, 191 181,219,237
benzoic acid, 242 Haloform reaction, 237, 296 M,191 study of, 49
ketones, 103 Halogenation C==O, 214 tetrahedral, 236
mesitoic acid, 243 alkanes, 300, 323 heat of, 16 trapping, 50, 175,286, 356
nitric acid, 134 alkenes, 179,186,313 homogeneous catalysis in, 192 Wheland, 41,131,151
Friedel-Crafts reaction benzene, 138,316 stereoselectivity in, 191 Intermolecular rearrangements, 143,
acylation, 143 ketones, 295 Hydrogen bonding 149,278
acylium ions in, 144 Hammett equation, 362 acidity and, 63,64 Intimate ion pairs, 91,249,291
alkylation, 141 additional parameters, 374, 388, 395 C==O and, 204,209,286 Intramolecular rearrangements, 116,
carbocations in, 108, 141, 145 derivation of, 362 intermolecular, 36,282 122, 126, 127, 128,217,232,279,
dealkylation in, 143 deviations from, 375 intramolecular, 36,208,281 355
formylation, 145 empirical nature of, 395 solvation and, 57,67,252,282 Inversion
intermediates in, 141, 144 implications of, 394 Hydrogen peroxide in SN1, 90
intramolecular, 243 reaction pathway, and, 375 Fenton's reagent, 306 in SN2,88,89, 190
Lewis acids in, 108, 141, 144 solvent effects and, 388 hydroxylation of *C, 189 Iodoform, 297
polarised complexes in, 108, 141,144 spectroscopic correlations, 392 oxidation of ketones, 127 Iodonium ions, cyclic, 186
polyalkylation, 143 standard reaction for, 362,395 Hydrogen shifts Ionisation
rearrangements in, 108, 142, 143, 163 steric effects and, 361,383 1,3-photochemical, 354 AG* and, 58
solvent and, 143, 144 thermodynamic implications of, 394 1,s-thermal, 353 solvent and, 56,102, 388
thermodynamic control in, 163 Hammett plots, 359 1,7-photochemical, 354 temperature and, 64
with alcohols, 142 change in rate-limiting step and, 383 1,7-thermal, 354 Ion pairs, 20,45,57,64,79,102,136,
with alkenes, 142 change in reaction pathway and, 378 Hydrolysis, 141
408 Index
n-excessive heterocycles, 166 SYN, 267 in Barton reaction, 337 types of, 30
Pinacolinic deamination, 113,118 Pyrrole in Gomberg reaction, 333 Reaction constant, p, 363
Pinacollpinacolone rearrangement, 113 basicity, 73 in halogenation, 323 attenuation of, 368
migratory aptitude in, 114 electrophilic substitution, 166 in hydroxylation, 332 determination of, 363
Pinacols protonation, 73 inhibitors, 300,318,321 effect of solvent on, 388
formation, 218 initiators, 314,321 physical significance of, 367
rearrangement, l13 Quantum numbers in phenol oxidation, 334 rate-limiting step and, 368,381
pK,, 54,270,362 principal, n, 2 in polymerisation, 308,320 reaction centre and, 368
temperature and, 64 spin, 2 in Pschorr reaction, 334 reaction pathway and, 378
P&, 65 subsidiary, l and m, 2 oxygen and, 300 sign of, 368
P~B*, Quinuclidine paramagnetic, 308 values of, 364
Plane trigonal hybridisation, 5 basicity, 72 pentachloroethyl, 314 variation with solvent, 388
Polarisability, 24,% complex with Me,B, 28 perbenzoate, 330 Reaction mechanism, investigation, 43,
Polarisation, 22,29 phenoxy, 302,334 375
Polarised complexes, 108,141,144 RaeemisPtion, 89 peroxy, 315,328,337 Reactive methylenes, 288
Polar non-protic solvents, 81 deuterium exchange and, 288 polar effects in, 325 Reagents, classification, 28
Polyenes in radical reactions, 326 rearrangement, 325 Rearrangements, 30,32,109-129,352-
hydrogen shifts in, 352 in S,1, 90 shape, 309,326 357
Polyisoprenes, 323 Radical addition, 312-323 solvent and, 309,324 alkanes, 108
Polymerisation carbon tetrachloride, 320 stability, 302,309,312,324 alkenes, 112
anionic, 200,226 halogens, 313 stereoselectivity and, 318,326,333 allylic, 109
branching, 321 hydrogen bromide, 316 terminators, 300,321 aryl, 128
cationic, 189 sulphenyl halides, 320 thiyl, 302,319 Beckmann, l23
chain length, 321 vinyl polymerisation, 320 trapping, 302 benzilic acid, 232
chain transfer, 321 Radical anions, 218 triphenylmethyl, 43,300,306,311 carbanions, 292
