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398 Select bibliography

WENIRUP, C . Reactive Molecules: The Neutral Reactive Intermediate


in Organic Chemistry (Wiley, 1984).
Index
Review series
Advances in Physical Organic Chemistry. WLD, v. and,-B D.
(Eds) (Academic Press, Vol. I, 1963- ).
Organic Reaction Mechanisms. KNIPE, A. C . and W A ~W. , E. (Eds)
(Interscience, Vol. I, 1966- ).
Progress in Physical Organic Chemistry. TAFT, R. W. (Ed.) (Inter-
science, Vol. 1, 1963- ).
Reactive Intermediates-A Serial Publication, JONES, M. and MOSS, R. Aeetals Activation parameters
A. (Eds) (Wiley-Interscience, Vol. I, 1978- ). cyclic, 210 energy, E,, 38
formation, 209,289 enthalpy, AH+, 38
Audio cassettes hydrolysis, 74,210 entropy, AS*, 39
Acid catalysis free energy, AG*, 38
The following titles in the 'Chemistry Cassette' series are published general, 74 Acyl cations, 102, 144,240,242, 379
by, and are available from, The Chemical Society, Blackhorse Road, specific, 74 Acyloin condensation, 218
Letchworth, Herts., SG6 lHN, England: AA,l pathway, 242,243 Addition, 30
AA,2 pathway, 241,244,384 1,3-dipolar, 192, 194,351
CC3 S W , P. Some Organic Reaction Pathways: ( A ) .Eliminatibn; electrophilic, 31, 50, 178-198
A?, pathway, 241
( B ) . Aromatic Substitution (1975). Aad~ty nucleophilic, 31, 198, 207-245
CC6 S W , P. Some Reaction Pathways of Double Bonds: ( A ) . anion stability and, 23,55,271 radical, 31,313-323
C=C; ( B ) . C=O (1977). aromaticity and, 275 to +C, 31,51, 103, 113, 178, 188
CC7 S W , P. Some Reaction Pathways of Carboxylic Acid Denva- Br0nsted and, 53 to (+C, 182
constant K,, 54,271 to -+C, 195
tives (1979). definitions of, 53 to ckc-c==O, 200
CC9 S-, P. Radicals and their Reaction Pathways (1979). A G and, ~ 58,60,61, 394 to e N ,244
CC11 SYKES, P. Linear Free Energy Relationships (1980). AWand, 58,394 to C+0, 31,50, 103,203
Ase and, 58,394 Adsorption, 191
effect of solvent, 56 Aldehyde ammonias, 220
effect of temperature, 64 Aldol reaction, 224
H-bonding in, 63,64 acid catalysed, 225
hybridisation and, 59,273 crossed, 226
in C-H comps., 251,270 intramolecular, 226
kinetic control of, 270,280 reversibility, 75, 224
Lewis and, 54 Alkenes
cycloaddition, 348
origin in organic comps., 55
steric effects in, 58 polar addition, 178-195
Acid strength protection in, 265
alcohols, 55, 56 radical addition, 313-323
aliphatic acids, 54, 55, 57, 59 relative stability, 26,256
alkanes, 55,271 Alkylchlorosulphites, decomp.. 93
alkenes, 272 Alkyl shifts, 111, 113, 115,293,337
alkynes, 223,273,289,294 Alkynes
aromatic acids, 62 acidity, 223,272
catalysis and, 74 addition to -0,223
dicarboxylic acids, 63 alkylation, 289
imides, 68 dimerisation, 294
nitroalkanes, 272,280,283 ozonolysis, 194
phenols, 23, 56,61
triphenylmethane, 271 cation, 85, 105, 196
Acrylonitrile, 199 radical, 311
Activated complex, 38 rearrangement, 109
398 Select bibliography

WENIRUP, C . Reactive Molecules: The Neutral Reactive Intermediate


in Organic Chemistry (Wiley, 1984).
Index
Review series
Advances in Physical Organic Chemistry. WLD, v. and,-B D.
(Eds) (Academic Press, Vol. I, 1963- ).
Organic Reaction Mechanisms. KNIPE, A. C . and W A ~W. , E. (Eds)
(Interscience, Vol. I, 1966- ).
Progress in Physical Organic Chemistry. TAFT, R. W. (Ed.) (Inter-
science, Vol. 1, 1963- ).
Reactive Intermediates-A Serial Publication, JONES, M. and MOSS, R. Aeetals Activation parameters
A. (Eds) (Wiley-Interscience, Vol. I, 1978- ). cyclic, 210 energy, E,, 38
formation, 209,289 enthalpy, AH+, 38
Audio cassettes hydrolysis, 74,210 entropy, AS*, 39
Acid catalysis free energy, AG*, 38
The following titles in the 'Chemistry Cassette' series are published general, 74 Acyl cations, 102, 144,240,242, 379
by, and are available from, The Chemical Society, Blackhorse Road, specific, 74 Acyloin condensation, 218
Letchworth, Herts., SG6 lHN, England: AA,l pathway, 242,243 Addition, 30
AA,2 pathway, 241,244,384 1,3-dipolar, 192, 194,351
CC3 S W , P. Some Organic Reaction Pathways: ( A ) .Eliminatibn; electrophilic, 31, 50, 178-198
A?, pathway, 241
( B ) . Aromatic Substitution (1975). Aad~ty nucleophilic, 31, 198, 207-245
CC6 S W , P. Some Reaction Pathways of Double Bonds: ( A ) . anion stability and, 23,55,271 radical, 31,313-323
C=C; ( B ) . C=O (1977). aromaticity and, 275 to +C, 31,51, 103, 113, 178, 188
CC7 S W , P. Some Reaction Pathways of Carboxylic Acid Denva- Br0nsted and, 53 to (+C, 182
constant K,, 54,271 to -+C, 195
tives (1979). definitions of, 53 to ckc-c==O, 200
CC9 S-, P. Radicals and their Reaction Pathways (1979). A G and, ~ 58,60,61, 394 to e N ,244
CC11 SYKES, P. Linear Free Energy Relationships (1980). AWand, 58,394 to C+0, 31,50, 103,203
Ase and, 58,394 Adsorption, 191
effect of solvent, 56 Aldehyde ammonias, 220
effect of temperature, 64 Aldol reaction, 224
H-bonding in, 63,64 acid catalysed, 225
hybridisation and, 59,273 crossed, 226
in C-H comps., 251,270 intramolecular, 226
kinetic control of, 270,280 reversibility, 75, 224
Lewis and, 54 Alkenes
cycloaddition, 348
origin in organic comps., 55
steric effects in, 58 polar addition, 178-195
Acid strength protection in, 265
alcohols, 55, 56 radical addition, 313-323
aliphatic acids, 54, 55, 57, 59 relative stability, 26,256
alkanes, 55,271 Alkylchlorosulphites, decomp.. 93
alkenes, 272 Alkyl shifts, 111, 113, 115,293,337
alkynes, 223,273,289,294 Alkynes
aromatic acids, 62 acidity, 223,272
catalysis and, 74 addition to -0,223
dicarboxylic acids, 63 alkylation, 289
imides, 68 dimerisation, 294
nitroalkanes, 272,280,283 ozonolysis, 194
phenols, 23, 56,61
triphenylmethane, 271 cation, 85, 105, 196
Acrylonitrile, 199 radical, 311
Activated complex, 38 rearrangement, 109
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
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

addition to, 194-198


cisoid conformation, 197,350
conjugated, 11
Cope rearrangement, 354
cyclisation, 346
cycloaddition to, 348
Diels-Alder reaction, 197,349
excited state, 13
heat of hydrogenation, 16,194
isolated, 11
m.0.s of, 12
polymerisation, 323
Dienone intermediates, 356
Dienonelphenol rearrangement, 115
Dienophiles, 198,350
Digonal hybridisation, 5
Dimedone, 202
Dimroth's E, parameter, 391
solvatochromic shifts, 391
solvent polarity, 391
Y and, 392
Dinitrofluorobenzene
proteins and, 172
1,2-Diols
formation, 189
rearrangement, 113
1,l-Diphenyl-2-picrylhydrazyl,
Diphenylpolyenes, 13
301

