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C
...
WENIRUP,
Review series
Advances in Physical Organic Chemistry
...
and,B
D
...
I, 1963- )
...
KNIPE, A
...
and W A ~ , E
...
(Interscience, Vol
...
Progress in Physical Organic Chemistry
...
W
...
) (Interscience, Vol
...
Reactive Intermediates-A Serial Publication, JONES, M
...
A
...
I, 1978- )
...
, SG6 lHN, England:
CC3 S W , P
...
Eliminatibn;
( B )
...
CC6 S W , P
...
C=C; ( B )
...
CC7 S W , P
...
CC9 S-,
P
...
CC11 SYKES, P
...
Index
Aeetals
cyclic, 210
formation, 209,289
hydrolysis, 74,210
Acid catalysis
general, 74
specific, 74
AA,l pathway, 242,243
AA,2 pathway, 241,244,384
A
?
,
pathway, 241
Aad~ty
anion stability and, 23,55,271
aromaticity and, 275
Br0nsted and, 53
constant K,, 54,271
definitions of, 53
A G and, 58,60,61, 394
~
AWand, 58,394
Ase and, 58,394
effect of solvent, 56
effect of temperature, 64
H-bonding in, 63,64
hybridisation and, 59,273
in C-H comps
...
, 55
steric effects in, 58
Acid strength
alcohols, 55, 56
aliphatic acids, 54, 55, 57, 59
alkanes, 55,271
alkenes, 272
alkynes, 223,273,289,294
aromatic acids, 62
catalysis and, 74
dicarboxylic acids, 63
imides, 68
nitroalkanes, 272,280,283
phenols, 23, 56,61
triphenylmethane, 271
Acrylonitrile, 199
Activated complex, 38
Activation parameters
energy, E,, 38
enthalpy, AH+, 38
entropy, AS*, 39
free energy, AG*, 38
Acyl cations, 102, 144,240,242, 379
Acyloin condensation, 218
Addition, 30
1,3-dipolar, 192, 194,351
electrophilic, 31, 50, 178-198
nucleophilic, 31, 198, 207-245
radical, 31,313-323
to +C, 31,51, 103, 113, 178, 188
to (+C, 182
+,
195
to - C
200
to ckc-c==O,
to e N ,244
to C+0, 31,50, 103,203
Adsorption, 191
Aldehyde ammonias, 220
Aldol reaction, 224
acid catalysed, 225
crossed, 226
intramolecular, 226
reversibility, 75, 224
Alkenes
cycloaddition, 348
polar addition, 178-195
protection in, 265
radical addition, 313-323
relative stability, 26,256
Alkylchlorosulphites, decomp
...
Reactive Molecules: The Neutral Reactive Intermediate
in Organic Chemistry (Wiley, 1984)
...
WLD, v
...
(Eds) (Academic Press, Vol
...
Organic Reaction Mechanisms
...
C
...
(Eds)
W
...
I, 1966- )
...
TAFT, R
...
(Ed
...
1, 1963- )
...
and MOSS, R
...
(Eds) (Wiley-Interscience, Vol
...
Audio cassettes
The following titles in the 'Chemistry Cassette' series are published
by, and are available from, The Chemical Society, Blackhorse Road,
Letchworth, Herts
...
Some Organic Reaction Pathways: ( A )
...
Aromatic Substitution (1975)
...
Some Reaction Pathways of Double Bonds: ( A )
...
C=O (1977)
...
Some Reaction Pathways of Carboxylic Acid Denvatives (1979)
...
Radicals and their Reaction Pathways (1979)
...
Linear Free Energy Relationships (1980)
...
, 251,270
kinetic control of, 270,280
Lewis and, 54
origin in organic comps
...
93
Alkyl shifts, 111, 113, 115,293,337
Alkynes
acidity, 223,272
addition to -0,223
alkylation, 289
dimerisation, 294
ozonolysis, 194
cation, 85, 105, 196
radical, 311
rearrangement, 109
Index
Ambident nucleophiles, 97
Amides
from Beckmann, 123
Hofmann reaction, 49, 122
hydrolysis, 239,245, 388
reduction, 214
Amidines
basicity, 69
formation, 244
Aminoazo comps, 148
Anionic polymerisation, 200,226
Antarafacial shifts, 353
Anthracene, 17
photodimer, 337
transannular peroxide, 331
Anti-bonding orbitals, 6, 292
Anti-knock agents, 305
Anti-Markownikov addition, 317
Anti-oxidants, 330
Antiperiplanar conformation, 118,253
Arenium ions, 131
Arenonium ions, 131
Arndt-Eistert reaction, 119
Aromaticity, l 4
cycloheptatrienyl cation, 18, 104, 106
cyclopentadienyl anion, 18, 275
cyclopropenyl cation, 18, 106
n
...
r
...
, 66
ortho effects in, 71
softness, 96
steric effects in, 70,71
Basic strength
aliphatic amines, 66
amides, 68
amidines, 69
aromatic bases, 69
catalysis and, 75
conjugate acids, 65
AP 66
and,
guanidine, 68
heterocyclic bases, 72, 166
tetraakyhmm~~~m
hydroxides, 67
Beckmann rearrangement, 123
acid catalysis, 124
~,'80 125
in,
intramolecularity, 126
solvent polarity and, 126
stereoselectivity, 124
Benzene
aromaticity and, 14
bond lengths, 15
charge cloud, 15, 130
delocalisation in, 14, 130
heat of hydrogenation, 16
KekulC structures, 14, 194
m
...
s of, 14
n
...
r
...
, 176
structure, 175
Biosynthetic pathways, 48
Biphenylene, 176
Bipolar non-protic solvents, 81,98,173,
252
Biradicals, 315,331, 337
oxygen, 315,330
stable, 338
Bisulphite addition comps
...
m
...
and, 102, 181,393
phenonium, l05
phenyl, l69
propyl, 83,104,107,109
rearrangement, 32,102,107,109-119
reduction, 306
solvation, 45
Index
Ambident nucleophiles, 97
Amides
from Beckmann, 123
Hofmann reaction, 49, 122
hydrolysis, 239,245, 388
reduction, 214
Amidines
basicity, 69
formation, 244
Aminoazo comps, 148
Anionic polymerisation, 200,226
Antarafacial shifts, 353
Anthracene, 17
photodimer, 337
transannular peroxide, 331
Anti-bonding orbitals, 6, 292
Anti-knock agents, 305
Anti-Markownikov addition, 317
Anti-oxidants, 330
Antiperiplanar conformation, 118,253
Arenium ions, 131
Arenonium ions, 131
Arndt-Eistert reaction, 119
Aromaticity, l 4
cycloheptatrienyl cation, 18, 104, 106
cyclopentadienyl anion, 18, 275
cyclopropenyl cation, 18, 106
n
...
r
...
