692
INDEX
Pyrophosphates, see diphosphates
Pyrophosphoric acid, see diphosphoric acid
Pyrrole
acidity 421
aromaticity 44, 406
basicity 143, 407, 420
cyclic tetramers with aldehydes and ketones
423
dipole 407, 427
electrophilic substitution 421
Frost circle 406
Knorr synthesis 460
in Mannich reaction 422
molecular structure 406
Paal–Knorr synthesis 461
polymerization 422
N-substitutions 423
reactivity 420–3
resonance structures 407, 420
Pyrrolidine
basicity 143
dipole 407, 427
structure 404
Pyruvate
carboxylation to oxaloacetate 610
in glycolysis 584
stereospecific reduction to lactic acid 238
Pyruvate decarboxylase, in glycolysis 584
Pyruvate dehydrogenase
as enzyme complex 607
in Krebs cycle 585
as TPP-dependent reaction 605
Pyrylium cation, molecular structure 418
Quantum number
combinations, Table 21
magnetic 21
orbital momentum 21
principal 20
spin 21
Quaternary ammonium salts 201
curare-like 202
E2 reactions 210
Quercetin, structure 418
Quinic acid, conformational isomers 70
Quinoline
aminoquinolines 441
aromaticity 45
basicity 440
Chichibabin reaction 441
electrophilic substitution 440
nucleophilic substitution 440
reactivity 440
Skraup synthesis 458
systematic name 439
Quinolones 441
quinolone antibiotics 442
R, S convention, see configuration
Racemase enzymes, PLP-dependent 600
Racemate, see racemic mixture
Racemic mixture
definition 76
in electrophilic addition reactions 285
in S N1 reactions 192
in radical reactions 325
Racemization
amino acids, PLP-dependent 600
carboxylic acid derivatives 374
definition 76
involving enols and enolate anions 352
rate of reaction 353
hyoscyamine to atropine 375
ibuprofen, metabolic 377
2-iodobutane 184
Radicals 33
allyl 322, 325
benzyl 322, 325
tert-butoxyl 319
definition 319
methyl, electronic structure 33
benzoyloxyl 319
2-cyano-2-propyl 319
formation 319–21
phenyl 319
resonance delocalization 322
stability 321
structure 321
Radical reactions 171
abstraction, of hydrogen 320
addition reactions 328–31
to alkenes 321
HBr to alkenes 328
HBr to conjugated dienes 330
chain reaction 322
coupling, in phenolic oxidative coupling
341
initiation 172
oxidation, in prostaglandin biosynthesis
339
polymerization, of alkenes 331
propagation 172
termination 172
stereochemistry 325
substitution reactions 322–8
Ranitidine, structure 436
Rate constant 173
Rate expression 173
Rate of reaction 173
E1 reactions 212
E2 reactions 207
electrophilic addition reactions 283
halogenation involving enols and enolate
anions 356
racemization involving enols and enolate
anions 353
S N 1 reactions 191
S N 2 reactions 183
variables 184
Rate-determining step 173
E1 reactions 212
E2 reactions 207
electrophilic addition reactions 283
S N1 reactions 191
S N 2 reactions 183
Re, Si convention, see configuration
Reaction intermediates, see intermediates
Reaction kinetics 173
and mechanism 173
Reaction mechanism, see mechanism
Reaction order, definition 173
Reaction rate, see rate of reaction
Reaction types 174
addition, see addition reactions
elimination, see elimination reactions
ionic 167–71
radical 171
rearrangement, see rearrangement reactions
substitution, see substitution reactions
Rearrangement reactions 175
biosynthesis of lanosterol 219
carbocation (Wagner–Meerwein) 214–20
in electrophilic addition reactions 217, 296
in Friedel–Crafts alkylations 217, 307
and ring strain 217
in steroid side-chain biosynthesis 295
synthesis of camphor 218
Reductive amination, in amino acid
biosynthesis 598
Regiochemistry, in electrophilic addition
reactions 286
Regioselectivity,
definition 211
in electrophilic aromatic substitution 313
Regiospecificity, definition 211
Reserpine, structure 448
Resolution, of enantiomers 99
using chromatography 100
using diastereoisomeric salts 99
using enzymes 100
Resonance
arrow 46
energy 49
hybrid 45
Resonance effects
influence on acidity 129–34
influence on basicity 139–42
in electrophilic aromatic substitution 310
from functional groups, Table 134
Resonance stabilization
energy 49
enolate anions 349
peptide bond 508
radicals 322
Resonance structures 45–9
acetone 49
allylic cation 49
conjugated carbonyl derivatives 393
formaldehyde 49
furan 426
pyridine 406
pyrrole 407
rules governing use 47–9
Restriction endonucleases 564
Resveratrol, as antioxidant 338
Retinal, structure 40
Retinol (vitamin A 1 ), structure 40
Retroviruses 559
Reverse aldol reaction 361
in biochemistry 363
in glycolysis 581
PLP-dependent 603
Reverse Claisen reaction 386, 391
in biochemistry 387
in fatty acid β-oxidation 592, 594
Reverse transcriptase 559
Reversible reactions, of carbonyl group 223
Rhamnose, hemiacetal form, structure 471
Rhodopsin, structure 40
Ribitol, in FAD and FMN 560
