678
INDEX
Anomeric forms, see anomers
Antagonist, definition 514
Anthracene
aromaticity 45
electrophilic aromatic substitution 316
anti
addition, definition 287
anti-periplanar, definition 208
conformer 59
interaction, substituted cyclohexanes 67
Antibonding molecular orbitals, see molecular
orbitals, antibonding
anti-Markovnikov addition, radical addition of
HBr to alkenes 329
Antioxidants 40, 336–8
carotenoids 337
flavonoids 337
vitamin C 338
vitamin E 336
Aprotic polar solvents, Table 188
Arabinose
hemiacetal form, structure 471
structure and stereochemistry 465
Arachidonic acid, in prostaglandin
biosynthesis 339
Arenium cation 304
stability 309
Arginine,
ionization 502
at pH 7 152
structure and pK a values 500
Aromatic amino acid decarboxylase 602
Aromatic compounds, polycyclic, electrophilic
substitution 315
Aromatic electrophilic substitution, see
electrophilic aromatic substitution
Aromatic nucleophilic substitution, see
nucleophilic aromatic substitution
Aromatic rings
Kekul´ e forms 2
nomenclature 8
Aromaticity 41–5
annulenes 42
cyclopentadienyl anion 43
cyclopropenyl cation 43
fused rings 44
heterocycles 44
H¨ uckel’s rule 42
pyrrole, furan and thiophene 426
ring currents 44
Arrows
checklist 175
curly, see curly arrow
resonance 46
Ascorbic acid, see vitamin C
Asparagine
as amide 261
structure and pK a values 500
Aspartic acid
ionization 502
at pH 7 152
structure and pK a values 500
Aspirin (acetylsalicylic acid)
hydrolysis 257
synthesis 257
transesterification of COX 254
Asymmetry, torsional 92
Atoms 19
Atomic number 19
Atomic orbitals 20–23
allocating electrons to 23
carbon
sp hybrid 30
sp
2 hybrid 28–30
sp
3 hybrid 26–8
degenerate 22
hybrid 26–35
hydrogen atom 21
radial probability density plots 21
linear combination 25
nitrogen sp
3 hybrid 33
nodes 22
overlap 24
oxygen sp
3 hybrid 33
phase sign 22
quantum number combinations, Table 21
relative energies 22
shapes 22
Atomic spectra 22
Atomic structure 19
ATP (adenosine triphosphate)
as N-glycoside 478
hydrolysis 278
energy release 279, 574
mechanism 575
as nucleotide 559
in SAM biosynthesis 200
structure 229, 278
synthesis, oxidation reactions 575
Atracurium
elimination reactions 211
structure 211
Atropine
as racemate of hyoscyamine 78
racemization of hyoscyamine 375
Autoxidation 333
Axial groups, cyclohexane 64
Azetidine, structure 404
Azinane, structure 404
Aziridine, structure 404
Azo compounds, radical formation 319
Azoisobutyronitrile 319
Azolane, structure 404
Azoles
definition 432
numbering 432
1,2-Azoles, basicity 438
1,3-Azoles
acylation 436
alkylation 436
electrophilic substitution 436
nucleophilic substitution 437
reactivity 436
AZT (zidovudine), structure 559
Baeyer–Villiger oxidation, mechanism 335
Barbaloin, structure 477
Bases
Brønsted–Lowry definition 121
conjugate see conjugate base
Lewis definition 121
polyfunctional 144
strong, pH calculation 147
weak, pH calculation 147–8
Base pairs, nucleic acids 552
Base sequence, see nucleic acid, base
sequence
Basic reagents, Table 157
Basicity
definition 121
electronegativity effects 136
hybridization effects 138
inductive effects 137
influence of electronic and structural
features 136–42
and nucleophilicity 185, 207,
Table 186
of N and O nucleophiles, Table 186
pK a values 135
pK b 135
resonance / delocalization effects 139–42
Basicity (compounds)
acetaldehyde 139
acetamide 139
acetone 138
acetonitrile 138
adenine 449
alcohols 138
amides 139, 259
amidines 140
amines, aliphatic 137
amines, aromatic 141
amines, aromatic, substituted 142
aminopyridines 418
aniline 141
1,2-azoles 438
1,3-azoles 433
carbonyl compounds 139
carboxylic acids and esters 139
cyclohexylamine 141
diamines, aliphatic 145
diamines, aromatic 145
diazines 427
ethers 138
guanidines 141
guanine 449
heterocycles, nitrogen 143
heterocycles, non-aromatic 404
histidine 434
imidazole 143, 433
imines 138
indole 443
isoquinoline 442
isothiazole 438
isoxazole 438
oxazole 433
piperidine 143
purines 449
pyrazine 427
pyrazole 438
pyridazine 427
pyridine 143, 408
pyridones 416
pyrimidine 427
pyrrole 143, 407, 420
pyrrolidine 143
quinoline 440
thiazole 433
thioacids and thioesters 140
Bendroflumethazide (bendrofluazide) 275
Benzene
bond lengths 44, 45