, 66
ortho effects in, 71
softness, 96
steric effects in, 70,71
Basic strength
aliphatic amines, 66
amides, 68
amidines, 69
aromatic bases, 69
catalysis and, 75
conjugate acids, 65
AP 66
and,
guanidine, 68
heterocyclic bases, 72, 166
tetraakyhmm~~~m
hydroxides, 67
Beckmann rearrangement, 123
acid catalysis, 124
~,'80 125
in,
intramolecularity, 126
solvent polarity and, 126
stereoselectivity, 124
Benzene
aromaticity and, 14
bond lengths, 15
charge cloud, 15, 130
delocalisation in, 14, 130
heat of hydrogenation, 16
KekulC structures, 14, 194
m
...
s of, 14
n
...
r
...
, 176
structure, 175
Biosynthetic pathways, 48
Biphenylene, 176
Bipolar non-protic solvents, 81,98,173,
252
Biradicals, 315,331, 337
oxygen, 315,330
stable, 338
Bisulphite addition comps
...
m
...
and, 102, 181,393
phenonium, l05
phenyl, l69
propyl, 83,104,107,109
rearrangement, 32,102,107,109-119
reduction, 306
solvation, 45
402
Index
Carbocations (contd
...
r
...
, reactions, 236244
acid hydrolysis, 240
base hydrolysis, 238
electronic effects in, 237
Grignard reagents, 238
leaving groups and, 237
reduction, 215
steric effects in, 238
tetrahedral intermediates in, 236
Catalysts
acid, 42, 74
base, 75
cyanide ion, 231
heterogeneous, 143, 191,264
Lewis acid, 131, 189
metal, 191
nucleophilic, 99
reaction pathway and, 41
thiazolium ylids, 232
Cationic polymerisation, 189
Cellulose oxidation, 37
Chain length, 314, 324
Chain reactions, 300, 314
Chain transfer agents, 321
Chair conformation, 355
Charge transfer complexes, 131
Chelation, 291
Chirality, 87, 116,235,254, 278, 326
Chloral hydrate, 208
Chromatography, 43, 258
Index
Chugaev reaction, 268
Cisoid conformation, 197,344, 350
Claisen ester condensation, 229
Claisen rearrangement, 355
Claisen-Schmidt reaction, 226
Clemmensen reduction, 146
Colour
conjugation and, 13,331, 391
Combustion, heat of, 12
Competition experiments, 157
Complexes, dissociation, 27
Concerted reactions, 341
stereoselectivity in, 341
symmetry allowed, 348
symmetry forbidden, 348, 357
Configuration, 38, 88
apparent retention, 94
carbanions, 276
carbocations, 104
determination of relative, 88, 90
inversion, 87, 90, 190
oximes, 124
racemisation, 89, 90, 326
radicals, 309
retention, 93, 326
Conformation
antiperiplanar, 118,253
chair, 355
cisoid, 197, 344, 350
eclipsed, 7,254
staggered, 7,254
synperiplanar, 253,269
tram diaxial, 255
transoid, 197, 350
Conjugate
acids, 53, 65
bases, 53
Conjugate addition, 201
Conjugated carbonyl cornps
...
m
...
signal, 18
shape, l7
Cyclopentadiene
acidity, 275
in Diels-Alder, 197, 350
tricyclic dimer, 351
Cyclopentadienyl anion, 18,275
Cyclopropanes
from carbenes, 50,266
thermolysis, 337
Cyclopropanone
hydration, 209
intermediates, 294
Cyclopropenyl cation, 18, 106
Danens reaction, 290
Dealkylation, 143
Debromination, 264
Decarbonylation, 145, 335
Decarboxylation, 271,285
carbanions in, 271,285
cyclic T
...
s in, 286
electronic effects on, 286
trapping in, 286
Dehydration
acid-catalysed, 103,220,225,247, 380
base-catalysed, 225,262
Delocalisation, 13
amidines, 69
benzene, 14,130
canonical structures and, 19
carbanions, 21,23,229,274
carbocations, 21, 83, 84, 87, 104, 110
carbonyl a m p s
...
, 147
rearrangement, 148
Diazo coupling, 26,28, 146
amines, 26, 147
electron density in, 148
intramolecular, 148
kinetics, 147, 148
p H and, 146
phenols, 147, 155
steric effects in, 27
Diazoketones, rearrangement, 119
Diazonium cations, 27, 119, 146
akyl, 107, 120
aryl, 121, 146
coupling by, 27, 146
decomposition, 104, 107, 120, 333
stability of, 120, 146
nucleophilic substitution, 169, 306
Diazotate anions, 146
Diazotisation
aliphatic amines, 107, 119
aromatic amines, 121, 146
Dichlorocarbenes, 4,50,267,290
Dieckmann reaction, 230
Diels-Alder reaction, 175, 197, 340, 349
cyclopentadiene in, 197
electronic effects in
...
exo addition, 350
4 n e 2 n e , 349
reversibility, 351
secondary orbital interaction, 350
stereoselectivity in, 198, 349
steric effects in, 198,350
symmetry control in, 348
trapping in, 175
zwitterion intermediate, 351
+
402
Index
Carbocations (contd
...
r
...
, reactions, 236244
acid hydrolysis, 240
base hydrolysis, 238
electronic effects in, 237
Grignard reagents, 238
leaving groups and, 237
reduction, 215
steric effects in, 238
tetrahedral intermediates in, 236
Catalysts
acid, 42, 74
base, 75
cyanide ion, 231
heterogeneous, 143, 191,264
Lewis acid, 131, 189
metal, 191
nucleophilic, 99
reaction pathway and, 41
thiazolium ylids, 232
Cationic polymerisation, 189
Cellulose oxidation, 37
Chain length, 314, 324
Chain reactions, 300, 314
Chain transfer agents, 321
Chair conformation, 355
Charge transfer complexes, 131
Chelation, 291
Chirality, 87, 116,235,254, 278, 326
Chloral hydrate, 208
Chromatography, 43, 258
Index
Chugaev reaction, 268
Cisoid conformation, 197,344, 350
Claisen ester condensation, 229
Claisen rearrangement, 355
Claisen-Schmidt reaction, 226
Clemmensen reduction, 146
Colour
conjugation and, 13,331, 391
Combustion, heat of, 12
Competition experiments, 157
Complexes, dissociation, 27
Concerted reactions, 341
stereoselectivity in, 341
symmetry allowed, 348
symmetry forbidden, 348, 357
Configuration, 38, 88
apparent retention, 94
carbanions, 276
carbocations, 104
determination of relative, 88, 90
inversion, 87, 90, 190
oximes, 124
racemisation, 89, 90, 326
radicals, 309
retention, 93, 326
Conformation
antiperiplanar, 118,253
chair, 355
cisoid, 197, 344, 350
eclipsed, 7,254
staggered, 7,254
synperiplanar, 253,269
tram diaxial, 255
transoid, 197, 350
Conjugate
acids, 53, 65
bases, 53
Conjugate addition, 201
Conjugated carbonyl cornps
...