1,3-Dipolar addition, 192, 194,351


Dipole moments, 22, 156, 165,203
Diradicals, 315, 330, 337
stable, 338
Displacement, 30
Disproportionation, 216,305,321
Disrotation, 345
Dissociative process, 241

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

proton, 103, 184, 187


rate, 183, 185
C+,
addition to C===Cand, 183
addition to C=O and, 205,226
aromatic substitution and, 151, 158
basicity and, 67,70
elimination and, 251, 262
Electrophiles, 29

1,3-dipolar, 192, 194, 351

rearrangements in, 185, 187


solvent and, 182
31, 178-

carbocations, 113, 180, 184, 187, 188,


225
cationic polymerisation, 189
cyclic bromonium ions, 180

effect of added nucleophiles, 179


hydration, 187
hydroboration, 187
hydrogenation, 191
hydrogen bromide, 184,201
hydroxylation, 189
inductive effect in, 185
Lewis acids, 181
mesomeric effect in, 182
orientation, 184
ozone, 192
peroxy acids, 190
n complexes in, 180, 184

stereoselectivity, 51, 180, 182, 186,


188,189, 191
steric effects, 181
vinyl halides, 185
Electrophilic addition to C=Ca,
194
Electrophilic substitution, aromatic, 31,
130-167,381
1,2-v. l ,4-addition, 195
as additionlelimination, 133
complexing with substituent, 160
deuterium exchange, 131, 158
electronic effects in, 148, 158, 159
energetics of, 132, 136
field effect in, 152
hyperconjugation in, 153
inductive effect in, 22, 152, 153, 156,
160
intermediates, isolation, 136, 142
internal, 381
ipso, 161
isotope effects, 46, 139
kinetic control, 151, 163, 164
Lewis acids in, 131, 138, 141,144, 163
mesomeric effect in, 154, 155, 164
o-/p-ratios, 159
n complexes in, 131
partial rate factors, 156
selectivity in, 158
a complexes in, 41, 131,151,159
solvent and, 161
steric effects in, 153, 158, 159, 162,
165
substituent effects, 150-163
thermodynamic control, 163, 164
transition states, 135, 151, 158
1,3-Elimination, 293
E l elimination, 248,381
alkene stability and, 249,256
carbocations and, 247,248
orientation in, 249
Saytzev mode, 249
SN1and, 248,260
steric effects in, 261
structure and, 249
v. E2,249,252
ElcB elimination, 249
activation energy, 250
carbanions and, 248,249,257
electron-withdrawal and, 251
in aldol dehydration, 225,251
in benzyne formation, 251
isotopic exchange and, 250
leaving group and, 251
structure and, 251
E2 elimination, 251-260
alkene stability and, 253,256
base strength and, 252
bond strength and, 252
conformation and, 253,255
electronic effects in, 257
Hofmann mode, 256
in cyclic comps., 255
kinetic isotope effect, 252
leaving group and, 252,257
orientation in, 256
Saytzev mode, 256
SN2and, 252,254,260
solvent and, 252,255
stereoselectivity in, 253,264
steric effects in, 258
strength of base and, 257
variable T.S. in, 256
E,(1 ,l-)elimination, 266
bases and, 266
carbenes in, 50,266
isotopic labelling in, 266
Ei elimination, pyrolytic, 268, 340
Cope reaction, 268
stereoselectivity, 268,269
Elimination v. substitution, 100, 260
base size and, 261

entropy and, 262

temperature and, 36
Index

alkene stability and, 261

change of pathway, 260


E1/SN1ratio, 260
E2/SN2ratio, 260

leaving group and, 261


solvent and, 260
steric effects in, 261,262
structure and, 260,261
temperature and, 262
Enamines, 221
End group analysis, 172
Endo addition, 350
Energetics of reaction, 33
Energy barriers, 37
Energy profiles, 37
Enolate anions, 279, 290,295

translational, 36, 58, 239


Epoxides,
as intermediates, 94, 190
hydrolysis, 190
Epoxyesters, U$-, 290
E; 373
Eauilibrium
acidity and, 54
basicity and, 65
constant, K, 35
405

basicitylnucleophilicity in, 262

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

control, 43, 163, 165, 171, 195


entropy and, 36
free energy and, 35
E.s.r. spectroscopy, 308
spin trapping in, 309
splitting in, 308
E, steric parameter, 386
Ester hydrolysis
acid-catalysed, 240
acyl-oxygen fission, 47,239
alkyl-oxygen fission, 47,241
BAC2pathway, 239,384
base-catalysed, 239,366, 367,374
isotopic labels in, 47, 89, 238
steric effects in, 241,361,385
Esterification
AAC1pathway, 242,379
404

Dienes, 11
Index

addition to, 194-198


cisoid conformation, 197,350
conjugated, 11
Cope rearrangement, 354
cyclisation, 346
cycloaddition to, 348
Diels-Alder reaction, 197,349
excited state, 13
heat of hydrogenation, 16,194
isolated, 11
m.0.s of, 12
polymerisation, 323
Dienone intermediates, 356
Dienonelphenol rearrangement, 115
Dienophiles, 198,350
Digonal hybridisation, 5
Dimedone, 202
Dimroth's E, parameter, 391
solvatochromic shifts, 391
solvent polarity, 391
Y and, 392
Dinitrofluorobenzene
proteins and, 172
1,2-Diols
formation, 189
rearrangement, 113
1,l-Diphenyl-2-picrylhydrazyl,
Diphenylpolyenes, 13
301

1,3-Dipolar addition, 192, 194,351


Dipole moments, 22, 156, 165,203
Diradicals, 315, 330, 337
stable, 338
Displacement, 30
Disproportionation, 216,305,321
Disrotation, 345
Dissociative process, 241

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

proton, 103, 184, 187


rate, 183, 185
C+,
addition to C===Cand, 183
addition to C=O and, 205,226
aromatic substitution and, 151, 158
basicity and, 67,70
elimination and, 251, 262
Electrophiles, 29