coordination, 322 Radical rearrangements, 335 Radical substitution, 323-335 carbocations, 109-119
copolymerisation, 322 Radicals, 20,30,299-339 aromatic, 331 Claisen, 355
cross-linking, 323 acyl, 306,330,335 autoxidation, 328 configuration in, 116,123
induction period, 321 addition to C=c, 313-323 halogenation, 323 conformation in, 115,118
initiation, 321 alkoxyl, 303 Radiolysis, 304 Cope, 354
propagation, 320 alkyl, 301,303,304,324 Raman spectra, 134 Curtius, l22
radical, 308,320 allylic, 311,325,327,329 Raney nickel catalyst, 212 diazoamino comps., 148
stereochemistry, 322,323 benzoyl, 330 Rate constant, k,38,39 diazoketones, 119
termination, 320 benzylic, 311,316,329 Rate equation, 39 dienone-phenol, 115
Products, nature of, 43 biradicals, 315,330,337 mixed order, 82,91 Favorskii, 294
Propane, rearrangement, 108 bridged, 310 T.S. and, 41 Hofmam, 122
Protecting groups, 155,210,211,265 chain reactions, 300,313,314,328 Rate-limiting step, 39,40,134,148,171, hydroperoxides, l28
requirements, 211 combustion and, 299 381 in Friedel-Crafts, 108,142,145,163
Protodesilylation, 149,161 conformational equilibrium, 319 Rate of reaction intermolecular, 117,143,149,278
Protodesulphonylation, 140,161 cycloheptatrienyl, 308 activation energy and, 37 intramolecular, 116,122,126,127,
Proton transfer cyclohexadienyl, 331 catalysts and, 41 279,355
catalysed, 74 detection, 308 measurement of, 39 Lossen, 122
to C=c, 103 dimerisation, 300,305,311,313,314, a and, 366 migratory aptitude in, 114
to lone pairs, 103,112,116 320,332,334 temperature and, 38 neopentyl, 110
Prototropy, 277 l ,l-diphenyl-2-picrylhydrazyl,301 Reaction pinacol-pinacolone, 113
Pschorr reaction, 334 disproportionation, 305,313,320,332 collisions in, 38 radical, 335
Pyridine e.s.r. spectroscopy and, 308 concerted, 341 Schmidt, 122
basicity, 72 formation, 303 energetics of, 33,37 sigmatropic, 352
delocalisation in, 18,165 half-life, 301,305 energy profile of, 37 stereochemistry of, 116,117,119
electrophilic substitution, 165 halomethyl, 320 heat of, 34 steric effects in, 115
nucleophilic substitution, 168 hetero, 302 intermediates, 38,49 Stevens, 293
Pyrolytic elimination, 267,340 hydroxyl, 306 kinetics of, 36 Wagner-Meemein, 111
carbocationic character T.s., 269,340 in acyloxylation, 333 molecularity, 79 Wittig, 293
Cope, 268 in aromatic substitution, 331,334 order, 39,79 Wolff, 119
chugaev, 268 in arylation, 332 rate constant, 38 Redox reactions, 306
Ei, 261 in autoxidation, 306,318,328 rate-limiting step, 39 Reimer-Tiemann reaction, 290
Zndex 413
n-excessive heterocycles, 166 SYN, 267 in Barton reaction, 337 types of, 30
Pinacolinic deamination, 113,118 Pyrrole in Gomberg reaction, 333 Reaction constant, p, 363
Pinacollpinacolone rearrangement, 113 basicity, 73 in halogenation, 323 attenuation of, 368
migratory aptitude in, 114 electrophilic substitution, 166 in hydroxylation, 332 determination of, 363
Pinacols protonation, 73 inhibitors, 300,318,321 effect of solvent on, 388
formation, 218 initiators, 314,321 physical significance of, 367
rearrangement, l13 Quantum numbers in phenol oxidation, 334 rate-limiting step and, 368,381
pK,, 54,270,362 principal, n, 2 in polymerisation, 308,320 reaction centre and, 368
temperature and, 64 spin, 2 in Pschorr reaction, 334 reaction pathway and, 378
P&, 65 subsidiary, l and m, 2 oxygen and, 300 sign of, 368
P~B*, Quinuclidine paramagnetic, 308 values of, 364
Plane trigonal hybridisation, 5 basicity, 72 pentachloroethyl, 314 variation with solvent, 388
Polarisability, 24,% complex with Me,B, 28 perbenzoate, 330 Reaction mechanism, investigation, 43,
Polarisation, 22,29 phenoxy, 302,334 375
Polarised complexes, 108,141,144 RaeemisPtion, 89 peroxy, 315,328,337 Reactive methylenes, 288
Polar non-protic solvents, 81 deuterium exchange and, 288 polar effects in, 325 Reagents, classification, 28
Polyenes in radical reactions, 326 rearrangement, 325 Rearrangements, 30,32,109-129,352-