m
...
signal, 18
shape, l7
Cyclopentadiene
acidity, 275
in Diels-Alder, 197, 350
tricyclic dimer, 351
Cyclopentadienyl anion, 18,275
Cyclopropanes
from carbenes, 50,266
thermolysis, 337
Cyclopropanone
hydration, 209
intermediates, 294
Cyclopropenyl cation, 18, 106
Danens reaction, 290
Dealkylation, 143
Debromination, 264
Decarbonylation, 145, 335
Decarboxylation, 271,285
carbanions in, 271,285
cyclic T
...
s in, 286
electronic effects on, 286
trapping in, 286
Dehydration
acid-catalysed, 103,220,225,247, 380
base-catalysed, 225,262
Delocalisation, 13
amidines, 69
benzene, 14,130
canonical structures and, 19
carbanions, 21,23,229,274
carbocations, 21, 83, 84, 87, 104, 110
carbonyl a m p s
...
, 147
rearrangement, 148
Diazo coupling, 26,28, 146
amines, 26, 147
electron density in, 148
intramolecular, 148
kinetics, 147, 148
p H and, 146
phenols, 147, 155
steric effects in, 27
Diazoketones, rearrangement, 119
Diazonium cations, 27, 119, 146
akyl, 107, 120
aryl, 121, 146
coupling by, 27, 146
decomposition, 104, 107, 120, 333
stability of, 120, 146
nucleophilic substitution, 169, 306
Diazotate anions, 146
Diazotisation
aliphatic amines, 107, 119
aromatic amines, 121, 146
Dichlorocarbenes, 4,50,267,290
Dieckmann reaction, 230
Diels-Alder reaction, 175, 197, 340, 349
cyclopentadiene in, 197
electronic effects in
...
exo addition, 350
4 n e 2 n e , 349
reversibility, 351
secondary orbital interaction, 350
stereoselectivity in, 198, 349
steric effects in, 198,350
symmetry control in, 348
trapping in, 175
zwitterion intermediate, 351
+
Index
Dienes, 11
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
...
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,
301
Diphenylpolyenes, 13
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~sed
conformation
...
254
,
~le~troc~clic
reactions, 341, 344-348
Electrolytic oxidation, 307
Electrolytic reduction, 3 V
C
Electromeric effect, 24
Electron configuration, 3
Electron density, 21,26, 29,393
Electron-donating groups, 23,26
addition to
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
-
,C+C
404
and, 183
addition to C===C
addition to C=O and, 205,226
aromatic substitution and, 151, 158
basicity and, 67,70
elimination and, 251, 262
Electrophiles, 29
31, 178Electrophilic addition to
194
bromine, 51, 179
carbocations, 113, 180, 184, 187, 188,
225
cationic polymerisation, 189
cyclic bromonium ions, 180
1,3-dipolar, 192, 194, 351
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
proton, 103, 184, 187
rate, 183, 185
rearrangements in, 185, 187
solvent and, 182
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
...
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
...
S
...
substitution, 100, 260
405
alkene stability and, 261
base size and, 261
basicitylnucleophilicity in, 262
change of pathway, 260
E1/SN1ratio, 260
E2/SN2ratio, 260
entropy and, 262
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
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
temperature and, 36
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
control, 43, 163, 165, 171, 195
entropy and, 36
free energy and, 35
E
...
r
...
0
...
7
...
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
Index
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
...
, 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
...
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
...
s
...
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
Esterification (contd
...
207
heat of, 97
Hydride transfer, 108,109,214,215,216
Hvdroboration, 187
~ i d r o ~ abstiaction, 309,316,321
en
Hydrogenation
*C,
191
M 191
,
C==O, 214
heat of, 16
homogeneous catalysis in, 192
stereoselectivity in, 191
Hydrogen bonding
acidity and, 63,64
C==O and, 204,209,286
intermolecular, 36,282
intramolecular, 36,208,281
solvation and, 57,67,252,282
Hydrogen peroxide
Fenton's reagent, 306
189
hydroxylation of *C,
oxidation of ketones, 127
Hydrogen shifts
1,3-photochemical, 354
1,s-thermal, 353
1,7-photochemical, 354
1,7-thermal, 354
Hydrolysis,
407
esters, 238, 374
halides, 77
Hydroperoxides
formation, 328
in autoxidation, 328
rearrangement, l28
Hydroxamic acids, Lossen degradation,
123
Hydroxylation, 189
Hyperconjugation, 25
alkene stability and, 26
aromatic substitution and, 153
carbocation stability and, 83
Hypochlorites, alkyl, 327
Hiickel's rule, 17, 106
Hund's rule, 3,275
Imino-ethers, 245
Inductive effect, 21
acidity and, 273
basicity and, 66
electronegativity and, 22
electrophilic substitution and, 152,
156,160
Inductomeric effect, 24
Insertion reactions, 50,266,267
Intermediates
bridged, 105,118,129,335,377
catalysts and, 42
criteria for, 49
cyclic, 180,189,227
isolation, 48, 136, 142, 171,290
models for T
...
, 41, 51,78,137, 151
spectroswpic detection, 50, 144, 171,
181,219,237
study of, 49
tetrahedral, 236
trapping, 50, 175,286, 356
Wheland, 41,131,151
Intermolecular rearrangements, 143,
149,278
Intimate ion pairs, 91,249,291
Intramolecular rearrangements, 116,
122, 126, 127, 128,217,232,279,
355
Inversion
in SN1, 90
in SN2,88,89, 190
Iodoform, 297
Iodonium ions, cyclic, 186
Ionisation
AG* and, 58
solvent and, 56,102, 388
temperature and, 64
Ion pairs, 20,45,57,64,79,102,136,
141
406
Index
Index
Esterification (contd
...