1,3-dipolar, 192, 194, 351

rearrangements in, 185, 187


solvent and, 182
31, 178-

carbocations, 113, 180, 184, 187, 188,


225
cationic polymerisation, 189
cyclic bromonium ions, 180

effect of added nucleophiles, 179


hydration, 187
hydroboration, 187
hydrogenation, 191
hydrogen bromide, 184,201
hydroxylation, 189
inductive effect in, 185
Lewis acids, 181
mesomeric effect in, 182
orientation, 184
ozone, 192
peroxy acids, 190
n complexes in, 180, 184

stereoselectivity, 51, 180, 182, 186,


188,189, 191
steric effects, 181
vinyl halides, 185
Electrophilic addition to C=Ca,
194
Electrophilic substitution, aromatic, 31,
130-167,381
1,2-v. l ,4-addition, 195
as additionlelimination, 133
complexing with substituent, 160
deuterium exchange, 131, 158
electronic effects in, 148, 158, 159
energetics of, 132, 136
field effect in, 152
hyperconjugation in, 153
inductive effect in, 22, 152, 153, 156,
160
intermediates, isolation, 136, 142
internal, 381
ipso, 161
isotope effects, 46, 139
kinetic control, 151, 163, 164
Lewis acids in, 131, 138, 141,144, 163
mesomeric effect in, 154, 155, 164
o-/p-ratios, 159
n complexes in, 131
partial rate factors, 156
selectivity in, 158
a complexes in, 41, 131,151,159
solvent and, 161
steric effects in, 153, 158, 159, 162,
165
substituent effects, 150-163
thermodynamic control, 163, 164
transition states, 135, 151, 158
1,3-Elimination, 293
E l elimination, 248,381
alkene stability and, 249,256
carbocations and, 247,248
orientation in, 249
Saytzev mode, 249
SN1and, 248,260
steric effects in, 261
structure and, 249
v. E2,249,252
ElcB elimination, 249
activation energy, 250
carbanions and, 248,249,257
electron-withdrawal and, 251
in aldol dehydration, 225,251
in benzyne formation, 251
isotopic exchange and, 250
leaving group and, 251
structure and, 251
E2 elimination, 251-260
alkene stability and, 253,256
base strength and, 252
bond strength and, 252
conformation and, 253,255
electronic effects in, 257
Hofmann mode, 256
in cyclic comps., 255
kinetic isotope effect, 252
leaving group and, 252,257
orientation in, 256
Saytzev mode, 256
SN2and, 252,254,260
solvent and, 252,255
stereoselectivity in, 253,264
steric effects in, 258
strength of base and, 257
variable T.S. in, 256
E,(1 ,l-)elimination, 266
bases and, 266
carbenes in, 50,266
isotopic labelling in, 266
Ei elimination, pyrolytic, 268, 340
Cope reaction, 268
stereoselectivity, 268,269
Elimination v. substitution, 100, 260
base size and, 261

entropy and, 262

temperature and, 36
Index

alkene stability and, 261

change of pathway, 260


E1/SN1ratio, 260
E2/SN2ratio, 260

leaving group and, 261


solvent and, 260
steric effects in, 261,262
structure and, 260,261
temperature and, 262
Enamines, 221
End group analysis, 172
Endo addition, 350
Energetics of reaction, 33
Energy barriers, 37
Energy profiles, 37
Enolate anions, 279, 290,295

translational, 36, 58, 239


Epoxides,
as intermediates, 94, 190
hydrolysis, 190
Epoxyesters, U$-, 290
E; 373
Eauilibrium
acidity and, 54
basicity and, 65
constant, K, 35
405

basicitylnucleophilicity in, 262

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

control, 43, 163, 165, 171, 195


entropy and, 36
free energy and, 35
E.s.r. spectroscopy, 308
spin trapping in, 309
splitting in, 308
E, steric parameter, 386
Ester hydrolysis
acid-catalysed, 240
acyl-oxygen fission, 47,239
alkyl-oxygen fission, 47,241
BAC2pathway, 239,384
base-catalysed, 239,366, 367,374
isotopic labels in, 47, 89, 238
steric effects in, 241,361,385
Esterification
AAC1pathway, 242,379
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
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

Ion pairs (contd.) nitration, 43 X Lossen rearrangement, 123 Nitroalkanes


intimate, 91, 249, 291 protonation, 283 k LUMO, 344 acidity, 272, 280
solvation, 45, 57, 81, 390 Kinetic data, interpretation, 40, 44, 78 84
addition to C=O, 226
solvent separated, 91 Kinetic isotope effects, 46 Magnetic moment, electronic, 308 tautomerism, 283
Ipso substitution, 161, 169 carbon, 47 Markownikov addition, 184 Nitrodealkylation, 162
steric effects in, 162 chlorine, 47 Mass spectrometry, 176 Nitrodehalogenation, 162
Isocyanate intermediates, 49, 122 deuterium, 44,83,252,288,295 m, compound parameter, 390 Nitroeen, electron-deficient, migration
Isomer distribution, 158 primary, 44,252,288,295 diagnostic use of, 391 t;, l20
Isomerisation, cis +tram, 315 secondary, 83 Mechanistic borderline, 91 Nitroniurn ion, 45, 103,134
Isoprene, 323 Kinetics of reaction, 36 Meerwein-Ponndorf reaction, 215 Nitrosating agents, 119
Isotope effects, kinetic, 46,83,139, 252, isotope effects in, 46 Meisenheimer complexes, 171 Nitrosation
288,295 measurement of, 39,89 Mesomeric effect, 23, 154, 156, 172,238, phenol, 137
Isotopic labels, 47 rate-limiting step in, 39 278 primary aliphatic amines, 107, 119
bromide, 141 Knocking, 305 Meta (m)-directing groups, 150 ~rimaryaromatic amines, 120
carbon, 48, 108,233, 355 Knoevenagel reaction, 228 Metal alkyls secondary amines, 121
deuterium, 47, 117, 131, 174,216, Kolbe electrolytic synthesis, 307 carbonation, 284 tertiary amines, 121
217,224,233,250,264,278,288 Kolbe-Schmidt reaction, 291 thermolysis, 304 Nitrosoniurn ion, 120, 137
iodine, 89 Wurtz reaction and, 289 Nitro~otrialk~lammonium cation, 121
monitoring, 48,89 LaetPms, 126 Michael reaction, 200 Nitrous acid, protonated, 120
nitrogen, 170 Lactone intermediates, 94, 127, 228 Migration N.m.r. spectroscopy, 18,48, 102, 106,
oxygen, 47,89,125, 127,189,207,239 Lateral overlap, orbitals, 9 origin, 116 111, 126, 129, 159, 181,219
scrambling of, 108,141,169 Lead alkyls, 301 terminus, 116 aromaticity and, 18
sulphur, 165 anti-knock, 305 to electron-deficient C, 109, 110-119 13c, 49,106, 111,393
thermolysis, 301, 304, 324 to electron-deficient N, 122-126 carboxyl protonation and, 240
Leaving groups, 98,99, 127, 139,237 to electron-deficient 0 , 127-129 Grignard reagents and, 221
K, 35,359 ability of, 98, 251 Migratory aptitude, 114, 129 ozonolvsis and, 193, 194
k, 38, 359, 374 bromobenzene sulphonate ion, 375 conformation of T.S. and, 118 ox and; 393
K,, 54, 65 cyanide ion, 232 Mixed SN1/SN2pathway, 92 triphenylmethyl dimer, 44,301
AGe and, 58 ethanoate anion, 228 Models for T.S., 41,51,78,137,151, N-nitroso comwunds, 121
K*,65 ethoxide ion, 229 194,254 Nodal
AGe and, 66 hydride ion, l68 Molecularity, 79 plane, 3,343
Ketenes, 119 hydrogen bonding and, 252 Molecular orbitals, 5,343 surface, 2
B-Keto-acids, decarboxylation, 286 hydroxyl ion, 225,253 Molozonides, 193 Nodes, 343
Keto-enol tautomerism, 201,219,225 in elimination, 247,251,253 Monomers, 321 Non-bonded interaction, 7
carbanions in, 278 internal, 100 Mustard gas, 96 Nucleophiles, 29
catalysis of, 277 nitrogen, 100,104,107,114, 121,123, ambident, 97
equilibrium and structure, 280,297 169,305 Nucleophilic addition to =, 198
hydrogen bonding and, 281 protonated, 103, 125 Naphthalene, 17 carbanions in, l99
mechanism of, 278 relative ability, 98, 251, 253 nitration, 164 cyanoethylation, 199
solvent and, 282 tosylate, 89,98,100,253 sulphonation, 164 hydrogen cyanide, 199
Ketones, halogenation, 295 triflate, 98 N-brornosuccinimide, 327 methanol, 199
bromination, 41,51, 76,297 Levelling effect, water, 55 Neighbouring group participation, 93- Michael reaction, 200
electronic effects in, 2% Lewis acids, 29 96,181,377 Nucleo~hilicaddition to =m,
enolisation in, 297 Lewis bases, 29 Neopentyl rearrangements, 110 206
general acid catalysis, 297 Light absorption, colour and, 13 Newman projections, 7,235 conjugate addition, 201
general base catalysis, 76 Lindlar catalyst, 191,223 Nitration, 31,45, 133-138 Grignard reagents, 201
orientation in, 2%, 297 Linear free energy relationships, 358- dilute HNO, in, 137 Me,SiCN, 213
rate of, 295,2%, 297 395 isotope effects in, 46 Michael reaction, 202
Ketoximes, Beckmann rearrangement, Lithium kinetics of, 134, 135 steric effects in, 201
123 alkyls, 223, 238, 293 naphthalene, 164 Nucleophilic addition to 31,203-
Ketyls, 218 aryls, 223,233,293 nitronium Buoroborate in, 135 244
Kinetic acidity, 280 Lithium aluminium hydride, 214 NO? in, 134 a&tylide ions, 223
Kinetic control, 42, 151 Localised orbitals, 6 Nitrating mixture, 133 acid catalysis, 204,207,209,220,225
addition to C=0, 235 Lone pairs, 10,72 Nitrenes, 21, 122 additionlelimination, 219
addition to dienes, 195 in neighbouring groups, 94 carbonyl, l22 alcohols, 209
Diels-Alder, 350 protonated, 99,103 Nitriles, reactions, 244 aldol reaction, 224
408 Index

