INDEX
681
Corrins 423
corrin ring, general structure 425
Corticosteroids, semi-synthesis 291
Cortisol (hydrocortisone) 292
Coumarin, structure 418
Coumarins, as pyrones 418
Covalent bonding, see bonding, covalent
COX, see cyclooxygenase
Crossed aldol reaction, see aldol reaction
Crossed Claisen reaction, see Claisen reaction
Curare 202, 211, 342
Curly arrows 45–9, 167
and anions 46
and cations 46
fish-hook 172, 319
rules governing use 46, 168
Cyanide
bonding molecular orbitals 35
as nucleophile with aldehydes and ketones
238
as nucleophile in SN1 and SN2 reactions
204
Cyanidin, structure 418
Cyanocobalamin, see vitamin B12
Cyanogenic glycoside
definition 477
hydrolysis 239
Cyanohydrins
from aldehydes and ketones 238
hydrolysis to aldehydes / ketones 238
natural 239
cyclic AMP (cAMP)
and caffeine 452, 562
structure 561
Cyclobutane, conformational isomers 60
Cyclohexane
boat conformation 65
flagpole interaction 66
Newman projection 65
chair conformation 62
Newman projection 63
conformational isomers 62
rings, how to draw 70
twist-boat conformation 66
Cyclohexanecarboxylic acid, acidity 130
Cyclohexanol, acidity 133
Cyclohexene, half-chair conformation 67
Cyclohexylamine, basicity 141
Cyclooctatetraene, shape 42
Cyclooxygenase (COX)
in prostaglandin biosynthesis 339
transesterification by aspirin 254
Cyclopentadiene, acidity 421
Cyclopentadienyl anion, aromaticity 43,
44
Cyclopentane, conformational isomers 62
Cyclopropane, conformation 60
Cyclopropenyl cation, aromaticity 43
Cyclosporin A, structure 536
Cysteic acid, structure 506
Cysteine
disulfide bridges 505
instability in acid 261
ionization 503, 530
at pH 7 152
structure and pK a values 500
Cystine, structure 505
Cytidine, structure 550
Cytochromes
in electron transport chain 577
structure 425
Cytochrome P-450-dependent monooxygenase
in biological oxidations 425
in formation of methylenedioxy group 233
in phenolic oxidative coupling 343
Cytosine
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
D and L
amino acids, see amino acids
configurations, see configurations
glyceraldehyde, see glyceraldehyde
sugars, see sugars
DCC (dicyclohexylcarbodiimide)
in peptide synthesis 542
Decalin
cis and trans forms 107
cis, conformations 107
symmetry 109
cis-Decalone, isomerization 110
Decamethonium, structure 202
Decarboxylation
amino acids, PLP-dependent 601–2
during Claisen reaction involving
malonyl-CoA 595
of gem-diacids 390
of β-ketoacids 388
in biochemistry 389
in Krebs cycle 587
oxidative, see oxidative decarboxylation
reactions 387–93
Degenerate orbitals 22
Dehydroepiandrosterone, conversion into
androstenedione 355
Dehydrogenase enzymes 98, 237
Delocalization
electrons in benzene 41
electrons in conjugated systems 38
electrons, resonance structures 49
Delocalization effects
influence on acidity 129–134
influence on basicity 139–42
Deoxyadenosine, structure 550
Deoxyadenylic acid, structure 549
Deoxycytidine, structure 550
Deoxyguanosine, structure 550
Deoxyribonucleic acid, see DNA
Deoxyribonucleotides, biosynthesis 564
Deoxyribose, in DNA 550
2-Deoxystreptamine, structure 493
Deoxythymidine, structure 550
Deoxythymidylic acid, from deoxyuridylic
acid 455
Deoxyuridylic acid, in thymine formation 455
Desosamine, in erythromycin 256, 494
Dextropropoxyphene, nomenclature 13
Dextrorotatory enantiomer, definition 76
gem-Diacids, decarboxylation 390
Diamines
aliphatic, basicity 145
aromatic, basicity 145
