index

A substitution reactions, 137

Absolute configuration, 118 synthesis, 139, 244, 247, 263–273
Acetals, 336, 338 synthetic sequences, 273–275
Acetoacetate ester synthesis, 426 Aldaric acids, 540
Acid–base reactions Aldehydes
alcohols, 137, 150 aldol condensation of, 420
α-amino acids, 569, 574–576 α halogenation reaction, 420
anilines, 495, 503–506 conjugation, 421
phenols, 495, 503–506 nomenclature, 319–321
structure of, 31, 34–35 oxygen containing functional groups, 17
Acid chlorides physical properties, 313, 321–322
basicity, 385 redox reactions, 313, 322–325
Gilman reagent, 387 spectroscopy, 314, 330–333
Grignard reagents, 387 synthesis, 313–318, 326–329
reduction, 389 Aldol condensation
spectroscopy of, 387 of acid derivatives, 422, 424–426, 443–446
synthesis, 314 of aldehydes, 420
Acid derivatives Aldonic acids, 540
aldol-type condensations of, 425–426 Aldose chain elongation, 541, 545
α hydrogen atoms, 421 Aldose chain shortening, 541, 545
enolates of, 449–450 Alkanes
hydrogen atom of, 448–449 conformations, 47–48
Michael condensation, 422, 426 Newman projection formulas, 62
Acidity nomenclature, 47, 54–57
α hydrogen atoms, 421, 423, 425, 427 physical properties, 50
carboxylic acids, 361, 368–371 Alkenes
structure, 31, 37–40 addition reactions, 85
terminal alkynes, 105, 112 bromination, 95–97
Activation energy, 43–44 classification, 72–73
Acyclic conformations, 63–64 dihydroxylation, 87–88, 100–101
Acyl derivatives epoxidation, 86, 88, 99–100
α carbon atom, 421–422 heats of combustion, 79
basicity, 385, 419 hydration, 86, 93–94
hydrolysis of, 386, 388 hydrogenation, 80–82
physical properties, 385 nomenclature, 70, 76–78
reaction of, 386–388, 390, 400–407 oxidation, 70
reduction, 387, 408–410, 457–459 ozonolysis, 87, 89, 101–104
Acyl group, 361 physical properties, 70, 78–79
Acyl halides, 363, 365, 376 reduction, 70
Acyl side chain reduction, 213 structure and bonding, 69
Acyl transfer reaction, 385 unsaturation number, 69, 73
Addition–elimination reaction Wittig reaction, 337, 340, 358–360
aromatic compounds, 495, 498 Alkoxymercuration–demercuration, 277, 280
carbonyl compounds, 337 Alkylation
Addition polymers, 588, 591–592 alkynes, 108
Addition reactions enamines, 467, 470
alkenes, 85 enolate ions, 420
alkynes, 106–107, 114–115 esters, 425
carbonyl groups, 335–336 Alkyl halides, 138, 150–153. See also Haloalkanes
Alcohols Alkynes
acid–base reactions, 137, 150 electrophilic addition reactions, 106–107, 114–115
acyl derivatives, reaction of, 386, 388 hydration, 108
dehydration, 140, 162–164 hydrogenation, 106–107, 112–114
nomenclature, 135, 144–146, 148 nomenclature, 105, 110–112
oxidation, 243, 246, 257–260, 314–315 properties, 105, 110
oxygen containing functional groups, 17 structure, 105, 109
properties, 135, 146–147 synthesis, 106, 108, 115–116
spectroscopy, 297 Allosteric protein, 572
structure, 135 Allylic bromination reactions, 186
603
Allylic systems, 184, 191–195 Bending deformations, 20
α alkylation, esters, 425 Benzene
α-amino acids aromaticity, 203
acid–base properties, 569, 574–576 covalent structure, 203
chiral synthesis, 570 molecular orbitals, 203