207
heat of, 97
Hydride transfer, 108,109,214,215,216
Hvdroboration, 187
~ i d r o ~ abstiaction, 309,316,321
en
Hydrogenation
*C,
191
M 191
,
C==O, 214
heat of, 16
homogeneous catalysis in, 192
stereoselectivity in, 191
Hydrogen bonding
acidity and, 63,64
C==O and, 204,209,286
intermolecular, 36,282
intramolecular, 36,208,281
solvation and, 57,67,252,282
Hydrogen peroxide
Fenton's reagent, 306
189
hydroxylation of *C,
oxidation of ketones, 127
Hydrogen shifts
1,3-photochemical, 354
1,s-thermal, 353
1,7-photochemical, 354
1,7-thermal, 354
Hydrolysis,
407
esters, 238, 374
halides, 77
Hydroperoxides
formation, 328
in autoxidation, 328
rearrangement, l28
Hydroxamic acids, Lossen degradation,
123
Hydroxylation, 189
Hyperconjugation, 25
alkene stability and, 26
aromatic substitution and, 153
carbocation stability and, 83
Hypochlorites, alkyl, 327
Hiickel's rule, 17, 106
Hund's rule, 3,275
Imino-ethers, 245
Inductive effect, 21
acidity and, 273
basicity and, 66
electronegativity and, 22
electrophilic substitution and, 152,
156,160
Inductomeric effect, 24
Insertion reactions, 50,266,267
Intermediates
bridged, 105,118,129,335,377
catalysts and, 42
criteria for, 49
cyclic, 180,189,227
isolation, 48, 136, 142, 171,290
models for T
...
, 41, 51,78,137, 151
spectroswpic detection, 50, 144, 171,
181,219,237
study of, 49
tetrahedral, 236
trapping, 50, 175,286, 356
Wheland, 41,131,151
Intermolecular rearrangements, 143,
149,278
Intimate ion pairs, 91,249,291
Intramolecular rearrangements, 116,
122, 126, 127, 128,217,232,279,
355
Inversion
in SN1, 90
in SN2,88,89, 190
Iodoform, 297
Iodonium ions, cyclic, 186
Ionisation
AG* and, 58
solvent and, 56,102, 388
temperature and, 64
Ion pairs, 20,45,57,64,79,102,136,
141
408
Index
Ion pairs (contd
...
S
...
S
...
m
...
spectroscopy, 18,48, 102, 106,
111, 126, 129, 159, 181,219
aromaticity and, 18
13c, 49,106, 111,393
carboxyl protonation and, 240
Grignard reagents and, 221
ozonolvsis and, 193, 194
ox and; 393
triphenylmethyl dimer, 44,301
N-nitroso comwunds, 121
Nodal
plane, 3,343
surface, 2
Nodes, 343
Non-bonded interaction, 7
Nucleophiles, 29
ambident, 97
Nucleophilic addition to =
,
198
carbanions in, l99
cyanoethylation, 199
hydrogen cyanide, 199
methanol, 199
Michael reaction, 200
Nucleo~hilic
addition to =m,
206
conjugate addition, 201
Grignard reagents, 201
Me,SiCN, 213
Michael reaction, 202
steric effects in, 201
Nucleophilic addition to
31,203244
a&tylide ions, 223
acid catalysis, 204,207,209,220,225
additionlelimination, 219
alcohols, 209
aldol reaction, 224
408
Index
Ion pairs (contd
...
S
...
S
...
m
...
spectroscopy, 18,48, 102, 106,
111, 126, 129, 159, 181,219
aromaticity and, 18
13c, 49,106, 111,393
carboxyl protonation and, 240
Grignard reagents and, 221
ozonolvsis and, 193, 194
ox and; 393
triphenylmethyl dimer, 44,301
N-nitroso comwunds, 121
Nodal
plane, 3,343
surface, 2
Nodes, 343
Non-bonded interaction, 7
Nucleophiles, 29
ambident, 97
Nucleophilic addition to =
,
198
carbanions in, l99
cyanoethylation, 199
hydrogen cyanide, 199
methanol, 199
Michael reaction, 200
Nucleo~hilic
addition to =m,
206
conjugate addition, 201
Grignard reagents, 201
Me,SiCN, 213
Michael reaction, 202
steric effects in, 201
Nucleophilic addition to
31,203244
a&tylide ions, 223
acid catalysis, 204,207,209,220,225
additionlelimination, 219
alcohols, 209
aldol reaction, 224
410
Index
Nucleophilic addition to C==O (contd
...
, 219
base catalysis, 204,207,212, 216, 226
benzoin condensation, 231
bisulphite anion, 207,213
Cannizzaro reaction, 216
carbanions, 221-234
Claisen ester condensation, 229
Claisen-Schmidt reaction, 226
conjugate, 200,213
cyanide ion, 212
Dieckmann reaction, 230
electronic effects in, 205,208,226
electrons, 217
Grignard reagents, 221,235
halide ion, 214
hydration, 207
hydride ion, 214
hydrogen bonding in, 204,209
in carboxylic derivs
...
S
...
77-100
Aga catalysis, 97
ally1 halides, 85
ambident nucleophiles, 97
benzyl halides, 84,91
bridgehead halides, 86
bromomethane, 78
2-bromopropanoate, 94
l-bromotriptycene, 87
carbanions in, 100,288
Index
charge distribution in T
...
, 78, 80,83,
84
1,2-chlorohydrins,94
2-chloro-2-methylpropane, 78
configuration in, 88,89,90,92,93,94
electronic effects in, 82, 83, 84
entering group and, 96
He catalysis, 99
I~ catalysis, 98
isotopic label (I) in, 89
kinetics of, 45, 77, 89
leaving group and, 98
list of reactions, 99
mechanistic borderline, 91
mechanistic changeover, 82,84,96
neighbouring group participation, 93
neopentyl halides, 86
rate1li&ting step, 78
SNl, 79, 90
S ~ 2 , 7 8 , 8 793
,
solvation in, 45, 79, 80, 90, 91, 97
solvolysis, 80, 91
steric effects in, 82, 84,85,86, 109
stereochemistry of, 87-96
structure and, 82-87,90
tosylates, 89
triphenylmethyl halides, 84
v
...