Diastereoisomers, definition 85
Diastereoisomeric salts, in resolution of
enantiomers 99
Diastereomers, see diastereoisomers
Diastereotopic, definition 98
1,3-Diaxial interaction, substituted
cyclohexanes 68
Diazines
amino derivatives, tautomerism 430
aromaticity 427
basicity 427
definition 427
halo derivatives 428
hydroxy derivatives, tautomerism 429
reactivity 428
Diazinones, definition 429
Dibenzoyl peroxide 319
1,3-Dicarbonyl compounds, alkylation 357
Dicarboxylic acids
aliphatic, acidity 144
aromatic, acidity 145
Dicoumarol
formation 419
structure 419
Dicyclohexylcarbodiimide, see DCC
Dieckmann reaction, see Claisen reaction,
intramolecular
Dienes, conjugated, see conjugated dienes
Diethyl malonate
acidity 390
alkylation 390
Diethyl sulfate 272
Digitoxigenin, stereochemistry and shape 114
Digoxigenin, structure 478
Digoxin, structure 478
Dihydrocarvone, interconversion with
isodihydrocarvone 353
Dihydrofolate reductase
inhibitors 455
reduction of folic acid 453
Dihydroxyacetone phosphate
in glycolysis 581
tautomerism 350
Dihydroxyphenylalanine, see DOPA
Diisopropylamide anion, as strong base,
enolate anions 359
Diisopropylamine
acidity 359
in preparation of LDA 359
β-Diketones
from β-ketoester 392
reverse Claisen reaction 387
Dimethoxytrityl, as protecting group in
nucleic acid synthesis 567
Dimethyl sulfate
in alkylation reactions 272
formation 272
in methylation of morphine 187
in nucleic acid sequencing 564
Dimethylallyl diphosphate, allylic cation 196,
301
4-N,N-Dimethylaminopyridine, in
esterifications 409
1,4-Dimethylcyclohexane, conformational
isomers 68
Dimethylcyclohexanes, conformational
isomers 69
2,4-Dinitrofluorobenzene, Sanger reagent 544
gem-Diols (hydrates) 234
681
Corrins 423
corrin ring, general structure 425
Corticosteroids, semi-synthesis 291
Cortisol (hydrocortisone) 292
Coumarin, structure 418
Coumarins, as pyrones 418
Covalent bonding, see bonding, covalent
COX, see cyclooxygenase
Crossed aldol reaction, see aldol reaction
Crossed Claisen reaction, see Claisen reaction
Curare 202, 211, 342
Curly arrows 45–9, 167
and anions 46
and cations 46
fish-hook 172, 319
rules governing use 46, 168
Cyanide
bonding molecular orbitals 35
as nucleophile with aldehydes and ketones
238
as nucleophile in SN1 and SN2 reactions
204
Cyanidin, structure 418
Cyanocobalamin, see vitamin B12
Cyanogenic glycoside
definition 477
hydrolysis 239
Cyanohydrins
from aldehydes and ketones 238
hydrolysis to aldehydes / ketones 238
natural 239
cyclic AMP (cAMP)
and caffeine 452, 562
structure 561
Cyclobutane, conformational isomers 60
Cyclohexane
boat conformation 65
flagpole interaction 66
Newman projection 65
chair conformation 62
Newman projection 63
conformational isomers 62
rings, how to draw 70
twist-boat conformation 66
Cyclohexanecarboxylic acid, acidity 130
Cyclohexanol, acidity 133
Cyclohexene, half-chair conformation 67
Cyclohexylamine, basicity 141
Cyclooctatetraene, shape 42
Cyclooxygenase (COX)
in prostaglandin biosynthesis 339
transesterification by aspirin 254
Cyclopentadiene, acidity 421
Cyclopentadienyl anion, aromaticity 43,
44
Cyclopentane, conformational isomers 62
Cyclopropane, conformation 60
Cyclopropenyl cation, aromaticity 43
Cyclosporin A, structure 536
Cysteic acid, structure 506
Cysteine
disulfide bridges 505
instability in acid 261
ionization 503, 530
at pH 7 152
structure and pK a values 500
Cystine, structure 505
Cytidine, structure 550
