INDEX
679
Kekul´ e structures 44, 45
molecular orbitals 41
Benzoic acid
acidity 128, 130
substituted, acidity 131–3
Benzopyridines, definition 440
Benzoyl nitrate, in nitration reactions 444
Benzyl
esters, as protecting groups 541
radical 322, 325
Benzylic
carbocations 194, 218
halogenation, radical 327
radicals 325
Benzylpenicillin, structure 266, 448, 537
Betamethasone, structure 292
Bioresmethrin, structure 61
Biotin (vitamin H)
biotin-dependent carboxylations 609
in fatty acid biosynthesis 595
structure 609
Biphenyls, torsional asymmetry 92
Bischler–Napieralski isoquinoline synthesis
459
Blood glucose, monitoring 486
Blood groups, determinants 496
Blood plasma, buffering effect 154
Boat conformation, cyclohexane 65
BOC (tert-butoxycarbonyl), as protecting
group 541
Bond
conjugated 37
covalent 19
double 2, 20, 29
energy barrier to rotation 83
hydrogen, see hydrogen bonds
ionic 19
in protein tertiary structure 513
peptide, see peptide bond
pi (π) 24
molecular orbitals 25, 29
nitrogen and oxygen 34–5
sigma (σ) 24
molecular orbitals 25
nitrogen and oxygen 33–4
single 1, 19
triple 20, 30
cyanides / nitriles 35
wavy 226, 470
Bond angles
ammonia 34
and hybridization 51, 55
water 34
Bond energy, influence on acidity 125
Bond lengths
amidinium cation 141
benzene 44, 45
carboxylate anion 141
guanidinium cation 141
and hybridization 31, 51
hydrogen bonds 50
pyridine 405
Table 52
Bond polarity 35–7, 170
in SN2 reactions 183
Bond polarization 36
Bond-breaking mechanisms 167, 169
Bonding 19
covalent 24–35
ionic 23
Bond-making mechanisms 167, 169
Bornane, stereochemistry and shape 66, 116
Boron, electronic configuration 23
Bridged ring systems
nomenclature 116
stereochemistry 116–19
Bromonium ion, in addition of halogens to
alkenes 287
N-Bromosuccinimide (NBS)
in allylic brominations 327
bromine generation mechanism 327
Brønsted–Lowry definition of acids and bases
121
Brucine, in resolution of enantiomers 99
Buffer
combinations 154
definition 152
function 152
preparation 153
Buffering effect
blood plasma 154
calculation 153
1,3-Butadiene, molecular orbitals 37
Butane, conformational isomers 58
tert-Butoxycarbonyl, see BOC
n-Butyl lithium, in preparation of LDA 359
tert-Butylcyclohexane, conformation 68
Caffeine
and cyclic AMP 562
structure 451
Cahn–Ingold–Prelog system
configuration at chiral centres 80–2
configuration at double bonds 84
configuration in tropine 119
enantiotopic faces 97
prochirality 95
Camphor
stereochemistry and shape 117
synthesis from α-pinene 218
Camptothecin, structure 448
Canonical structures, see resonance structures
Capsanthin, structure 39
Captopril
as ACE inhibitor 532
structure 532
Carbamates, in amino group protection 541
Carbanions 32, 168
Carbocation
methyl, electronic structure 32
rearrangement reactions, see rearrangement
reactions, carbocation
Carbocations 32, 168
allylic 194
benzylic 194
in E1 reaction 212
as electrophiles 299
from electrophilic addition reactions 217
in electrophilic addition to alkenes 283
from Friedel–Crafts alkylations 217, 306
generation in nature 219
in S N 1 reaction 191
stabilization 193
Carbohydrate, definition 463
Carbon
electronic configuration 23
sp hybridized 30
sp
2 hybridized 28
sp
3 hybridized 27
sp hybrid orbitals 30
shape 31
stereochemistry 56
sp
2 hybrid orbitals 28–30
shape 29
stereochemistry 55
sp
3 hybrid orbitals 26–8
shape 27
stereochemistry 55
Carbonyl compounds, basicity 139
Carbonyl group
electronic structure 34
nucleophilic addition reactions 221–48
polarization 221
selective reduction 268
Carboxylation
of acetyl-CoA to malonyl-CoA 609
biotin-dependent 609
of pyruvate to oxaloacetate 610
Carboxylic acids
acidity 125
basicity 139
ester formation, acid-catalysed 252
halogenated, acidity 125
hydrogen bonding 50
from hydrolysis of derivatives 256–61
from hydrolysis of nitriles 244
Carboxylic acid derivatives
acidity, Table 372
alkylation 378
basicity 139
hydrogen exchange 374
hydrolysis 256–61
nucleophilic reactions 248–72
racemization involving enolate anions
374
reaction with amine nucleophiles 262–7
with oxygen nucleophiles 252–61
with sulfur nucleophiles 261
reduction with complex metal hydrides
267–9
β-Carotene, structure 39
Carotenoids 39
as antioxidants 337
Carvone, odour of enantiomers 78
Castanospermine, structure 448
Catalytic hydrogenation 332
Catecholamines, structures 602
Cation
allylic, see allylic cation
ammonium 34
arenium, see arenium cation
cyclopropenyl, aromaticity 43
hydronium 34
vinyl 292
Cations 19, 24
and curly arrows 46
Cationic polymerization 300
Cellulase 485
Cellulose
as polyacetal 232
structure 485
Cephalosporin C, structure 537