85
~ u c l ~ o ~ h s"bstitution, aromatic,
ilic
167-177
activated aryl halides, 170
anionic intermediates, 168, 170, 171
aryne intermediates, 173
as additionlelimination, 172
as eliminationladdition, 175
deuterium exchange, 174
diazonium salts, 121, 169
ipso, 169
nitrobenzene, 168
pyridine, 168
steric inhibition of delocalisation, 173
Nylon-6, 126
Oleum, 140
Oppenauer oxidation, 216
Orbitals
anti-bonding, 6, 292
atomic, 1
axial overlap, 6
bonding, 6
degenerate, 3
delocalised, 13
dumb-bell, 3
filled, l 7
frontier, 344
HOMO, 344
hybridisation of, 4
lasral overlap, 9
lobes, 9
localised, 6
LUMO, 344
molecular, 5
nodal planes and, 1,343
overlap integral, 5, 342
P, 2
phase of, 342
A, 9,337
S * , 9, 337
S, 2
shape, 3
0,
6
U*, 6
size, 2
secondary interaction, 350
spl, 5
sp2, 5
sp3, 4
spatial orientation, 2, 3
symmetry, 342
Order of reaction, 39, 79
first, 39
mixed, 82,91
molecularity and, 79
second, 39
Organometallic compounds, structure,
221,276,293
Orthoesters
acetals from, 210,289
hydrolysis, 75
Ortholpara (0-lp-)
directing groups, 150,159
ratios, 159
Osmic esters, cyclic, 189
Osmium tetroxide, 189
Overlap
axial, 6
integral, 5,342
lateral, 9
Oxaphosphetanes, 233
Oximes
configuration, 124,220
formation, 219
rearrangement, 123
Oxygen
diradical, 315
migration to electron-deficient, 127
Ozonides, 192
Ozonolysis, 192
stereochemistry, 193
411
Paramagnetism, 308
Paint, hardening, 328
Partial rate factors,f,, 156,159,333
Pauli principle, 2
Pericyclic reactions, 198,341
Perkin reaction, 227
Peroxide effect, 317
Peroxides
as initiators, 300, 317
heterolysis, 129, 306
homolysis, 129, 333
in ozonolysis, 193
photolysis, 304
rearrangement, l27
thermolysis, 304
trans-annular, 331
Peroxyacids, 190,330
Peroxy radicals, 315,328,337
Peroxy zwitterions, 193
Petroleum cracking, 112,305
Phase, orbital, 342
Phenanthrene, 17
Pschorr synthesis, 334
Phenol
acidity, 23,61,370
coupling, 334
diazo coupling, 147, 155
from cumene, 128
nitration, 137
oxidation, 334
Phenonium ion, 105,376
Phenylation, 332
Phenylnitromethane, tautomerism, 283
Phenyl radicals, 332
Phosphine oxides, 234
Phosphonium ylids, 233
Phosphoranes, 233
Phosphorus-oxygen bond, 233
Photochemical concerted reactions, 341,
346
1,3-hydrogen shifts, 354
1,7-hydrogenshifts, 354
2ne + 2ne, 349
Photochemical initiation, 300
Photo-dimerisation, 337
Photolysis, 303
Photo-oxidation, 330
Physical methods
analysis of products, 43,156,281
detection of intermediates, 50, 144,
171, 176,181,219,304,308
structure determination, 102, 106,
111, 134,193,221,240
n bond, 9, 178
n complexes, 131, 180, 184
n-deficient heterocycles, 165
410
Index
Nucleophilic addition to C==O (contd
...
, 219
base catalysis, 204,207,212, 216, 226
benzoin condensation, 231
bisulphite anion, 207,213
Cannizzaro reaction, 216
carbanions, 221-234
Claisen ester condensation, 229
Claisen-Schmidt reaction, 226
conjugate, 200,213
cyanide ion, 212
Dieckmann reaction, 230
electronic effects in, 205,208,226
electrons, 217
Grignard reagents, 221,235
halide ion, 214
hydration, 207
hydride ion, 214
hydrogen bonding in, 204,209
in carboxylic derivs
...
S
...
77-100
Aga catalysis, 97
ally1 halides, 85
ambident nucleophiles, 97
benzyl halides, 84,91
bridgehead halides, 86
bromomethane, 78
2-bromopropanoate, 94
l-bromotriptycene, 87
carbanions in, 100,288
Index
charge distribution in T
...
, 78, 80,83,
84
1,2-chlorohydrins,94
2-chloro-2-methylpropane, 78
configuration in, 88,89,90,92,93,94
electronic effects in, 82, 83, 84
entering group and, 96
He catalysis, 99
I~ catalysis, 98
isotopic label (I) in, 89
kinetics of, 45, 77, 89
leaving group and, 98
list of reactions, 99
mechanistic borderline, 91
mechanistic changeover, 82,84,96
neighbouring group participation, 93
neopentyl halides, 86
rate1li&ting step, 78
SNl, 79, 90
S ~ 2 , 7 8 , 8 793
,
solvation in, 45, 79, 80, 90, 91, 97
solvolysis, 80, 91
steric effects in, 82, 84,85,86, 109
stereochemistry of, 87-96
structure and, 82-87,90
tosylates, 89
triphenylmethyl halides, 84
v
...
85
~ u c l ~ o ~ h s"bstitution, aromatic,
ilic
167-177
activated aryl halides, 170
anionic intermediates, 168, 170, 171
aryne intermediates, 173
as additionlelimination, 172
as eliminationladdition, 175
deuterium exchange, 174
diazonium salts, 121, 169
ipso, 169
nitrobenzene, 168
pyridine, 168
steric inhibition of delocalisation, 173
Nylon-6, 126
Oleum, 140
Oppenauer oxidation, 216
Orbitals
anti-bonding, 6, 292
atomic, 1
axial overlap, 6
bonding, 6
degenerate, 3
delocalised, 13
dumb-bell, 3
filled, l 7
frontier, 344
HOMO, 344
hybridisation of, 4
lasral overlap, 9
lobes, 9
localised, 6
LUMO, 344
molecular, 5
nodal planes and, 1,343
overlap integral, 5, 342
P, 2
phase of, 342
A, 9,337
S * , 9, 337
S, 2
shape, 3
0,
6
U*, 6
size, 2
secondary interaction, 350
spl, 5
sp2, 5
sp3, 4
spatial orientation, 2, 3
symmetry, 342
Order of reaction, 39, 79
first, 39
mixed, 82,91
molecularity and, 79
second, 39
Organometallic compounds, structure,
221,276,293
Orthoesters
acetals from, 210,289
hydrolysis, 75
Ortholpara (0-lp-)
directing groups, 150,159
ratios, 159
Osmic esters, cyclic, 189
Osmium tetroxide, 189
Overlap
axial, 6
integral, 5,342
lateral, 9
Oxaphosphetanes, 233
Oximes
configuration, 124,220
formation, 219
rearrangement, 123
Oxygen
diradical, 315
migration to electron-deficient, 127
Ozonides, 192
Ozonolysis, 192
stereochemistry, 193
411
Paramagnetism, 308
Paint, hardening, 328
Partial rate factors,f,, 156,159,333
Pauli principle, 2
Pericyclic reactions, 198,341
Perkin reaction, 227
Peroxide effect, 317
Peroxides
as initiators, 300, 317
heterolysis, 129, 306
homolysis, 129, 333
in ozonolysis, 193
photolysis, 304
rearrangement, l27