Fischer projection formula, 573 resonance stabilization, 203
isoionic point and titration, 570 Benzylic bromination, 214
structure, 569 Bicyclic compounds, 61
synthesis, 570, 578–579 Biochemical reductions, 329
α,β unsaturated aldehydes, 421 Blood group antigens, 542
α,β unsaturated ketones, 421 Bond angles, 15–16
α carbon atom, 419, 421–422, 439–443, 450–453 Bond cleavage, 41–42
α halogenation Bond dissociation energy, 32
aldehydes, 420 Bond length, 4, 14–15
carboxylic acids, 425 Bond-line structures, 18, 24–25
ketones, 420, 423, 436–438 Bond strength, 4
Amides Branched alkanes, 47
classification, 465 Bromination, 95–97
reduction, 387, 389, 466, 486–487 Butane conformations, 48
spectroscopy of, 387
Amines C
acyl derivatives, reaction of, 386, 389 Carbanion, 33
basicity, 466, 476–478 Carbenes, 86, 88, 97–99
bonding and structure, 465, 472 Carbocation rearrangements
classification, 465, 472–473 alcohols, 164–165
molecular formulas, 475–476 alkenes, 86
nomenclature, 465, 474–475 bond cleavage, 32
properties, 465, 476 Carbohydrates, 539
spectroscopy, 468, 492–494 Carbon atoms, classification of, 57–59
synthesis, 466, 469–470, 478–483 Carbon compounds, bonding in, 4
Amino group side chain reactions, 214 Carbon-13 NMR spectroscopy, 232, 241
Ammonium salts, 466, 468, 488 Carbonyl compounds
Anilines, 495, 502–506, 515, 517 alcohol addition, 336, 344–347
Anti addition reactions, 85–86, 90 α carbon atom, 419
Anti conformation, 48 α halogenation, 423, 425, 436–438
Anti hydrogenation, 107 conjugate addition reactions, 424, 447
Arenes, 203–204 isomerization, 423
Aromatic compounds Michael condensation, 422, 424, 426
benzene rings, 203 nitrogen addition, 337, 340, 354–357
functional groups, 212 nomenclature, 319–321
nomenclature, 215–216 physical properties, 313, 321–322
properties, 495, 501–503 reactivity, 341
substituents, 211–212, 217 redox reactions, 313, 322–325
synthesis, 226–228 spectroscopy, 314, 330–333
Aromatic ions, 207–208 synthesis, 313–318, 326–329
Aromaticity Carboxylate ions, 362, 371
benzene, 203 Carboxyl group, 361
criteria for, 205 Carboxylic acid derivatives
Hückel rule, 203, 206–207 nomenclature, 385, 391–392
Aryl boronic acids, 303 properties of, 394–395
Aryldiazonium salts, 497, 499–500 spectroscopy of, 387, 412–418
Aryl ethers, 498 Carboxylic acids
Aryl halides, 496 α halogenation of, 425
Atomic orbitals, 3 α hydrogen atom of, 421
Atomic properties, 1, 6 nomenclature, 361, 366
Atomic structure, 1 nucleophilic acyl substitution, 362
Azo compounds, 497, 517–519 oxygen containing functional groups, 17
physical properties, 361, 367–368
B reduction, 362, 364, 374–375
Basicity spectroscopy, 363, 381–384
acid chlorides, 385 synthesis, 362, 371–374
amines, 466, 476–478 Catalytic hydrogenation, 71, 248
vs. nucleophilicity, 169 Chain growth polymers. See Addition polymers
β dicarbonyl compounds, 422, 459–461 Chain transfer reactions, 588, 593

604
Chair conformation, 551–552 D-monosaccharide, 539
Chemical equilibrium, 31 Dynamic processes, 231, 242
Chemical shifts, 229–230, 234–236
Chirality, 117, 120–122, 133 E
Claisen condensation, 425, 453–457 Elastomers, 587