Ion pairs (contd.) nitration, 43 X Lossen rearrangement, 123 Nitroalkanes


intimate, 91, 249, 291 protonation, 283 k LUMO, 344 acidity, 272, 280
solvation, 45, 57, 81, 390 Kinetic data, interpretation, 40, 44, 78 84
addition to C=O, 226
solvent separated, 91 Kinetic isotope effects, 46 Magnetic moment, electronic, 308 tautomerism, 283
Ipso substitution, 161, 169 carbon, 47 Markownikov addition, 184 Nitrodealkylation, 162
steric effects in, 162 chlorine, 47 Mass spectrometry, 176 Nitrodehalogenation, 162
Isocyanate intermediates, 49, 122 deuterium, 44,83,252,288,295 m, compound parameter, 390 Nitroeen, electron-deficient, migration
Isomer distribution, 158 primary, 44,252,288,295 diagnostic use of, 391 t;, l20
Isomerisation, cis +tram, 315 secondary, 83 Mechanistic borderline, 91 Nitroniurn ion, 45, 103,134
Isoprene, 323 Kinetics of reaction, 36 Meerwein-Ponndorf reaction, 215 Nitrosating agents, 119
Isotope effects, kinetic, 46,83,139, 252, isotope effects in, 46 Meisenheimer complexes, 171 Nitrosation
288,295 measurement of, 39,89 Mesomeric effect, 23, 154, 156, 172,238, phenol, 137
Isotopic labels, 47 rate-limiting step in, 39 278 primary aliphatic amines, 107, 119
bromide, 141 Knocking, 305 Meta (m)-directing groups, 150 ~rimaryaromatic amines, 120
carbon, 48, 108,233, 355 Knoevenagel reaction, 228 Metal alkyls secondary amines, 121
deuterium, 47, 117, 131, 174,216, Kolbe electrolytic synthesis, 307 carbonation, 284 tertiary amines, 121
217,224,233,250,264,278,288 Kolbe-Schmidt reaction, 291 thermolysis, 304 Nitrosoniurn ion, 120, 137
iodine, 89 Wurtz reaction and, 289 Nitro~otrialk~lammonium cation, 121
monitoring, 48,89 LaetPms, 126 Michael reaction, 200 Nitrous acid, protonated, 120
nitrogen, 170 Lactone intermediates, 94, 127, 228 Migration N.m.r. spectroscopy, 18,48, 102, 106,
oxygen, 47,89,125, 127,189,207,239 Lateral overlap, orbitals, 9 origin, 116 111, 126, 129, 159, 181,219
scrambling of, 108,141,169 Lead alkyls, 301 terminus, 116 aromaticity and, 18
sulphur, 165 anti-knock, 305 to electron-deficient C, 109, 110-119 13c, 49,106, 111,393
thermolysis, 301, 304, 324 to electron-deficient N, 122-126 carboxyl protonation and, 240
Leaving groups, 98,99, 127, 139,237 to electron-deficient 0 , 127-129 Grignard reagents and, 221
K, 35,359 ability of, 98, 251 Migratory aptitude, 114, 129 ozonolvsis and, 193, 194
k, 38, 359, 374 bromobenzene sulphonate ion, 375 conformation of T.S. and, 118 ox and; 393
K,, 54, 65 cyanide ion, 232 Mixed SN1/SN2pathway, 92 triphenylmethyl dimer, 44,301
AGe and, 58 ethanoate anion, 228 Models for T.S., 41,51,78,137,151, N-nitroso comwunds, 121
K*,65 ethoxide ion, 229 194,254 Nodal
AGe and, 66 hydride ion, l68 Molecularity, 79 plane, 3,343
Ketenes, 119 hydrogen bonding and, 252 Molecular orbitals, 5,343 surface, 2
B-Keto-acids, decarboxylation, 286 hydroxyl ion, 225,253 Molozonides, 193 Nodes, 343
Keto-enol tautomerism, 201,219,225 in elimination, 247,251,253 Monomers, 321 Non-bonded interaction, 7
carbanions in, 278 internal, 100 Mustard gas, 96 Nucleophiles, 29
catalysis of, 277 nitrogen, 100,104,107,114, 121,123, ambident, 97
equilibrium and structure, 280,297 169,305 Nucleophilic addition to =, 198
hydrogen bonding and, 281 protonated, 103, 125 Naphthalene, 17 carbanions in, l99
mechanism of, 278 relative ability, 98, 251, 253 nitration, 164 cyanoethylation, 199
solvent and, 282 tosylate, 89,98,100,253 sulphonation, 164 hydrogen cyanide, 199
Ketones, halogenation, 295 triflate, 98 N-brornosuccinimide, 327 methanol, 199
bromination, 41,51, 76,297 Levelling effect, water, 55 Neighbouring group participation, 93- Michael reaction, 200
electronic effects in, 2% Lewis acids, 29 96,181,377 Nucleo~hilicaddition to =m,
enolisation in, 297 Lewis bases, 29 Neopentyl rearrangements, 110 206
general acid catalysis, 297 Light absorption, colour and, 13 Newman projections, 7,235 conjugate addition, 201
general base catalysis, 76 Lindlar catalyst, 191,223 Nitration, 31,45, 133-138 Grignard reagents, 201
orientation in, 2%, 297 Linear free energy relationships, 358- dilute HNO, in, 137 Me,SiCN, 213
rate of, 295,2%, 297 395 isotope effects in, 46 Michael reaction, 202
Ketoximes, Beckmann rearrangement, Lithium kinetics of, 134, 135 steric effects in, 201
123 alkyls, 223, 238, 293 naphthalene, 164 Nucleophilic addition to 31,203-
Ketyls, 218 aryls, 223,233,293 nitronium Buoroborate in, 135 244
Kinetic acidity, 280 Lithium aluminium hydride, 214 NO? in, 134 a&tylide ions, 223
Kinetic control, 42, 151 Localised orbitals, 6 Nitrating mixture, 133 acid catalysis, 204,207,209,220,225
addition to C=0, 235 Lone pairs, 10,72 Nitrenes, 21, 122 additionlelimination, 219
addition to dienes, 195 in neighbouring groups, 94 carbonyl, l22 alcohols, 209