thermolysis, 304
trans-annular, 331
Peroxyacids, 190,330
Peroxy radicals, 315,328,337
Peroxy zwitterions, 193
Petroleum cracking, 112,305
Phase, orbital, 342
Phenanthrene, 17
Pschorr synthesis, 334
Phenol
acidity, 23,61,370
coupling, 334
diazo coupling, 147, 155
from cumene, 128
nitration, 137
oxidation, 334
Phenonium ion, 105,376
Phenylation, 332
Phenylnitromethane, tautomerism, 283
Phenyl radicals, 332
Phosphine oxides, 234
Phosphonium ylids, 233
Phosphoranes, 233
Phosphorus-oxygen bond, 233
Photochemical concerted reactions, 341,
346
1,3-hydrogen shifts, 354
1,7-hydrogenshifts, 354
2ne + 2ne, 349
Photochemical initiation, 300
Photo-dimerisation, 337
Photolysis, 303
Photo-oxidation, 330
Physical methods
analysis of products, 43,156,281
detection of intermediates, 50, 144,
171, 176,181,219,304,308
structure determination, 102, 106,
111, 134,193,221,240
n bond, 9, 178
n complexes, 131, 180, 184
n-deficient heterocycles, 165
Zndex
n-excessive heterocycles, 166
Pinacolinic deamination, 113,118
Pinacollpinacolone rearrangement, 113
migratory aptitude in, 114
Pinacols
formation, 218
rearrangement, l13
pK,, 54,270,362
temperature and, 64
P&, 65
P~B*,
Plane trigonal hybridisation, 5
Polarisability, 24,%
Polarisation, 22,29
Polarised complexes, 108,141,144
Polar non-protic solvents, 81
Polyenes
hydrogen shifts in, 352
Polyisoprenes, 323
Polymerisation
anionic, 200,226
branching, 321
cationic, 189
chain length, 321
chain transfer, 321
coordination, 322
copolymerisation, 322
cross-linking, 323
induction period, 321
initiation, 321
propagation, 320
radical, 308,320
stereochemistry, 322,323
termination, 320
Products, nature of, 43
Propane, rearrangement, 108
Protecting groups, 155,210,211,265
requirements, 211
Protodesilylation, 149,161
Protodesulphonylation, 140,161
Proton transfer
catalysed, 74
to C=c, 103
to lone pairs, 103,112,116
Prototropy, 277
Pschorr reaction, 334
Pyridine
basicity, 72
delocalisation in, 18,165
electrophilic substitution, 165
nucleophilic substitution, 168
Pyrolytic elimination, 267,340
carbocationic character T
...
, 269,340
Cope, 268
chugaev, 268
Ei, 261
SYN, 267
Pyrrole
basicity, 73
electrophilic substitution, 166
protonation, 73
Quantum numbers
principal, n, 2
spin, 2
subsidiary, l and m, 2
Quinuclidine
basicity, 72
complex with Me,B, 28
RaeemisPtion, 89
deuterium exchange and, 288
in radical reactions, 326
in S,1, 90
Radical addition, 312-323
carbon tetrachloride, 320
halogens, 313
hydrogen bromide, 316
sulphenyl halides, 320
vinyl polymerisation, 320
Radical anions, 218
Radical rearrangements, 335
Radicals, 20,30,299-339
acyl, 306,330,335
addition to C=c, 313-323
alkoxyl, 303
alkyl, 301,303,304,
324
allylic, 311,325,327,
329
benzoyl, 330
benzylic, 311,316,
329
biradicals, 315,330,337
bridged, 310
chain reactions, 300,313,
314,328
combustion and, 299
conformational equilibrium, 319
cycloheptatrienyl, 308
cyclohexadienyl, 331
detection, 308
dimerisation, 300,305,311,313,314,
320,332,334
l ,l-diphenyl-2-picrylhydrazyl,301
disproportionation, 305,313,
320,332
e
...
r
...
S
...
, 148
diazoketones, 119
dienone-phenol, 115
Favorskii, 294
Hofmam, 122
hydroperoxides, l28
in Friedel-Crafts, 108,142,145,163
intermolecular, 117,143,149,278
intramolecular, 116,122,126,127,
279,355
Lossen, 122
migratory aptitude in, 114
neopentyl, 110
pinacol-pinacolone, 113
radical, 335
Schmidt, 122
sigmatropic, 352
stereochemistry of, 116,117,119
steric effects in, 115
Stevens, 293
Wagner-Meemein, 111
Wittig, 293
Wolff, 119
Redox reactions, 306
Reimer-Tiemann reaction, 290
Zndex
n-excessive heterocycles, 166
Pinacolinic deamination, 113,118
Pinacollpinacolone rearrangement, 113
migratory aptitude in, 114
Pinacols
formation, 218
rearrangement, l13
pK,, 54,270,362
temperature and, 64
P&, 65
P~B*,
Plane trigonal hybridisation, 5
Polarisability, 24,%
Polarisation, 22,29
Polarised complexes, 108,141,144
Polar non-protic solvents, 81
Polyenes
hydrogen shifts in, 352
Polyisoprenes, 323
Polymerisation
anionic, 200,226
branching, 321
cationic, 189
chain length, 321
chain transfer, 321
coordination, 322
copolymerisation, 322
cross-linking, 323
induction period, 321
initiation, 321
propagation, 320
radical, 308,320
stereochemistry, 322,323
termination, 320
Products, nature of, 43
Propane, rearrangement, 108
Protecting groups, 155,210,211,265
requirements, 211
Protodesilylation, 149,161
Protodesulphonylation, 140,161
Proton transfer
catalysed, 74
to C=c, 103
to lone pairs, 103,112,116
Prototropy, 277
Pschorr reaction, 334
Pyridine
basicity, 72
delocalisation in, 18,165
electrophilic substitution, 165
nucleophilic substitution, 168
Pyrolytic elimination, 267,340
carbocationic character T
...
, 269,340
Cope, 268
chugaev, 268
Ei, 261
SYN, 267
Pyrrole
basicity, 73
electrophilic substitution, 166
protonation, 73
Quantum numbers
principal, n, 2
spin, 2
subsidiary, l and m, 2
Quinuclidine
basicity, 72
complex with Me,B, 28
RaeemisPtion, 89
deuterium exchange and, 288
in radical reactions, 326
in S,1, 90
Radical addition, 312-323
carbon tetrachloride, 320
halogens, 313
hydrogen bromide, 316
sulphenyl halides, 320
vinyl polymerisation, 320
Radical anions, 218
Radical rearrangements, 335
Radicals, 20,30,299-339
acyl, 306,330,335
addition to C=c, 313-323
alkoxyl, 303
alkyl, 301,303,304,
324
allylic, 311,325,327,
329
benzoyl, 330
benzylic, 311,316,
329
biradicals, 315,330,337
bridged, 310
chain reactions, 300,313,
314,328
combustion and, 299
conformational equilibrium, 319
cycloheptatrienyl, 308
cyclohexadienyl, 331
detection, 308
dimerisation, 300,305,311,313,314,
320,332,334
l ,l-diphenyl-2-picrylhydrazyl,301
disproportionation, 305,313,
320,332
e
...
r
...