679
Kekul´ e structures 44, 45
molecular orbitals 41
Benzoic acid
acidity 128, 130
substituted, acidity 131–3
Benzopyridines, definition 440
Benzoyl nitrate, in nitration reactions 444
Benzyl
esters, as protecting groups 541
radical 322, 325
Benzylic
carbocations 194, 218
halogenation, radical 327
radicals 325
Benzylpenicillin, structure 266, 448, 537
Betamethasone, structure 292
Bioresmethrin, structure 61
Biotin (vitamin H)
biotin-dependent carboxylations 609
in fatty acid biosynthesis 595
structure 609
Biphenyls, torsional asymmetry 92
Bischler–Napieralski isoquinoline synthesis
459
Blood glucose, monitoring 486
Blood groups, determinants 496
Blood plasma, buffering effect 154
Boat conformation, cyclohexane 65
BOC (tert-butoxycarbonyl), as protecting
group 541
Bond
conjugated 37
covalent 19
double 2, 20, 29
energy barrier to rotation 83
hydrogen, see hydrogen bonds
ionic 19
in protein tertiary structure 513
peptide, see peptide bond
pi (π) 24
molecular orbitals 25, 29
nitrogen and oxygen 34–5
sigma (σ) 24
molecular orbitals 25
nitrogen and oxygen 33–4
single 1, 19
triple 20, 30
cyanides / nitriles 35
wavy 226, 470
Bond angles
ammonia 34
and hybridization 51, 55
water 34
Bond energy, influence on acidity 125
Bond lengths
amidinium cation 141
benzene 44, 45
carboxylate anion 141
guanidinium cation 141
and hybridization 31, 51
hydrogen bonds 50
pyridine 405
Table 52
Bond polarity 35–7, 170
in SN2 reactions 183
Bond polarization 36
Bond-breaking mechanisms 167, 169
Bonding 19
covalent 24–35
ionic 23
Bond-making mechanisms 167, 169
Bornane, stereochemistry and shape 66, 116
Boron, electronic configuration 23
Bridged ring systems
nomenclature 116
stereochemistry 116–19
Bromonium ion, in addition of halogens to
alkenes 287
N-Bromosuccinimide (NBS)
in allylic brominations 327
bromine generation mechanism 327
Brønsted–Lowry definition of acids and bases
121
Brucine, in resolution of enantiomers 99
Buffer
combinations 154
definition 152
function 152
preparation 153
Buffering effect
blood plasma 154
calculation 153
1,3-Butadiene, molecular orbitals 37
Butane, conformational isomers 58
tert-Butoxycarbonyl, see BOC
n-Butyl lithium, in preparation of LDA 359
tert-Butylcyclohexane, conformation 68
Caffeine
and cyclic AMP 562
structure 451
Cahn–Ingold–Prelog system
configuration at chiral centres 80–2
configuration at double bonds 84
configuration in tropine 119
enantiotopic faces 97
prochirality 95
Camphor
stereochemistry and shape 117
synthesis from α-pinene 218
Camptothecin, structure 448
Canonical structures, see resonance structures
Capsanthin, structure 39
Captopril
as ACE inhibitor 532
structure 532
Carbamates, in amino group protection 541
Carbanions 32, 168
Carbocation
methyl, electronic structure 32
rearrangement reactions, see rearrangement
reactions, carbocation
Carbocations 32, 168
allylic 194
benzylic 194
in E1 reaction 212
as electrophiles 299
from electrophilic addition reactions 217
in electrophilic addition to alkenes 283
from Friedel–Crafts alkylations 217, 306
generation in nature 219
in S N 1 reaction 191
stabilization 193
Carbohydrate, definition 463
Carbon
electronic configuration 23
sp hybridized 30
sp
2 hybridized 28
sp
3 hybridized 27
sp hybrid orbitals 30
shape 31
stereochemistry 56
sp
2 hybrid orbitals 28–30
shape 29
stereochemistry 55
sp
3 hybrid orbitals 26–8
shape 27
stereochemistry 55
Carbonyl compounds, basicity 139
Carbonyl group
electronic structure 34
nucleophilic addition reactions 221–48
polarization 221
selective reduction 268
Carboxylation
of acetyl-CoA to malonyl-CoA 609
biotin-dependent 609
of pyruvate to oxaloacetate 610
Carboxylic acids
acidity 125
basicity 139
ester formation, acid-catalysed 252
halogenated, acidity 125
hydrogen bonding 50
from hydrolysis of derivatives 256–61
from hydrolysis of nitriles 244
Carboxylic acid derivatives
acidity, Table 372
alkylation 378
basicity 139
hydrogen exchange 374
hydrolysis 256–61
nucleophilic reactions 248–72
racemization involving enolate anions
374
reaction with amine nucleophiles 262–7
with oxygen nucleophiles 252–61
with sulfur nucleophiles 261
reduction with complex metal hydrides
267–9
β-Carotene, structure 39
Carotenoids 39
as antioxidants 337
Carvone, odour of enantiomers 78
Castanospermine, structure 448
Catalytic hydrogenation 332
Catecholamines, structures 602
Cation
allylic, see allylic cation
ammonium 34
arenium, see arenium cation
cyclopropenyl, aromaticity 43
hydronium 34
vinyl 292
Cations 19, 24
and curly arrows 46
Cationic polymerization 300
Cellulase 485
Cellulose
as polyacetal 232
structure 485
Cephalosporin C, structure 537