Diels-Alder, 350 protonated, 99,103 Nitriles, reactions, 244 aldol reaction, 224
410 Index
Index 411
Nucleophilic addition to C==O (contd.) charge distribution in T.S., 78, 80,83,
ammonia derivs., 219 84 filled, l 7 Paramagnetism, 308
base catalysis, 204,207,212, 216, 226 1,2-chlorohydrins,94 frontier, 344 Paint, hardening, 328
benzoin condensation, 231 2-chloro-2-methylpropane, 78 HOMO, 344 Partial rate factors,f,, 156,159,333
bisulphite anion, 207,213 configuration in, 88,89,90,92,93,94 hybridisation of, 4 Pauli principle, 2
Cannizzaro reaction, 216 electronic effects in, 82, 83, 84 lasral overlap, 9 Pericyclic reactions, 198,341
carbanions, 221-234 entering group and, 96 lobes, 9 Perkin reaction, 227
Claisen ester condensation, 229 He catalysis, 99 localised, 6 Peroxide effect, 317
Claisen-Schmidt reaction, 226 I~ catalysis, 98 LUMO, 344 Peroxides
conjugate, 200,213 isotopic label (I) in, 89 molecular, 5 as initiators, 300, 317
cyanide ion, 212 kinetics of, 45, 77, 89 nodal planes and, 1,343 heterolysis, 129, 306
Dieckmann reaction, 230 leaving group and, 98 overlap integral, 5, 342 homolysis, 129, 333
electronic effects in, 205,208,226 list of reactions, 99 P, 2 in ozonolysis, 193
electrons, 217 mechanistic borderline, 91 phase of, 342 photolysis, 304
Grignard reagents, 221,235 mechanistic changeover, 82,84,96 A, 9,337 rearrangement, l27
halide ion, 214 neighbouring group participation, 93 S * , 9, 337 thermolysis, 304
hydration, 207 neopentyl halides, 86 S, 2 trans-annular, 331
hydride ion, 214 rate1li&ting step, 78 shape, 3 Peroxyacids, 190,330
hydrogen bonding in, 204,209 SNl, 79, 90 0,6 Peroxy radicals, 315,328,337
in carboxylic derivs., 236-244 S ~ 2 , 7 8 , 8 793
, U*, 6 Peroxy zwitterions, 193
intermediates in, 50,219 size, 2 Petroleum cracking, 112,305
intramolecular, 217,232 secondary interaction, 350 Phase, orbital, 342
irreversible, 215, 222 solvation in, 45, 79, 80, 90, 91, 97 spl, 5 Phenanthrene, 17
Knoevenagel reaction, 228 solvolysis, 80, 91 sp2, 5 Pschorr synthesis, 334
Lewis acids in, 204,222 steric effects in, 82, 84,85,86, 109 sp3, 4 Phenol
Meerwein-Ponndorf reaction, 215 stereochemistry of, 87-96 spatial orientation, 2, 3 acidity, 23,61,370
Me3SiCN, 213 structure and, 82-87,90 symmetry, 342 coupling, 334
nitroalkanes, 226 tosylates, 89 Order of reaction, 39, 79 diazo coupling, 147, 155
Perkin reaction, 227 triphenylmethyl halides, 84 first, 39 from cumene, 128
pH and, 204,208,219 v. elimination, 100,248, 260 mixed, 82,91 nitration, 137
protection, 211 vinvl halides. 85 molecularity and, 79 oxidation, 334
rate-limiting step, 205,212,216,220 ~ u c l ~ o ~ h s"bstitution,
ilic aromatic, second, 39 Phenonium ion, 105,376
reversibility, 206,210,212, 224 167-177 Organometallic compounds, structure, Phenylation, 332
size of nucleophile in, 207, 213 activated aryl halides, 170 221,276,293 Phenylnitromethane, tautomerism, 283
spectroscopy and, 50,219 anionic intermediates, 168, 170, 171 Orthoesters Phenyl radicals, 332
stereoselectivity, 234 aryne intermediates, 173 acetals from, 210,289 Phosphine oxides, 234
steric effects in, 205,213,222,243 as additionlelimination, 172 hydrolysis, 75 Phosphonium ylids, 233
Stobbe reaction, 228 as eliminationladdition, 175 Ortholpara (0-lp-) Phosphoranes, 233
thiols, 211 deuterium exchange, 174 directing groups, 150,159 Phosphorus-oxygen bond, 233
T.S. in, 205 diazonium salts, 121, 169 ratios, 159 Photochemical concerted reactions, 341,
Wittig reaction, 233 ipso, 169 Osmic esters, cyclic, 189 346
Nucleophilic catalysis, 99 nitrobenzene, 168 Osmium tetroxide, 189 1,3-hydrogen shifts, 354
Nucleophilicity, 96, 211 pyridine, 168 Overlap 1,7-hydrogenshifts, 354
basicity and, 96 steric inhibition of delocalisation, 173 axial, 6 2ne + 2ne, 349
soft bases and, 96 Nylon-6, 126 integral, 5,342 Photochemical initiation, 300
Nucleophilic substitution, aliphatic, 31, lateral, 9 Photo-dimerisation, 337
45.77-100 Oleum, 140 Oxaphosphetanes, 233 Photolysis, 303
Aga catalysis, 97 Oppenauer oxidation, 216 Oximes Photo-oxidation, 330
ally1 halides, 85 Orbitals configuration, 124,220 Physical methods
ambident nucleophiles, 97 anti-bonding, 6, 292 formation, 219 analysis of products, 43,156,281
benzyl halides, 84,91 atomic, 1 rearrangement, 123 detection of intermediates, 50, 144,
bridgehead halides, 86 axial overlap, 6 Oxygen 171, 176,181,219,304,308
bromomethane, 78 bonding, 6 diradical, 315 structure determination, 102, 106,
2-bromopropanoate, 94 degenerate, 3 migration to electron-deficient, 127 111, 134,193,221,240
l-bromotriptycene, 87 delocalised, 13 Ozonides, 192 n bond, 9, 178
carbanions in, 100,288 dumb-bell, 3 Ozonolysis, 192 n complexes, 131, 180, 184
stereochemistry, 193 n-deficient heterocycles, 165
410 Index