S
...
, 148
diazoketones, 119
dienone-phenol, 115
Favorskii, 294
Hofmam, 122
hydroperoxides, l28
in Friedel-Crafts, 108,142,145,163
intermolecular, 117,143,149,278
intramolecular, 116,122,126,127,
279,355
Lossen, 122
migratory aptitude in, 114
neopentyl, 110
pinacol-pinacolone, 113
radical, 335
Schmidt, 122
sigmatropic, 352
stereochemistry of, 116,117,119
steric effects in, 115
Stevens, 293
Wagner-Meemein, 111
Wittig, 293
Wolff, 119
Redox reactions, 306
Reimer-Tiemann reaction, 290
414
Index
Relative configuration, determination,
88
Resonance energy, 17
Retro Diels-Alder reaction, 351
Retro pinacol rearrangement, 115
P, 363
p*, 385
Rotational entropy, 36
Rotation frequency, 8
Rubber
natural, 323
perishing of, 328
synthetic, 189,322
vulcanisation, 323
Sandmeyer reaction, 306
Sandwich comoounds
...
81
...
252
Solvatochromicshifts, 391
Solvent
bipolar non-protic, 81,98, 173,252
effect of, 45,80, 161,252,260,388
E, and, 391
ionising power, 390
ion-solvating ability, 80,260, 390
Zndex
parameter, Y, 389
Solvent separated ion pair, 90
Solvolysis, 80, 91, 109, 389
Specific acid catalysis, 74,209
Specific base catalysis, 75
Spectrosco ic correlations, 392
a and P n
...
r
...
m
...
, 393
,
a and i
...
shifts, 392
,
Spin, electronic, paired, 2
Stabilisation energy, 13
Stability, thermodynamic, 12
Staggered conformation, 7
Standing waves, electronic, 342
Stereochemicalcriteria, 51
Stereoselectivity, 52
in acetolysis, 377
,
51,180, 182,318
in addition to in addition to C==0,234
in Beckmann, 124
in concerted reactions, 341
in Diels-Alder, 198,349
in elimination, 253, 264, 267
in ozonolysis, 193
in rearrangements, 118
Steric effects, 26
crowding, 27,115,235,301,350
delocalisation and, 26,71, 172
in acidity, 58
in addition to C=C, 181
in addition to
205,235
in aromatic substitution, 152, 159,
162, 165
in diazo coupling, 27
in elimination, 261
in ester hydrolysis, 241
in rearrangements, 115
non-bonded interaction, 7
Steric hindrance, 27,79, 110, 159, 162,
222,235,243,301,312,356
Steric parameters, 386
E,, 386
6, 387
Sterigrnatocystin,48
Stevens rearrangements, 293
Stobbe reaction, 228
Substituent constant, a,362
'constancy' of, 368,372
determination of, 363
physical significance of, 364
pK, and, 362
polar effects and, 366
sign of, 364
spectroscopic shifts and, 392
values of, 363
Substituent effects, 150, 388
'
Substitution
electrophilic, aromatic, 41, 130-167
nucleophilic
...
31
...
stepwise, 342,351
conrotation, 345
Cope rearrangement, 354
cycloaddition, 348
Diels-Alder reaction, 349
disrotation, 345
electrocyclic, 344
'forbidden', 348
residual bonding in, 342
secondary orbital interaction, 350
sigmatropic rearrangements, 352
suprafacial shifts, 353
Symmetry, orbital, 344
Synperiplanar conformation, 253,269
Taft equation, 384
amide hydrolysis and, 388
derivation of, 386
6 parameter in, 387
E, parameter in, 386
ester hydrolysis and, 384
polar effects in, 385
p* in, 385
a& in, 385
standard substituent in, 385
Tautomerism, 277
catalysis of, 277
equilibrium and structure, 280
intermolecular, 278
intramolecular, 278,279
keto-enol, 201,219,225,277
mechanisms of, 278
nitroalkanes, 277,283
rate and structure, 279
rate-limiting step, 279
Terminators, 300,320
415
Tetraalkylammonium salts
basicity, 67
elimination from, 254,256
Tetrahedral hybridisation, 4
Tetrahedral intermediates
...
361
isolation, 237
Thermal concerted reactions, 341
Claisen rearrangement, 355
Cope rearrangement, 354
1,Shydrogen shifts, 353
1,7-hydrogenshifts, 354
4xe 2xe, 348
Thermodynamic control, 43, 163
addition to C==0,235
addition to dienes, 195
Diels-Alder , 350
Friedel-Crafts, l63
napthalene sulphonation, 43, 164
nitroalkane formation, 283
Thermodynamics, second law, 34
Thermodynamic stability, 12
alkenes, 26, 249
benzene, 15
delocalisation and, 26
dienes, 12
hyperconjugation and, 26
keto-enol forms, 282
Thiazolium ylids, 232
Thioacetals, 211
desulphurisation, 212
Thiols, addition to C==O, 211
Thionyl chloride, in chlorination, 92
Through-conjugation, 368
r and, 373
a and, 370
a+ and, 372,393
Transesterification, 239
Transition state, 24, 38
bridged, 118, 129,292,335
composition of, 41
conformation and, 118,235
crowding in, 27,83, 86, 183,206,235,
259,385
cyclic, 216,222,254,268,287, 352,
356
energy level of, 40, 137,235,283
models for, 41,49, 137, 151
orbital interaction in, 350
organisation in, 39
residual bonding in, 342
solvation of, 253
variable, 92,256,257
Translational entropy, 35,58,239,241
Transoid conformation, 197
Trapping of intermediates
arynes, 176
+
414
Index
Relative configuration, determination,
88
Resonance energy, 17
Retro Diels-Alder reaction, 351
Retro pinacol rearrangement, 115
P, 363
p*, 385
Rotational entropy, 36
Rotation frequency, 8
Rubber
natural, 323
perishing of, 328
synthetic, 189,322
vulcanisation, 323
Sandmeyer reaction, 306
Sandwich comoounds
...
81
...
252
Solvatochromicshifts, 391
Solvent
bipolar non-protic, 81,98, 173,252
effect of, 45,80, 161,252,260,388
E, and, 391
ionising power, 390
ion-solvating ability, 80,260, 390
Zndex
parameter, Y, 389
Solvent separated ion pair, 90
Solvolysis, 80, 91, 109, 389
Specific acid catalysis, 74,209
Specific base catalysis, 75
Spectrosco ic correlations, 392
a and P n
...
r
...
m
...