Cytochromes
in electron transport chain 577
structure 425
Cytochrome P-450-dependent monooxygenase
in biological oxidations 425
in formation of methylenedioxy group 233
in phenolic oxidative coupling 343
Cytosine
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
D and L
amino acids, see amino acids
configurations, see configurations
glyceraldehyde, see glyceraldehyde
sugars, see sugars
DCC (dicyclohexylcarbodiimide)
in peptide synthesis 542
Decalin
cis and trans forms 107
cis, conformations 107
symmetry 109
cis-Decalone, isomerization 110
Decamethonium, structure 202
Decarboxylation
amino acids, PLP-dependent 601–2
during Claisen reaction involving
malonyl-CoA 595
of gem-diacids 390
of β-ketoacids 388
in biochemistry 389
in Krebs cycle 587
oxidative, see oxidative decarboxylation
reactions 387–93
Degenerate orbitals 22
Dehydroepiandrosterone, conversion into
androstenedione 355
Dehydrogenase enzymes 98, 237
Delocalization
electrons in benzene 41
electrons in conjugated systems 38
electrons, resonance structures 49
Delocalization effects
influence on acidity 129–134
influence on basicity 139–42
Deoxyadenosine, structure 550
Deoxyadenylic acid, structure 549
Deoxycytidine, structure 550
Deoxyguanosine, structure 550
Deoxyribonucleic acid, see DNA
Deoxyribonucleotides, biosynthesis 564
Deoxyribose, in DNA 550
2-Deoxystreptamine, structure 493
Deoxythymidine, structure 550
Deoxythymidylic acid, from deoxyuridylic
acid 455
Deoxyuridylic acid, in thymine formation 455
Desosamine, in erythromycin 256, 494
Dextropropoxyphene, nomenclature 13
Dextrorotatory enantiomer, definition 76
gem-Diacids, decarboxylation 390
Diamines
aliphatic, basicity 145
aromatic, basicity 145
Diastereoisomers, definition 85
Diastereoisomeric salts, in resolution of
enantiomers 99
Diastereomers, see diastereoisomers
Diastereotopic, definition 98
1,3-Diaxial interaction, substituted
cyclohexanes 68
Diazines
amino derivatives, tautomerism 430
aromaticity 427
basicity 427
definition 427
halo derivatives 428
hydroxy derivatives, tautomerism 429
reactivity 428
Diazinones, definition 429
Dibenzoyl peroxide 319
1,3-Dicarbonyl compounds, alkylation 357
Dicarboxylic acids
aliphatic, acidity 144
aromatic, acidity 145
Dicoumarol
formation 419
structure 419
Dicyclohexylcarbodiimide, see DCC
Dieckmann reaction, see Claisen reaction,
intramolecular
Dienes, conjugated, see conjugated dienes
Diethyl malonate
acidity 390
alkylation 390
Diethyl sulfate 272
Digitoxigenin, stereochemistry and shape 114
Digoxigenin, structure 478
Digoxin, structure 478
Dihydrocarvone, interconversion with
isodihydrocarvone 353
Dihydrofolate reductase
inhibitors 455
reduction of folic acid 453
Dihydroxyacetone phosphate
in glycolysis 581
tautomerism 350
Dihydroxyphenylalanine, see DOPA
Diisopropylamide anion, as strong base,
enolate anions 359
Diisopropylamine
acidity 359
in preparation of LDA 359
β-Diketones
from β-ketoester 392
reverse Claisen reaction 387
Dimethoxytrityl, as protecting group in
nucleic acid synthesis 567
Dimethyl sulfate
in alkylation reactions 272
formation 272
in methylation of morphine 187
in nucleic acid sequencing 564
Dimethylallyl diphosphate, allylic cation 196,
301
4-N,N-Dimethylaminopyridine, in
esterifications 409
1,4-Dimethylcyclohexane, conformational
isomers 68
Dimethylcyclohexanes, conformational
isomers 69
2,4-Dinitrofluorobenzene, Sanger reagent 544
gem-Diols (hydrates) 234