Index 411
Nucleophilic addition to C==O (contd.) charge distribution in T.S., 78, 80,83,
ammonia derivs., 219 84 filled, l 7 Paramagnetism, 308
base catalysis, 204,207,212, 216, 226 1,2-chlorohydrins,94 frontier, 344 Paint, hardening, 328
benzoin condensation, 231 2-chloro-2-methylpropane, 78 HOMO, 344 Partial rate factors,f,, 156,159,333
bisulphite anion, 207,213 configuration in, 88,89,90,92,93,94 hybridisation of, 4 Pauli principle, 2
Cannizzaro reaction, 216 electronic effects in, 82, 83, 84 lasral overlap, 9 Pericyclic reactions, 198,341
carbanions, 221-234 entering group and, 96 lobes, 9 Perkin reaction, 227
Claisen ester condensation, 229 He catalysis, 99 localised, 6 Peroxide effect, 317
Claisen-Schmidt reaction, 226 I~ catalysis, 98 LUMO, 344 Peroxides
conjugate, 200,213 isotopic label (I) in, 89 molecular, 5 as initiators, 300, 317
cyanide ion, 212 kinetics of, 45, 77, 89 nodal planes and, 1,343 heterolysis, 129, 306
Dieckmann reaction, 230 leaving group and, 98 overlap integral, 5, 342 homolysis, 129, 333
electronic effects in, 205,208,226 list of reactions, 99 P, 2 in ozonolysis, 193
electrons, 217 mechanistic borderline, 91 phase of, 342 photolysis, 304
Grignard reagents, 221,235 mechanistic changeover, 82,84,96 A, 9,337 rearrangement, l27
halide ion, 214 neighbouring group participation, 93 S * , 9, 337 thermolysis, 304
hydration, 207 neopentyl halides, 86 S, 2 trans-annular, 331
hydride ion, 214 rate1li&ting step, 78 shape, 3 Peroxyacids, 190,330
hydrogen bonding in, 204,209 SNl, 79, 90 0,6 Peroxy radicals, 315,328,337
in carboxylic derivs., 236-244 S ~ 2 , 7 8 , 8 793
, U*, 6 Peroxy zwitterions, 193
intermediates in, 50,219 size, 2 Petroleum cracking, 112,305
intramolecular, 217,232 secondary interaction, 350 Phase, orbital, 342
irreversible, 215, 222 solvation in, 45, 79, 80, 90, 91, 97 spl, 5 Phenanthrene, 17
Knoevenagel reaction, 228 solvolysis, 80, 91 sp2, 5 Pschorr synthesis, 334
Lewis acids in, 204,222 steric effects in, 82, 84,85,86, 109 sp3, 4 Phenol
Meerwein-Ponndorf reaction, 215 stereochemistry of, 87-96 spatial orientation, 2, 3 acidity, 23,61,370
Me3SiCN, 213 structure and, 82-87,90 symmetry, 342 coupling, 334
nitroalkanes, 226 tosylates, 89 Order of reaction, 39, 79 diazo coupling, 147, 155
Perkin reaction, 227 triphenylmethyl halides, 84 first, 39 from cumene, 128
pH and, 204,208,219 v. elimination, 100,248, 260 mixed, 82,91 nitration, 137
protection, 211 vinvl halides. 85 molecularity and, 79 oxidation, 334
rate-limiting step, 205,212,216,220 ~ u c l ~ o ~ h s"bstitution,
ilic aromatic, second, 39 Phenonium ion, 105,376
reversibility, 206,210,212, 224 167-177 Organometallic compounds, structure, Phenylation, 332
size of nucleophile in, 207, 213 activated aryl halides, 170 221,276,293 Phenylnitromethane, tautomerism, 283
spectroscopy and, 50,219 anionic intermediates, 168, 170, 171 Orthoesters Phenyl radicals, 332
stereoselectivity, 234 aryne intermediates, 173 acetals from, 210,289 Phosphine oxides, 234
steric effects in, 205,213,222,243 as additionlelimination, 172 hydrolysis, 75 Phosphonium ylids, 233
Stobbe reaction, 228 as eliminationladdition, 175 Ortholpara (0-lp-) Phosphoranes, 233
thiols, 211 deuterium exchange, 174 directing groups, 150,159 Phosphorus-oxygen bond, 233
T.S. in, 205 diazonium salts, 121, 169 ratios, 159 Photochemical concerted reactions, 341,
Wittig reaction, 233 ipso, 169 Osmic esters, cyclic, 189 346
Nucleophilic catalysis, 99 nitrobenzene, 168 Osmium tetroxide, 189 1,3-hydrogen shifts, 354
Nucleophilicity, 96, 211 pyridine, 168 Overlap 1,7-hydrogenshifts, 354
basicity and, 96 steric inhibition of delocalisation, 173 axial, 6 2ne + 2ne, 349
soft bases and, 96 Nylon-6, 126 integral, 5,342 Photochemical initiation, 300
Nucleophilic substitution, aliphatic, 31, lateral, 9 Photo-dimerisation, 337
45.77-100 Oleum, 140 Oxaphosphetanes, 233 Photolysis, 303
Aga catalysis, 97 Oppenauer oxidation, 216 Oximes Photo-oxidation, 330
ally1 halides, 85 Orbitals configuration, 124,220 Physical methods
ambident nucleophiles, 97 anti-bonding, 6, 292 formation, 219 analysis of products, 43,156,281
benzyl halides, 84,91 atomic, 1 rearrangement, 123 detection of intermediates, 50, 144,
bridgehead halides, 86 axial overlap, 6 Oxygen 171, 176,181,219,304,308
bromomethane, 78 bonding, 6 diradical, 315 structure determination, 102, 106,
2-bromopropanoate, 94 degenerate, 3 migration to electron-deficient, 127 111, 134,193,221,240
l-bromotriptycene, 87 delocalised, 13 Ozonides, 192 n bond, 9, 178
carbanions in, 100,288 dumb-bell, 3 Ozonolysis, 192 n complexes, 131, 180, 184
stereochemistry, 193 n-deficient heterocycles, 165
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
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