Concerted reactions, 521 Electrocyclic reactions, 521–522, 528–533
Condensation polymers, 588–589, 595–597 Electronegativity scale, 1
Condensed structural formulas, 17 Electrophiles, 216–217
Conjugate addition reactions, 195–199, 421, Electrophilic addition reactions
447, 467 alkynes, 106–107, 114–115
Conjugated dienes hydrogen halides, 85, 88, 90–93
electrophilic addition, 184 Electrophilic aromatic substitution reactions, 211–212, 217–218
molecular orbitals, 183, 190 Electrophilic conjugate addition reactions, 184, 186, 195–199
stability, 183, 189–190 Elimination–addition reactions, 496, 498
Constitutional isomers, 18 Elimination reactions, 138, 170–171, 178–182
Coordinate covalent bond, 299 Enamines, 467, 470, 484–485
Coordination number, 299 Enantiomers, 117–118, 132–133
Copolymers, 588, 593–594 Enantiotopic hydrogen atoms, 230
Coupling constants, 231 End group analysis, 584–585
Coupling reaction, 139 Enolates, 419, 429–433, 449–450
Covalent bonds, 1, 6–8 Enolization, 419
Cross-coupling reactions, 300, 302 Enols, 419, 427–428
Cross-linked polymers, 587–588, 594–595 Enthalpy change, 32
Cumulated dienes, 183 Enzymatic hydrolysis, 582–584
Cyanohydrins, 335, 338, 342–344 Epimerization, 539
Cyclic acyl derivatives, 393–400 Epoxides, 86, 88, 99–97, 278–281, 292–296
Cyclic compounds, 118, 132 Equilibrium constants, 31, 35–36, 40
Cycloaddition reactions, 521–522 Equivalent sterogenic centers, 118
Cycloalkanes conformation, 47–49, 60–61, 65–66 Esters
Cycloalkenes, 69 alcohols, 243, 246, 250–252
Cyclohexanes α alkylation, 425
conformation, 49, 540 α hydrogen atoms exchange, 425
dynamic processes, 231 oxygen containing functional groups, 17
phenols, 499
D reduction, 387, 389
Decarboxylation reactions, 362, 365, 375–376 synthesis, 363, 365, 377–379
Degphos, 570 Ethane
Degree of substitution, 69 conformations, 47–48
Dehydration sp3-hybridized carbon atoms, 4
alcohols, 140, 162–167 Ethene, 4
alkenes, 86 Ethers
Dehydrohalogenation nomenclature, 277, 282–283
alkyne synthesis, 108 oxygen containing functional groups, 17
haloalkanes, 140 physical properties, 277, 283
mechanisms, 138 protecting groups, 278, 280
regioselectivity in, 138, 154–157 spectroscopy, 279, 297
stereoelectronic effects, 157–161 structure, 277
Delta scale, 229 synthesis, 280, 285–289
Deuterium exchange reaction, 434–436 synthetic sequences, 289–290
Dextrorotatory chiral substance, 117 Ethyne, 4
Diastereomers, 118–119, 128–131 Exhaustive methylation, 468
Diastereotopic chiral center, 119 E,Z configuration system, 74–76
Diastereotopic hydrogen atoms, 230
Diazonium compounds, 516–517 F
Dieckmann condensation, 422 Fibers, 587
Diels–Alder reaction Fischer esterification reaction, 363
conjugated double bonds, 185–186 Fischer projection formulas, 117, 124, 548–549
cycloaddition reactions, 521–522 Formal charge, 2, 9–10
Dienes. See Conjugated dienes Free energy, 31, 40
Dihydroxylation, 87–88, 100–101 Friedel–Crafts acylation, 211, 213, 220–221, 314, 316
Dipole moments, 3, 12–13 Friedel–Crafts alkylation, 211, 213, 218–220
Disaccharides, 539, 541–542, 562, 566–567 Functional groups
Disubstituted benzene compounds, 211 aromatic compounds, 212