INDEX
Pyrophosphates, see diphosphates
Pyrophosphoric acid, see diphosphoric acid
Pyrrole
acidity 421
aromaticity 44, 406
basicity 143, 407, 420
cyclic tetramers with aldehydes and ketones
423
dipole 407, 427
electrophilic substitution 421
Frost circle 406
Knorr synthesis 460
in Mannich reaction 422
molecular structure 406
Paal–Knorr synthesis 461
polymerization 422
N-substitutions 423
reactivity 420–3
resonance structures 407, 420
Pyrrolidine
basicity 143
dipole 407, 427
structure 404
Pyruvate
carboxylation to oxaloacetate 610
in glycolysis 584
stereospecific reduction to lactic acid 238
Pyruvate decarboxylase, in glycolysis 584
Pyruvate dehydrogenase
as enzyme complex 607
in Krebs cycle 585
as TPP-dependent reaction 605
Pyrylium cation, molecular structure 418
Quantum number
combinations, Table 21
magnetic 21
orbital momentum 21
principal 20
spin 21
Quaternary ammonium salts 201
curare-like 202
E2 reactions 210
Quercetin, structure 418
Quinic acid, conformational isomers 70
Quinoline
aminoquinolines 441
aromaticity 45
basicity 440
Chichibabin reaction 441
electrophilic substitution 440
nucleophilic substitution 440
reactivity 440
Skraup synthesis 458
systematic name 439
Quinolones 441
quinolone antibiotics 442
R, S convention, see configuration
Racemase enzymes, PLP-dependent 600
Racemate, see racemic mixture
Racemic mixture
definition 76
in electrophilic addition reactions 285
in S N1 reactions 192
in radical reactions 325
Racemization
amino acids, PLP-dependent 600
carboxylic acid derivatives 374
definition 76
involving enols and enolate anions 352
rate of reaction 353
hyoscyamine to atropine 375
ibuprofen, metabolic 377
2-iodobutane 184
Radicals 33
allyl 322, 325
benzyl 322, 325
tert-butoxyl 319
definition 319
methyl, electronic structure 33
benzoyloxyl 319
2-cyano-2-propyl 319
formation 319–21
phenyl 319
resonance delocalization 322
stability 321
structure 321
Radical reactions 171
abstraction, of hydrogen 320
addition reactions 328–31
to alkenes 321
HBr to alkenes 328
HBr to conjugated dienes 330
chain reaction 322
coupling, in phenolic oxidative coupling
341
initiation 172
oxidation, in prostaglandin biosynthesis
339
polymerization, of alkenes 331
propagation 172
termination 172
stereochemistry 325
substitution reactions 322–8
Ranitidine, structure 436
Rate constant 173
Rate expression 173
Rate of reaction 173
E1 reactions 212
E2 reactions 207
electrophilic addition reactions 283
halogenation involving enols and enolate
anions 356
racemization involving enols and enolate
anions 353
S N 1 reactions 191
S N 2 reactions 183
variables 184
Rate-determining step 173
E1 reactions 212
E2 reactions 207
electrophilic addition reactions 283
S N1 reactions 191
S N 2 reactions 183
Re, Si convention, see configuration
Reaction intermediates, see intermediates
Reaction kinetics 173
and mechanism 173
Reaction mechanism, see mechanism
Reaction order, definition 173
Reaction rate, see rate of reaction
Reaction types 174
addition, see addition reactions
elimination, see elimination reactions
ionic 167–71
radical 171
rearrangement, see rearrangement reactions
substitution, see substitution reactions
Rearrangement reactions 175
biosynthesis of lanosterol 219
carbocation (Wagner–Meerwein) 214–20
in electrophilic addition reactions 217, 296
in Friedel–Crafts alkylations 217, 307
and ring strain 217
in steroid side-chain biosynthesis 295
synthesis of camphor 218
Reductive amination, in amino acid
biosynthesis 598
Regiochemistry, in electrophilic addition
reactions 286
Regioselectivity,
definition 211
in electrophilic aromatic substitution 313
Regiospecificity, definition 211
Reserpine, structure 448
Resolution, of enantiomers 99
using chromatography 100
using diastereoisomeric salts 99
using enzymes 100
Resonance
arrow 46
energy 49
hybrid 45
Resonance effects
influence on acidity 129–34
influence on basicity 139–42
in electrophilic aromatic substitution 310
from functional groups, Table 134
Resonance stabilization
energy 49
enolate anions 349
peptide bond 508
radicals 322
Resonance structures 45–9
acetone 49
allylic cation 49
conjugated carbonyl derivatives 393
formaldehyde 49
furan 426
pyridine 406
pyrrole 407
rules governing use 47–9
Restriction endonucleases 564
Resveratrol, as antioxidant 338
Retinal, structure 40
Retinol (vitamin A 1 ), structure 40
Retroviruses 559
Reverse aldol reaction 361
in biochemistry 363
in glycolysis 581
PLP-dependent 603
Reverse Claisen reaction 386, 391
in biochemistry 387
in fatty acid β-oxidation 592, 594
Reverse transcriptase 559
Reversible reactions, of carbonyl group 223
Rhamnose, hemiacetal form, structure 471
Rhodopsin, structure 40
Ribitol, in FAD and FMN 560