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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
...
m
...
spectrum and, 18
requirements for, 17
Aromatic substitution, 41
electrophilic, 130-167
internal, 334, 381
nucleophilic, 167-177
radical, 331-335
Arrhenius equation, 38
Arrows
curved, l9
double-headed, 19
Arylation, 332
Aryne intermediates, 21, 174
Associative process, 239, 241
Atactic polymers, 322
Atomic orbitals, 1, 342
Aufbau principle, 3
Autoxidation, 306, 318,328
alkenes, 329
benzaldehyde, 306,330
cumene, l28
ethers, 329
tetralin, 329
Axial overlap, 6
h i d e s , 123, 194
Azoalkanes
photolysis, 304
thermolysis, 305

Index
BAc2 pathway, 239,384
Baeyer-Villiger oxidation, 127
Barton reaction, 337
Base catalysis
general, 75
ion exchange resins, 226
specific, 75
Basicity
aromaticity and, 69,72
Brensted and, 53
cation stability and, 67, 68, 72, 73
constant, 65
effect of solvent on, 66,67
H-bonding in, 67
inductive effect and, 22,66
Lewis and, 54
multiply bonded N and, 72
nucleophilicity and, 96
origin in organic comps
...
0
...
m
...
signal, 18
ozonolysis, 194
planarity, 14
stability, 15
Benzilic acid rearrangement, 232
Benzoin condensation, 231
cyanide ion in, 231
thiazolium ylids in, 232

Benzotriazoles, 148, 176
Benzyne, 175,251
dimerisation, 176
isolation, 175
mass spec
...
, 207, 213
Bond
angles, 4
energy, 9,304
heterolytic fission, 20,299
homolytic fission, 20, 299
Bond-breaking
AH+ and, 38
Bond lengths, 7
hybridisation and, 7
Bonding orbitals, 6
Branching, 321
Bredt's rule, 259
Bridged species, 105,118,129,335,377
Bromodealkylation, 162
Bromonium ions, cyclic, 180
detection, 181
isolation, 181
l-Bromotriptycene, 87
Brensted
acids, 53
bases, 53
Butyl rubber, 189

Cadmium Alkyls, 238
Cannizzaro reaction, 47,216
intramolecular, 217
isotopic labels in, 47,217
crossed, 216
Canonical structures, 19, 152
Carbamic acids, 122
Carbanions, 21,270-298
acetylide anion, 223,272,289,294
acidity and, 272,277
200
addition to
addition to C=O, 221-236,284
alkylation of, 288
as nucleophiles, 288
configuration, 276
cyclooctatetraenyl dianion, 275

,C+C

400

401

cyclopentadienyl anion, 275
deuterium exchange, 288
displacement reactions, 287
ElcB elimination and, 248,285
electronic effects in, 272
enolate anions, 279,290,295
formation, 271
in carbonation, 284
in Danens reaction, 290
in decarboxylation, 285
in Favorskii reaction, 294
in halogenation of ketones, 295
in Kolbe-Schmidt reaction, 291
in Michael reaction, 200
in Reimer-Tiemann reaction, 290
intermediates, 41,200,229,295
in Wurtz reaction, 289
oxidation, 294,307
rearrangement, 292
solvation, 45
stabilisation, 251,257,262,273,2%
steric effects in, 276
tautomerism and, 277
trapping of, 286
triphenylmethyl, 271,272
Carbenes, 21
dichlorocarbene, 4,50, 267,290
intermediates, 119,266
Carbinolamine intermediates, 50,219
Carbocations, 21, 101-119
acyl, 102, 144,242,379
addition to
113, 188,225
allylic, 85, 105, 1%
benzylic, 84,91, 102, 105, 112,371
bridged, 105,118,129,377
cycloheptatrienyl, 18, 104, 106
cyclohexadienyl, 159
cyclopropenyl, 18, 106
decomposition, 102
ethyl, 83, 104,380
formation, 101, 107, 120
hydride shifts in, 108, 109
in E l pathway, 248,261
in Friedel-Crafts, 108, 141, 145
in S,1 pathway, 78, 81, 83,90,371
loss of H@, 107, 111
methyl, 83, 104,380
2-methylpropyl, 78,83, 102, 104
n
...
r
...
)
stabilisation, 21,84, 87, 104, 109,371,
382
stereochemistry of, 79, 84, 86, 104
structure, 104
triphenylmethyl, 84,87, 102, 103, 381
tropylium, 104
Carbon acids, 270
Carbonation, 284
Carbon, electron-deficient migration to,
108
Carbonyl group, 203-244
bond length, 11
characterisation, 219
conjugated, 12,23,200,205,223
dipole, 23,203
hydrates, 207
hydrogen bonding, 204,209
i
...
spectrum, 219
nucleophilic addition, 31, 200, 203244
protection, 210,211
protonation, 103,204
reactivity, 205
reduction, 212,214-219
structure, 23,203
Carboxylic derivs
...
, 12, 23,
200, 223
Conjugated dienes, 11
Conjugation, 11, 368
Conrotation, 345
Coordination polymerisation, 322
Copolymerisation, 322
Cope reaction, 268
Cope rearrangement, 354
Cracking, 112, 305
Cram's rule, 235
Cross-linking, 323
Crossover experiments, 116, 122, 126
Crowding, 8,110,162,165,183,206,235,
259, 261, 301, 311
Cumene, phenol from, 128
Curtius rearrangement, 122
Curved arrows, 19

Cyanides, addition to, 244
Cyanoethylation, 199
Cyanohydrins, 212
Cyclic bromonium ions, 180
Cycloadditions, 341, 348-352
2ne + 2ze, 348
4ne + 2 n e , 348,349
symmetry allowed, 349
symmetry forbidden, 348
Cycloheptatrienyl cation, 18, 104, 106
Cyclohexadienyl cation, 159
Cyclohexadienyl radical, 331
Cyclooctatetraene, 16
dianion, 275
n
...
r
...
S
...
, 23,205
carboxylate anions, 19,55,57
conditions necessary for, 18
dienes, 13, 194
energy, 13, 16
guanidine, 68
hyperconjugation and, 25

403

in a complexes, 132, 151, 164
steric inhibition of, 26, 71, 172
tropylium cation, 18, 104, 106
6 steric parameter, 386
AG, 34
AG+, 38, 152, 158, 342, 394
AGe, 36,58,66,394
AH, 16,34
bond energy and, 35
AH+, 38,239,241,342,394
h p , 58,66, 394

Desulphurisation, 212
Deuterium
exchange, 131,158,174,211,288
kinetic isotope effect, 46, 136,139,288
Diamagnetism, 308
Diaryls, synthesis, 333
Diazoamino cornps
...
198, 349
endo v
...
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

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

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

+

'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



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