Disubstituted cyclohexanes, 49 bond-line structures, 24–25

605
Functional groups—continued carbonyl compounds, 335
identification, 19–20 equilibrium constants, 341–342
infrared spectroscopy, 28–29 Hydride ion shifts, 86
molecular formulas, 22 Hydroboration–oxidation, 244–245, 248, 269–271, 314, 316–317
structural formulas, 22–24 Hydrocarbons
classes, 47
G identification, 19
properties, 62
Gabriel synthesis, 466, 469
sp3-hybridized carbon atom, 135
Gauche conformation, 48
Hydrogenation
Geometric isomers, 48, 69–70, 74
alkenes, 80–82
Gibbs free energy, 32, 40
alkynes, 106–107, 112–114
Gilman reagents, 139, 299, 302, 305–306
heats of, 71
Glycosides, 541, 544, 558–561
stereochemistry and stereoselectivity, 83–84
Grignard reagents. See also Organometallic reagents
Hydrogen halides, electrophilic addition of
alcohols, 245, 249
alkenes, 85, 88
carbonyl compounds, 271–273
alkynes, 107
carboxylic acids, 362, 371–372
Hydrogen molecule, molecular orbitals of, 4
phenols, 496
Hydrogenolysis, 570
Grubbs metathesis reaction, 89, 301, 304, 309–311
I
H
Indirect hydration methods, 244
Haloalkanes Infrared spectroscopy, 19, 28–29, 233–234
alcohols, 243, 246, 254–257 Intramolecular aldol condensation, 420
carboxylic acids, 364 Ionic compounds, 1, 6
dehydrohalogenation, 140 Ion impact mass spectrometry, 231
nomenclature, 135, 143–144 Isoionic points
nucleophilic substitution reactions, 136, 139 α-amino acids, 570
properties, 135, 146 peptides and proteins, 577
reaction, 136 Isolated dienes, 183
structure, 135 Isomerization
substitution reaction, 466, 469 carbonyl compounds, 423
synthesis, 139–140 monosaccharides, 539
Halogenation Isomers, 18, 26–27, 57
alkenes, 86, 88
alkynes, 107
K
electrophilic substitution reactions, 213
Halogen compounds Kahn–Ingold–Prelog configurational nomenclature system, 118
coupling reaction, 139 Ketals, 336, 338
functional groups, 17 Ketones
Hammond postulate, 46 α halogenation reaction, 420
Haworth projection formula, 549–551 biochemical reductions, 329
Heats of combustion, 79 conjugation, 421
Heck reaction, 300, 303, 307 nomenclature, 319–321
Hell–Volhard–Zelinsky reaction, 421–422, 425 Noyori asymmetric reduction, 301, 304
Hemiacetals, 336, 540 oxygen containing functional groups, 17
Hemiketals, 336, 540 physical properties, 313, 321–322
Hemoglobin, 572 redox reactions, 313, 322–325
Heteroatoms, 47 spectroscopy, 314, 330–333
Heterocyclic aromatic compounds, 204, 209–210 synthesis, 313–318, 326–329
Heterogeneous catalytic hydrogenation, 71 tautomers, 419
Hinsberg test, 467 Kiliani–Fischer synthesis, 545
Hofmann elimination, 468, 471, 489–492 Kinetic order of reaction, 44
Hofmann rearrangement, 467, 470 Knoevenagel condensation, 422
Homogeneous catalytic hydrogenation, 71, 300 Kolbe synthesis, 499
Homopolysaccharides, 541
Hückel rule, 203, 206–207 L
Hybridization Leaving group, 170
bond length and bond strength, 4 Levorotatory chiral substance, 117
of carbon, 4, 13–14 Lewis structure, 1–2, 6–8, 85
of nitrogen, 5, 14 Lithium aluminum hydride reduction
of oxygen, 5, 13 alcohols, 248
Hydration amines, 466, 480–482
alkenes, 86, 88, 93–94 L-monosaccharide, 539