hydrogen shifts in, 352 in S,1, 90 shape, 309,326 357
Polyisoprenes, 323 Radical addition, 312-323 solvent and, 309,324 alkanes, 108
Polymerisation carbon tetrachloride, 320 stability, 302,309,312,324 alkenes, 112
anionic, 200,226 halogens, 313 stereoselectivity and, 318,326,333 allylic, 109
branching, 321 hydrogen bromide, 316 terminators, 300,321 aryl, 128
cationic, 189 sulphenyl halides, 320 thiyl, 302,319 Beckmann, l23
chain length, 321 vinyl polymerisation, 320 trapping, 302 benzilic acid, 232
chain transfer, 321 Radical anions, 218 triphenylmethyl, 43,300,306,311 carbanions, 292
coordination, 322 Radical rearrangements, 335 Radical substitution, 323-335 carbocations, 109-119
copolymerisation, 322 Radicals, 20,30,299-339 aromatic, 331 Claisen, 355
cross-linking, 323 acyl, 306,330,335 autoxidation, 328 configuration in, 116,123
induction period, 321 addition to C=c, 313-323 halogenation, 323 conformation in, 115,118
initiation, 321 alkoxyl, 303 Radiolysis, 304 Cope, 354
propagation, 320 alkyl, 301,303,304,324 Raman spectra, 134 Curtius, l22
radical, 308,320 allylic, 311,325,327,329 Raney nickel catalyst, 212 diazoamino comps., 148
stereochemistry, 322,323 benzoyl, 330 Rate constant, k,38,39 diazoketones, 119
termination, 320 benzylic, 311,316,329 Rate equation, 39 dienone-phenol, 115
Products, nature of, 43 biradicals, 315,330,337 mixed order, 82,91 Favorskii, 294
Propane, rearrangement, 108 bridged, 310 T.S. and, 41 Hofmam, 122
Protecting groups, 155,210,211,265 chain reactions, 300,313,314,328 Rate-limiting step, 39,40,134,148,171, hydroperoxides, l28
requirements, 211 combustion and, 299 381 in Friedel-Crafts, 108,142,145,163
Protodesilylation, 149,161 conformational equilibrium, 319 Rate of reaction intermolecular, 117,143,149,278
Protodesulphonylation, 140,161 cycloheptatrienyl, 308 activation energy and, 37 intramolecular, 116,122,126,127,
Proton transfer cyclohexadienyl, 331 catalysts and, 41 279,355
catalysed, 74 detection, 308 measurement of, 39 Lossen, 122
to C=c, 103 dimerisation, 300,305,311,313,314, a and, 366 migratory aptitude in, 114
to lone pairs, 103,112,116 320,332,334 temperature and, 38 neopentyl, 110
Prototropy, 277 l ,l-diphenyl-2-picrylhydrazyl,301 Reaction pinacol-pinacolone, 113
Pschorr reaction, 334 disproportionation, 305,313,320,332 collisions in, 38 radical, 335
Pyridine e.s.r. spectroscopy and, 308 concerted, 341 Schmidt, 122
basicity, 72 formation, 303 energetics of, 33,37 sigmatropic, 352
delocalisation in, 18,165 half-life, 301,305 energy profile of, 37 stereochemistry of, 116,117,119
electrophilic substitution, 165 halomethyl, 320 heat of, 34 steric effects in, 115
nucleophilic substitution, 168 hetero, 302 intermediates, 38,49 Stevens, 293
Pyrolytic elimination, 267,340 hydroxyl, 306 kinetics of, 36 Wagner-Meemein, 111
carbocationic character T.s., 269,340 in acyloxylation, 333 molecularity, 79 Wittig, 293
Cope, 268 in aromatic substitution, 331,334 order, 39,79 Wolff, 119
chugaev, 268 in arylation, 332 rate constant, 38 Redox reactions, 306
Ei, 261 in autoxidation, 306,318,328 rate-limiting step, 39 Reimer-Tiemann reaction, 290
414 Index Zndex 415
416 Index
416 Index
Page
Foreword by Professor Lord Todd, O.M., P.P.R.S. ix
Preface to sixth edition xi
1 Structure, reactivity, and mechanism 1
2 Energetics, kinetics, and the investigation of mechanism 33
3 The strengths of acids and bases 53
4 Nucleophilic substitution at a saturated carbon atom 77
5 Carbocations, electron-deficient N and O atoms and their 101
reactions
6 Electrophilic and nucleophilic substitution in aromatic 130
systems
7 Electrophilic and nucleophilic addition to C=C 178
8 Nucleophilic addition to C = O 203
9 Elimination reactions 246
10 Carbanions and their reactions 270
11 Radicals and their reactions 299
12 Symmetry controlled reactions 340
13 Linear free energy relationships 358
Select bibliography 396
Index 399