INDEX
Anomeric forms, see anomers
Antagonist, definition 514
Anthracene
aromaticity 45
electrophilic aromatic substitution 316
anti
addition, definition 287
anti-periplanar, definition 208
conformer 59
interaction, substituted cyclohexanes 67
Antibonding molecular orbitals, see molecular
orbitals, antibonding
anti-Markovnikov addition, radical addition of
HBr to alkenes 329
Antioxidants 40, 336–8
carotenoids 337
flavonoids 337
vitamin C 338
vitamin E 336
Aprotic polar solvents, Table 188
Arabinose
hemiacetal form, structure 471
structure and stereochemistry 465
Arachidonic acid, in prostaglandin
biosynthesis 339
Arenium cation 304
stability 309
Arginine,
ionization 502
at pH 7 152
structure and pK a values 500
Aromatic amino acid decarboxylase 602
Aromatic compounds, polycyclic, electrophilic
substitution 315
Aromatic electrophilic substitution, see
electrophilic aromatic substitution
Aromatic nucleophilic substitution, see
nucleophilic aromatic substitution
Aromatic rings
Kekul´ e forms 2
nomenclature 8
Aromaticity 41–5
annulenes 42
cyclopentadienyl anion 43
cyclopropenyl cation 43
fused rings 44
heterocycles 44
H¨ uckel’s rule 42
pyrrole, furan and thiophene 426
ring currents 44
Arrows
checklist 175
curly, see curly arrow
resonance 46
Ascorbic acid, see vitamin C
Asparagine
as amide 261
structure and pK a values 500
Aspartic acid
ionization 502
at pH 7 152
structure and pK a values 500
Aspirin (acetylsalicylic acid)
hydrolysis 257
synthesis 257
transesterification of COX 254
Asymmetry, torsional 92
Atoms 19
Atomic number 19
Atomic orbitals 20–23
allocating electrons to 23
carbon
sp hybrid 30
sp
2 hybrid 28–30
sp
3 hybrid 26–8
degenerate 22
hybrid 26–35
hydrogen atom 21
radial probability density plots 21
linear combination 25
nitrogen sp
3 hybrid 33
nodes 22
overlap 24
oxygen sp
3 hybrid 33
phase sign 22
quantum number combinations, Table 21
relative energies 22
shapes 22
Atomic spectra 22
Atomic structure 19
ATP (adenosine triphosphate)
as N-glycoside 478
hydrolysis 278
energy release 279, 574
mechanism 575
as nucleotide 559
in SAM biosynthesis 200
structure 229, 278
synthesis, oxidation reactions 575
Atracurium
elimination reactions 211
structure 211
Atropine
as racemate of hyoscyamine 78
racemization of hyoscyamine 375
Autoxidation 333
Axial groups, cyclohexane 64
Azetidine, structure 404
Azinane, structure 404
Aziridine, structure 404
Azo compounds, radical formation 319
Azoisobutyronitrile 319
Azolane, structure 404
Azoles
definition 432
numbering 432
1,2-Azoles, basicity 438
1,3-Azoles
acylation 436
alkylation 436
electrophilic substitution 436
nucleophilic substitution 437
reactivity 436
AZT (zidovudine), structure 559
Baeyer–Villiger oxidation, mechanism 335
Barbaloin, structure 477
Bases
Brønsted–Lowry definition 121
conjugate see conjugate base
Lewis definition 121
polyfunctional 144
strong, pH calculation 147
weak, pH calculation 147–8
Base pairs, nucleic acids 552
Base sequence, see nucleic acid, base
sequence
Basic reagents, Table 157
Basicity
definition 121
electronegativity effects 136
hybridization effects 138
inductive effects 137
influence of electronic and structural
features 136–42
and nucleophilicity 185, 207,
Table 186
of N and O nucleophiles, Table 186
pK a values 135
pK b 135
resonance / delocalization effects 139–42
Basicity (compounds)
acetaldehyde 139
acetamide 139
acetone 138
acetonitrile 138
adenine 449
alcohols 138
amides 139, 259
amidines 140
amines, aliphatic 137
amines, aromatic 141
amines, aromatic, substituted 142
aminopyridines 418
aniline 141
1,2-azoles 438
1,3-azoles 433
carbonyl compounds 139
carboxylic acids and esters 139
cyclohexylamine 141
diamines, aliphatic 145
diamines, aromatic 145
diazines 427
ethers 138
guanidines 141
guanine 449
heterocycles, nitrogen 143
heterocycles, non-aromatic 404
histidine 434
imidazole 143, 433
imines 138
indole 443
isoquinoline 442
isothiazole 438
isoxazole 438
oxazole 433
piperidine 143
purines 449
pyrazine 427
pyrazole 438
pyridazine 427
pyridine 143, 408
pyridones 416
pyrimidine 427
pyrrole 143, 407, 420
pyrrolidine 143
quinoline 440
thiazole 433
thioacids and thioesters 140
Bendroflumethazide (bendrofluazide) 275
Benzene
bond lengths 44, 45