alkynes, 108 Long-chain branching, 588
606
M Optical purity, 117
Malonate ester synthesis, 426 Organic nitrogen compounds, 465
Markovnikov addition reaction, 85, 90–93, 244 Organometallic reagents
Mercaptans. See Thiols acyl derivatives, reaction of, 387, 390, 410–411
Meso compounds, 118 aromatic compounds, 495, 498
Methane, 4 carbonyl compounds, 496, 498
Michael condensation, 421–422, 424, 426, 448, 461–463 haloalkanes, 136, 139, 147
Microscopic reversibility principle, 86 Organopalladium-catalyzed cross-coupling reactions, 300
Mirror images, 117–118, 465 Osazones, 545
Mixed aldol condensation, 420 Oxidation
Molecular orbitals alcohols, 243, 246, 257–260
allylic systems, 184, 194–195 aldehydes, 315
vs. atomic orbitals, 3 alkenes, 70
benzene, 203 monosaccharides, 540, 543
conjugated dienes, 183 Oxidative cleavage, 314, 316
pericyclic reactions, 521–522, 525 Oxidative methods, 364
Molecular shapes, 12 Oxygen-containing functional groups, 17, 19
Monosaccharides Oxygen hybridization, 5
chemical determination, 541 Oxymercuration–demercuration, 244, 247, 268–269
chirality, 539 Ozonolysis, 87, 89, 101–104, 314, 316
classification, 547–548
P
conformation, 551–552
isomerization, 539, 544 Peptides
oxidation, 540, 543 bond line structure, 579–581
reduction, 540, 543, 554–557 enzymatic hydrolysis, 582–584
ring size determination, 542 hydrolysis, 581–582
structure determination, 562–565 isoionic points, 577
Monosubstituted benzene compounds, 211 primary structure determination, 581–582
Monosubstituted cyclohexanes, 49 synthesis, 571
Multiple pericyclic reactions, 535–537 Pericyclic reactions, 521, 524–525
Multiplicity, 237–238 Periodate oxidation, 544
Multistep synthesis, 380 Permethylation, 546
Mutarotation, 540, 553–554 Phenolate/phenoxide ions, 497, 513
Myoglobin, 572 Phenol-formaldehyde polymers, 589
Phenols
N acyl derivatives, reaction of, 388
esters of, 499
Natural macromolecules, 587 pKa values, 495, 503–504
Nitration, 213 reactions, 496
Nitriles reduction pH value, 31, 36–37
carbonyl compounds, 314, 318 Pinacol rearrangement, 246
carboxylic acid derivatives, 387, 390 pK value, 31, 36–37
Nitrogen-containing functional groups, 17, 20 Plane of symmetry, 117, 123
Nitro group side chain reduction, 214 Plastics, 587
Nonequivalent hydrogen atoms, 230 Polyamides, 589, 598–599
Normal alkanes, 47 Polycarbonates, 589
Noyori asymmetric reduction, 301, 304 Polycyclic aromatic compounds, 204, 209
Nuclear magnetic resonance, 229 Polycyclic molecules, 50, 61
Nucleophile Polyenes. See Conjugated dienes
vs. bases, 169 Polyesters, 589, 597–598
epoxides, 278 Polyether antibiotics, 277
haloalkanes, 136 Polyethers, 600–601
SN2 versus SN1 reactions, 170 Polysaccharides, 539, 541
Nucleophilic acyl substitution, 362, 385–386 Polyurethanes, 589, 601
Nucleophilic addition reactions, 335 Priority rules, 125–127
Nucleophilic aromatic substitution, 496, 498, 507–513 Prochiral centers, 119
Nucleophilic substitution reactions Propane conformations, 48
haloalkanes, 136–137, 139, 148–150 Proteins
reactivity in, 176–178 amino acid compositions, 571
solvent effect in, 171, 178 amino acid sequences, 571–572