Relative configuration, determination, parameter, Y, 389


88 Solvent separated ion pair, 90 Substitution Tetraalkylammonium salts
Resonance energy, 17 Solvolysis, 80, 91, 109, 389 electrophilic, aromatic, 41, 130-167 basicity, 67
Retro Diels-Alder reaction, 351 Specific acid catalysis, 74,209 nucleophilic. aliphatic. 31.77-100 elimination from, 254,256
Retro pinacol rearrangement, 115 Specific base catalysis, 75 nucleophilic; aromatic; 167-177 Tetrahedral hybridisation, 4
P, 363 Spectrosco ic correlations, 392 radical, 323-335 Tetrahedral intermediates., 236.. 361
p*, 385 a, and PC n.m.r., 393
' Sulphenyl compounds, 320 isolation, 237
Rotational entropy, 36 a, and 'H n.m.r., 393 Sulphonation, 29, 140, 164 Thermal concerted reactions, 341
Rotation frequency, 8 a, and i.r. shifts, 392 Sulphonium salts, 95, 99 Claisen rearrangement, 355
Rubber Spin, electronic, paired, 2 cyclic, 95 Cope rearrangement, 354
natural, 323 Stabilisation energy, 13 elimination from, 258 1,Shydrogen shifts, 353
perishing of, 328 Stability, thermodynamic, 12 Sulphur trioxide, in sulphonation, 140 1,7-hydrogenshifts, 354
synthetic, 189,322 Staggered conformation, 7 Sulphuryl chloride, in chlorination, 327 +
4xe 2xe, 348
vulcanisation, 323 Standing waves, electronic, 342 Super acids, 102, 129, 181 Thermodynamic control, 43, 163
Stereochemicalcriteria, 51 Suprafacial shifts, 353 addition to C==0,235
Sandmeyer reaction, 306 Stereoselectivity, 52 Symmetry controlled reactions, 340-357 addition to dienes, 195
Sandwich comoounds. 275 in acetolysis, 377 activation parameters, 342 Diels-Alder , 350
Sawhorse projections, 7 in addition to -, 51,180, 182,318 'allowed', 348 Friedel-Crafts, l63
Saytzev elimination, 249, 256 antarafacial shifts, 353 napthalene sulphonation, 43, 164
in addition to C==0,234
Schiff bases, 221 in Beckmann, 124 Claisen rearrangement, 355 nitroalkane formation, 283
Schmidt rearrangement, 122 concerted v. stepwise, 342,351 Thermodynamics, second law, 34
in concerted reactions, 341
Selectivity, 156, 169, 326 in Diels-Alder, 198,349 conrotation, 345 Thermodynamic stability, 12
a,362 in elimination, 253, 264, 267 Cope rearrangement, 354 alkenes, 26, 249
a-,370 in ozonolysis, 193 cycloaddition, 348 benzene, 15
a+,372 in rearrangements, 118 Diels-Alder reaction, 349 delocalisation and, 26
a;, 385 Steric effects, 26 disrotation, 345 dienes, 12
o bonds, 6 crowding, 27,115,235,301,350 electrocyclic, 344 hyperconjugation and, 26
U complexes, 41, 131 delocalisation and, 26,71, 172 'forbidden', 348 keto-enol forms, 282
Sigmatropic rearrangements, 352-357 in acidity, 58 residual bonding in, 342 Thiazolium ylids, 232
antarafacial, 353 in addition to C=C, 181 secondary orbital interaction, 350 Thioacetals, 211
carbon shifts, 354 in addition to 205,235 sigmatropic rearrangements, 352 desulphurisation, 212
hydrogen shifts, 352 in aromatic substitution, 152, 159, suprafacial shifts, 353 Thiols, addition to C==O, 211
orbital symmetry in, 352 162, 165 Symmetry, orbital, 344 Thionyl chloride, in chlorination, 92
photochemical, 354 in diazo coupling, 27 Synperiplanar conformation, 253,269 Through-conjugation, 368
suprafacial, 353 in elimination, 261 r and, 373
thermal, 353 in ester hydrolysis, 241 a and, 370
Silicon-oxygen bond, 213 in rearrangements, 115 Taft equation, 384 a+ and, 372,393
SE1 pathway, 288,295 non-bonded interaction, 7 amide hydrolysis and, 388 Transesterification, 239
SN1pathway, 79,370,389 Steric hindrance, 27,79, 110, 159, 162, derivation of, 386 Transition state, 24, 38
SN2pathway, 78,376 222,235,243,301,312,356 6 parameter in, 387 bridged, 118, 129,292,335
SN2' pathway, 110 Steric parameters, 386 E, parameter in, 386 composition of, 41
SN2(aromatic) pathway, 170 E,, 386 ester hydrolysis and, 384 conformation and, 118,235
SNipathway, 92 6, 387 polar effects in, 385 crowding in, 27,83, 86, 183,206,235,
Sodium borohydride, 215 Sterigrnatocystin,48 p* in, 385 259,385
Soft bases, 96 Stevens rearrangements, 293 a& in, 385 cyclic, 216,222,254,268,287, 352,
Solvation, 45,56,79,253,299,388 Stobbe reaction, 228 standard substituent in, 385 356
H-bonded, 57,67,81,253 Substituent constant, a,362 Tautomerism, 277 energy level of, 40, 137,235,283
AS^ and, 58,60,63,66 'constancy' of, 368,372 catalysis of, 277 models for, 41,49, 137, 151
polar non-protic. 81. 173.252 determination of, 363 equilibrium and structure, 280 orbital interaction in, 350
Solvatochromicshifts, 391 physical significance of, 364 intermolecular, 278 organisation in, 39
Solvent pK, and, 362 intramolecular, 278,279 residual bonding in, 342
bipolar non-protic, 81,98, 173,252 polar effects and, 366 keto-enol, 201,219,225,277 solvation of, 253
effect of, 45,80, 161,252,260,388 sign of, 364 mechanisms of, 278 variable, 92,256,257
E, and, 391 spectroscopic shifts and, 392 nitroalkanes, 277,283 Translational entropy, 35,58,239,241
ionising power, 390 values of, 363 rate and structure, 279 Transoid conformation, 197
ion-solvating ability, 80,260, 390 Substituent effects, 150, 388 rate-limiting step, 279 Trapping of intermediates
Terminators, 300,320 arynes, 176
414 Index Zndex 415