, 393
,
a and i
...
shifts, 392
,
Spin, electronic, paired, 2
Stabilisation energy, 13
Stability, thermodynamic, 12
Staggered conformation, 7
Standing waves, electronic, 342
Stereochemicalcriteria, 51
Stereoselectivity, 52
in acetolysis, 377
,
51,180, 182,318
in addition to in addition to C==0,234
in Beckmann, 124
in concerted reactions, 341
in Diels-Alder, 198,349
in elimination, 253, 264, 267
in ozonolysis, 193
in rearrangements, 118
Steric effects, 26
crowding, 27,115,235,301,350
delocalisation and, 26,71, 172
in acidity, 58
in addition to C=C, 181
in addition to
205,235
in aromatic substitution, 152, 159,
162, 165
in diazo coupling, 27
in elimination, 261
in ester hydrolysis, 241
in rearrangements, 115
non-bonded interaction, 7
Steric hindrance, 27,79, 110, 159, 162,
222,235,243,301,312,356
Steric parameters, 386
E,, 386
6, 387
Sterigrnatocystin,48
Stevens rearrangements, 293
Stobbe reaction, 228
Substituent constant, a,362
'constancy' of, 368,372
determination of, 363
physical significance of, 364
pK, and, 362
polar effects and, 366
sign of, 364
spectroscopic shifts and, 392
values of, 363
Substituent effects, 150, 388
'
Substitution
electrophilic, aromatic, 41, 130-167
nucleophilic
...
31
...
stepwise, 342,351
conrotation, 345
Cope rearrangement, 354
cycloaddition, 348
Diels-Alder reaction, 349
disrotation, 345
electrocyclic, 344
'forbidden', 348
residual bonding in, 342
secondary orbital interaction, 350
sigmatropic rearrangements, 352
suprafacial shifts, 353
Symmetry, orbital, 344
Synperiplanar conformation, 253,269
Taft equation, 384
amide hydrolysis and, 388
derivation of, 386
6 parameter in, 387
E, parameter in, 386
ester hydrolysis and, 384
polar effects in, 385
p* in, 385
a& in, 385
standard substituent in, 385
Tautomerism, 277
catalysis of, 277
equilibrium and structure, 280
intermolecular, 278
intramolecular, 278,279
keto-enol, 201,219,225,277
mechanisms of, 278
nitroalkanes, 277,283
rate and structure, 279
rate-limiting step, 279
Terminators, 300,320
415
Tetraalkylammonium salts
basicity, 67
elimination from, 254,256
Tetrahedral hybridisation, 4
Tetrahedral intermediates
...
361
isolation, 237
Thermal concerted reactions, 341
Claisen rearrangement, 355
Cope rearrangement, 354
1,Shydrogen shifts, 353
1,7-hydrogenshifts, 354
4xe 2xe, 348
Thermodynamic control, 43, 163
addition to C==0,235
addition to dienes, 195
Diels-Alder , 350
Friedel-Crafts, l63
napthalene sulphonation, 43, 164
nitroalkane formation, 283
Thermodynamics, second law, 34
Thermodynamic stability, 12
alkenes, 26, 249
benzene, 15
delocalisation and, 26
dienes, 12
hyperconjugation and, 26
keto-enol forms, 282
Thiazolium ylids, 232
Thioacetals, 211
desulphurisation, 212
Thiols, addition to C==O, 211
Thionyl chloride, in chlorination, 92
Through-conjugation, 368
r and, 373
a and, 370
a+ and, 372,393
Transesterification, 239
Transition state, 24, 38
bridged, 118, 129,292,335
composition of, 41
conformation and, 118,235
crowding in, 27,83, 86, 183,206,235,
259,385
cyclic, 216,222,254,268,287, 352,
356
energy level of, 40, 137,235,283
models for, 41,49, 137, 151
orbital interaction in, 350
organisation in, 39
residual bonding in, 342
solvation of, 253
variable, 92,256,257
Translational entropy, 35,58,239,241
Transoid conformation, 197
Trapping of intermediates
arynes, 176
+
'V'
416
Index
Trapping of intermediates (contd
...
251
initiation, 320, 321
propagation, 320
termination, 320,321
Vulcanisation, 323
Wngner-Meerwein rearrangements, 111
Water
,
187
addition to --l
addition to &-C, 207
autolysis of, 54
ion solvation and, 57,58,60
levelling effect in, 55
polarisability, 57
Wave amplitude, 343
Wave functions, 2,342
Wave nodes, 343
Wheland intermediates, 41, 131, 151
Wittig reaction, 233
Wittig rearrangement, 293
Wolff rearrangement, 119
Woodward-Hoffmam rules, 344
Wurtz reaction, 289
Xanthates, pyrolysis, 268
X-ray crystallography
ethanoate anion, 19
Grignard reagents, 221
Meisenheimer complexes, 171
triphenylmethyl radicals, 311
Ylids, 232,233,287
Y,solvent parameter, 389
Van der Wads radii, 8
Vibrational modes, 342
Vinyl ethers, polymerisation, 189
Vinyl polymerisation, 320
branching in, 321
chain length in, 321
coordination, 322
induction period in, 321
Notes
values of, 390
Yukawa-Tsuno equation, 372
parameter, r, and, 373
Zinc alkyls, 223
Zwitterions, 94, 176
diazoanthranilate anion, 176
peroxy, 193
1
'V'
416
Index
Trapping of intermediates (contd
...
251
initiation, 320, 321
propagation, 320
termination, 320,321
Vulcanisation, 323
Wngner-Meerwein rearrangements, 111
Water
,
187
addition to --l
addition to &-C, 207
autolysis of, 54
ion solvation and, 57,58,60
levelling effect in, 55
polarisability, 57
Wave amplitude, 343
Wave functions, 2,342
Wave nodes, 343
Wheland intermediates, 41, 131, 151
Wittig reaction, 233
Wittig rearrangement, 293
Wolff rearrangement, 119
Woodward-Hoffmam rules, 344
Wurtz reaction, 289
Xanthates, pyrolysis, 268
X-ray crystallography
ethanoate anion, 19
Grignard reagents, 221
Meisenheimer complexes, 171
triphenylmethyl radicals, 311
Ylids, 232,233,287
Y,solvent parameter, 389
Van der Wads radii, 8
Vibrational modes, 342
Vinyl ethers, polymerisation, 189
Vinyl polymerisation, 320
branching in, 321
chain length in, 321
coordination, 322
induction period in, 321
Notes
values of, 390
Yukawa-Tsuno equation, 372
parameter, r, and, 373
Zinc alkyls, 223
Zwitterions, 94, 176
diazoanthranilate anion, 176
peroxy, 193
1
Contents*
Page
Foreword by Professor Lord Todd, O
...
, P
...
R
...
Preface to sixth edition
1 Structure, reactivity, and mechanism
ix
xi
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
5 Carbocations, electron-deficient N and O atoms and their
reactions
77
101
6 Electrophilic and nucleophilic substitution in aromatic
systems
130
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