stereochemistry of, 169, 173–175 bonds, 572
isoionic points, 577
O myoglobin and hemoglobin, 572
Oligosaccharides, 539 structure, 572, 585–586
Optical activity, 117, 123–124 Proton counting, 230
607
Q Stereoselectivity reaction, 119
Quaternary ammonium salts, 468, 488 Stereospecific reaction
Quinones, 497, 499, 514–516 cyclic compounds, 119
pericyclic reactions, 521–522
Steroids, 67
R
Strecker synthesis, 570
Reaction coordinate diagrams, 45–46 Structural formulas, 17, 22–24
Reaction mechanisms, 32–33, 44–45 Structure determination
Reactive carbon intermediate, 33, 41–43 disaccharides, 566–567
Reactivity, 33 monosaccharides, 562–565
Reduction spectroscopic methods, 229
acid chlorides, 387, 389 Substituted aromatic compounds, 212
acyl derivatives, 457–459 Substrate structure, 170–171
aldehydes, 315 Sulfonamides, 467, 487–488
alkenes, 70 Sulfonation, 213
amides, 387, 389 Sulfur compounds, 275–276
carboxylic acids, 362, 364, 374–375 Suzuki coupling reaction, 300, 303, 306
esters, 387, 389 Symmetry-allowed reactions, 522, 525–527
ketones, 315 Syn addition reactions, 85, 90
monosaccharides, 540, 543, 554–557 Syn hydrogenation, 107
nitriles, 387, 390 Synthetic macromolecules, 587
Reductive amination reaction, 466, 469–470 Synthetic polymers, 587–601
Reformatskii reaction, 422 Synthons, 301
Relative peak areas, 230
Resonance stabilization, 31 T
Resonance theory, 2, 10–11
Retrosynthesis, 301 Terminal alkynes, 105, 112
Ring size determination, monosaccharides, 542 Terpenes, 183, 188
Robinson annulation, 421, 448 Thermoplastics, 587
R,S configuration, 118, 127–128 Thermosetting plastics, 587
Thioacetals, 337, 339, 353–354
Thioethers, 17
S
Thioketals, 337, 339, 353–354
Saturated hydrocarbons, 47 Thiols, 17, 245
Side chain oxidation, 213 Transesterification reaction, 386
Sigmatropic rearrangements, 521, 523, 533–535 Transition metal complexes, 299
Silyl ethers, 278, 280
SN2 versus SN1 reactions, 169–170 U
Sodium borohydride reduction, 248
Ultraviolet–visible spectroscopy, 185, 199–201
Solid-phase peptide synthesis, 571
Unsaturated hydrocarbons, 47
Solvent effects, 170, 178
Unsaturation number, 69, 73
Sonogashira reaction, 300, 303, 308
Urethanes, 589
Spectroscopy
Uronic acids, 540
acid derivatives, 387, 412–418
alcohols, 297
aldehydes, 279, 330–333 V
amines, 468, 492–494 Valence-shell electron-pair repulsion (VSEPR) theory, 3
carboxylic acids, 363, 381–384 Vicinal diols, 244, 247, 260–262, 314, 316
conjugated double bonds, 185 VSEPR theory. See Valence-shell electron-pair repulsion (VSEPR) theory
epoxides, 279
ethers, 279, 297 W
functional group identification, 19 Wilkinson’s catalyst, 70, 300, 304, 308
ketones, 279, 330–333 Williamson ether synthesis, 278, 280
sp hybridization, 4 Wittig reaction, 337, 340, 358–360
sp3 hybridization, 4 Wohl degradation, 545
Spin-spin splitting, 230–231
Stability, 33 Y
Standard enthalpy change, 32
Standard free energy change, 32 Ylide chemistry, 358–360
Step-growth polymers. See Condensation polymers
Stereoelectronic effects, 157–161 Z
Stereogenic centers, 117–119 Zaitsev product, 138
Stereoisomers, 117 Ziegler–Natta catalysts, 588

608