Relative configuration, determination, parameter, Y, 389


88 Solvent separated ion pair, 90 Substitution Tetraalkylammonium salts
Resonance energy, 17 Solvolysis, 80, 91, 109, 389 electrophilic, aromatic, 41, 130-167 basicity, 67
Retro Diels-Alder reaction, 351 Specific acid catalysis, 74,209 nucleophilic. aliphatic. 31.77-100 elimination from, 254,256
Retro pinacol rearrangement, 115 Specific base catalysis, 75 nucleophilic; aromatic; 167-177 Tetrahedral hybridisation, 4
P, 363 Spectrosco ic correlations, 392 radical, 323-335 Tetrahedral intermediates., 236.. 361
p*, 385 a, and PC n.m.r., 393
' Sulphenyl compounds, 320 isolation, 237
Rotational entropy, 36 a, and 'H n.m.r., 393 Sulphonation, 29, 140, 164 Thermal concerted reactions, 341
Rotation frequency, 8 a, and i.r. shifts, 392 Sulphonium salts, 95, 99 Claisen rearrangement, 355
Rubber Spin, electronic, paired, 2 cyclic, 95 Cope rearrangement, 354
natural, 323 Stabilisation energy, 13 elimination from, 258 1,Shydrogen shifts, 353
perishing of, 328 Stability, thermodynamic, 12 Sulphur trioxide, in sulphonation, 140 1,7-hydrogenshifts, 354
synthetic, 189,322 Staggered conformation, 7 Sulphuryl chloride, in chlorination, 327 +
4xe 2xe, 348
vulcanisation, 323 Standing waves, electronic, 342 Super acids, 102, 129, 181 Thermodynamic control, 43, 163
Stereochemicalcriteria, 51 Suprafacial shifts, 353 addition to C==0,235
Sandmeyer reaction, 306 Stereoselectivity, 52 Symmetry controlled reactions, 340-357 addition to dienes, 195
Sandwich comoounds. 275 in acetolysis, 377 activation parameters, 342 Diels-Alder , 350
Sawhorse projections, 7 in addition to -, 51,180, 182,318 'allowed', 348 Friedel-Crafts, l63
Saytzev elimination, 249, 256 antarafacial shifts, 353 napthalene sulphonation, 43, 164
in addition to C==0,234
Schiff bases, 221 in Beckmann, 124 Claisen rearrangement, 355 nitroalkane formation, 283
Schmidt rearrangement, 122 concerted v. stepwise, 342,351 Thermodynamics, second law, 34
in concerted reactions, 341
Selectivity, 156, 169, 326 in Diels-Alder, 198,349 conrotation, 345 Thermodynamic stability, 12
a,362 in elimination, 253, 264, 267 Cope rearrangement, 354 alkenes, 26, 249
a-,370 in ozonolysis, 193 cycloaddition, 348 benzene, 15
a+,372 in rearrangements, 118 Diels-Alder reaction, 349 delocalisation and, 26
a;, 385 Steric effects, 26 disrotation, 345 dienes, 12
o bonds, 6 crowding, 27,115,235,301,350 electrocyclic, 344 hyperconjugation and, 26
U complexes, 41, 131 delocalisation and, 26,71, 172 'forbidden', 348 keto-enol forms, 282
Sigmatropic rearrangements, 352-357 in acidity, 58 residual bonding in, 342 Thiazolium ylids, 232
antarafacial, 353 in addition to C=C, 181 secondary orbital interaction, 350 Thioacetals, 211
carbon shifts, 354 in addition to 205,235 sigmatropic rearrangements, 352 desulphurisation, 212
hydrogen shifts, 352 in aromatic substitution, 152, 159, suprafacial shifts, 353 Thiols, addition to C==O, 211
orbital symmetry in, 352 162, 165 Symmetry, orbital, 344 Thionyl chloride, in chlorination, 92
photochemical, 354 in diazo coupling, 27 Synperiplanar conformation, 253,269 Through-conjugation, 368
suprafacial, 353 in elimination, 261 r and, 373
thermal, 353 in ester hydrolysis, 241 a and, 370
Silicon-oxygen bond, 213 in rearrangements, 115 Taft equation, 384 a+ and, 372,393
SE1 pathway, 288,295 non-bonded interaction, 7 amide hydrolysis and, 388 Transesterification, 239
SN1pathway, 79,370,389 Steric hindrance, 27,79, 110, 159, 162, derivation of, 386 Transition state, 24, 38
SN2pathway, 78,376 222,235,243,301,312,356 6 parameter in, 387 bridged, 118, 129,292,335
SN2' pathway, 110 Steric parameters, 386 E, parameter in, 386 composition of, 41
SN2(aromatic) pathway, 170 E,, 386 ester hydrolysis and, 384 conformation and, 118,235
SNipathway, 92 6, 387 polar effects in, 385 crowding in, 27,83, 86, 183,206,235,
Sodium borohydride, 215 Sterigrnatocystin,48 p* in, 385 259,385
Soft bases, 96 Stevens rearrangements, 293 a& in, 385 cyclic, 216,222,254,268,287, 352,
Solvation, 45,56,79,253,299,388 Stobbe reaction, 228 standard substituent in, 385 356
H-bonded, 57,67,81,253 Substituent constant, a,362 Tautomerism, 277 energy level of, 40, 137,235,283
AS^ and, 58,60,63,66 'constancy' of, 368,372 catalysis of, 277 models for, 41,49, 137, 151
polar non-protic. 81. 173.252 determination of, 363 equilibrium and structure, 280 orbital interaction in, 350
Solvatochromicshifts, 391 physical significance of, 364 intermolecular, 278 organisation in, 39
Solvent pK, and, 362 intramolecular, 278,279 residual bonding in, 342
bipolar non-protic, 81,98, 173,252 polar effects and, 366 keto-enol, 201,219,225,277 solvation of, 253
effect of, 45,80, 161,252,260,388 sign of, 364 mechanisms of, 278 variable, 92,256,257
E, and, 391 spectroscopic shifts and, 392 nitroalkanes, 277,283 Translational entropy, 35,58,239,241
ionising power, 390 values of, 363 rate and structure, 279 Transoid conformation, 197
ion-solvating ability, 80,260, 390 Substituent effects, 150, 388 rate-limiting step, 279 Trapping of intermediates
Terminators, 300,320 arynes, 176
'V'

416 Index

Trapping of intermediates (contd.) initiation, 320, 321


carbenes, 50,267
dienones, 356
propagation, 320
termination, 320,321
Notes
internal, 266 Vulcanisation, 323
peroxynvitterions, 193
Trichloromethane hydrolysis, 42,267 Wngner-Meerwein rearrangements, 111
Triphenylmethane Water
acidity, 271 addition to -, 187
carbanion from, 271,272 addition to &---Cl, 207
radical from, 43,300 autolysis of, 54
Triphenylmethyl cation, 84, 87, 102, ion solvation and, 57,58,60
103,381 levelling effect in, 55
reduction, 306 polarisability, 57
Triphenylmethyl peroxide, 300 Wave amplitude, 343
rearrangement, 336 Wave functions, 2,342
Triphenylmethyl radical, 43, 300 Wave nodes, 343
dimer, 44,301,311 Wheland intermediates, 41, 131, 151
shape, 311 Wittig reaction, 233
Tropylium cation, 18, 104, 106 Wittig rearrangement, 293
stability, 106 Wolff rearrangement, 119
Tschitschibabin reaction, 168 Woodward-Hoffmam rules, 344
Wurtz reaction, 289
Ultra-violet absorption, 13, 132,218
Umpolung, 211 Xanthates, pyrolysis, 268
Unsaturated acids X-ray crystallography
L$-, from Perkin reaction, 227
ethanoate anion, 19 1

By-, synthesis, 234 Grignard reagents, 221


Unsaturated carbonyl compounds, cub-, Meisenheimer complexes, 171
addition to, 200 triphenylmethyl radicals, 311
formation of. 251
Ylids, 232,233,287
Y,solvent parameter, 389
Van der Wads radii, 8 values of, 390
Vibrational modes, 342 Yukawa-Tsuno equation, 372
Vinyl ethers, polymerisation, 189 parameter, r, and, 373
Vinyl polymerisation, 320
branching in, 321 Zinc alkyls, 223
chain length in, 321 Zwitterions, 94, 176
coordination, 322 diazoanthranilate anion, 176
induction period in, 321 peroxy, 193
'V'

416 Index

Trapping of intermediates (contd.) initiation, 320, 321


carbenes, 50,267
dienones, 356
propagation, 320
termination, 320,321
Notes
internal, 266 Vulcanisation, 323
peroxynvitterions, 193
Trichloromethane hydrolysis, 42,267 Wngner-Meerwein rearrangements, 111
Triphenylmethane Water
acidity, 271 addition to -, 187
carbanion from, 271,272 addition to &---Cl, 207
radical from, 43,300 autolysis of, 54
Triphenylmethyl cation, 84, 87, 102, ion solvation and, 57,58,60
103,381 levelling effect in, 55
reduction, 306 polarisability, 57
Triphenylmethyl peroxide, 300 Wave amplitude, 343
rearrangement, 336 Wave functions, 2,342
Triphenylmethyl radical, 43, 300 Wave nodes, 343
dimer, 44,301,311 Wheland intermediates, 41, 131, 151
shape, 311 Wittig reaction, 233
Tropylium cation, 18, 104, 106 Wittig rearrangement, 293
stability, 106 Wolff rearrangement, 119
Tschitschibabin reaction, 168 Woodward-Hoffmam rules, 344
Wurtz reaction, 289
Ultra-violet absorption, 13, 132,218
Umpolung, 211 Xanthates, pyrolysis, 268
Unsaturated acids X-ray crystallography
L$-, from Perkin reaction, 227
ethanoate anion, 19 1

By-, synthesis, 234 Grignard reagents, 221


Unsaturated carbonyl compounds, cub-, Meisenheimer complexes, 171
addition to, 200 triphenylmethyl radicals, 311
formation of. 251
Ylids, 232,233,287
Y,solvent parameter, 389
Van der Wads radii, 8 values of, 390
Vibrational modes, 342 Yukawa-Tsuno equation, 372
Vinyl ethers, polymerisation, 189 parameter, r, and, 373
Vinyl polymerisation, 320
branching in, 321 Zinc alkyls, 223
chain length in, 321 Zwitterions, 94, 176
coordination, 322 diazoanthranilate anion, 176
induction period in, 321 peroxy, 193
Contents*

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