Jones M., Fleming S.A. Organic Chemistry
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2,3-Dimethyl-2-butene
catalyzed hydration of, 139–40, 381
hydroboration, 397
hydrogen chloride addition, 131–32, 133–36,
365–67, 374
N,N-Dimethyl acetamide, 889
Dimethylamine, 241
3,3-Dimethylbicyclo[3.2.1]octane, 215
2,3-Dimethyl-2-butene, 116, 117, 139–40, 381,
397
3,3-Dimethyl-1-butyne, 127
cis-5,6-dimethylcyclohexa-1,3-diene, 1041
1,1-Dimethylcyclohexane, 205
1,2-Dimethylcyclohexane, 205–8
1,2-Dimethylcyclopropane, 84–85, 148, 205–7,
208
4,4-Dimethyldiazocyclohexa-2,5-diene, 431
1,2-Dimethylenecyclohexane, 546
Dimethyl ether (methoxymethane), 250, 314
N,N-Dimethylformamide (DMF), 873, 882, 889,
928
6,6-Dimethylfulvene, 975
3,4-Dimethyl-1,5-hexadiene, 1062–63
Dimethylketene (2-methyl-1-propen-1-one), 883
1,5-Dimethylnaphthalene, 530
Dimethylpentane, structures, 82
4,4-Dimethyl-2-pentanone, 718
2,2-dimethylpropane (neopentane), 705
2,2-Dimethylpropanol, 719
Dimethyl sulfate, 285
Dimethyl sulfide, 253, 314, 440
Dimethyl sulfoxide (DMSO), 806
Dinitrobenzene, 663, 668
2,4-Dinitrofluorobenzene, 1196, 1197
Dinitrogen trioxide, 647
2,4-Dinitrophenol, 674
2,4-Dinitrophenylhydrazone, 793
Dinitrotoluene, 669
Dioclea megacarpa, 1177
Diols (glycols)
gem-diols, 776, 781, 783, 790
overview, 240
vicinal diols, oxidative cleavage, 807, 817, 818,
845
vicinal diols from alkene oxidation, 443, 459,
840
Diones, 768
1,4-Dioxane (1,4-dioxacyclohexane, 1,2-dioxan),
254, 329
1,3-Dioxolane (1,3-dioxacyclopentane), 254
Diphenyl ketone (benzophenone), 769
1,3-Dipolar reagents, 436–37, 459
See also Carbenes; Diazo compounds; Ozone;
Ozonolysis
Dipole moment, definition, 14–16
Diradicals
calicheamicin antitumor action, 980
carbenes, 434, 435
cyclobutadiene, 585, 586
cycloheptatrienyl anion, 591
cyclooctatetraene, 586
from cyclopropane, 474
oxygen (O
2
), 484
Disaccharides, 1161–68
Disproportionation reaction,471–72, 473–74, 506
Disrotation, 1037, 1039–40, 1041, 1042
Distillation, 695
Disulfide bridges, 1190, 1193, 1194–95, 1216
Disulfides from thiol oxidation, 809, 818
Dithianes (thioacetals), alkylation, 1001–2
Dithiolate ions, 324
Ditropyl ether, 620
1,2-Divinylcyclopropane, 1064–65, 1067
DNA. See Deoxyribonucleic acid (DNA)
Docosahexaenoic acid (DHA), 865
Dodecahedrane, 186, 216, 216
Doering, William, 274, 1056n3, 1062–63, 1069n7,
1071
Double bonds, overview
in alkenes, overview, 18, 98
Cahn–Ingold–Prelog priority system, 153–54
carbon–carbon double bonds as intramolecular
nucleophiles, 1099–1108
carbon dioxide, 15–16
conjugated double bonds, definition, 512
Lewis structures, 18–19
See also Alkenes; Dienes
Dynamic NMR, 746–49
See also Nuclear magnetic resonance
spectroscopy (NMR)
E1cB reactions, 309–10, 968–69
E1 reactions
comparison to E1cB reactions, 309
competition between S
N
1 and E1 reactions,
298–99
overview, 321, 322
rate law, 298–99
Saytzeff elimination, 300, 311, 322
selectivity for more substituted product,
299–300
E2 reactions
anti elimination, 305–6, 311, 322
tert-butyl bromide E2 reactions, 301–2
competition between S
N
2 and E2 reactions,
301, 321
effect of substrate branching on E2–S
N
2 mix,
301–2
Hofmann elimination, 308–9, 310–11
overview, 321, 322
rate law, 301
reaction mechanisms, 301
Saytzeff elimination, 306, 308, 310, 311
selectivity in E2 reactions, 306–11
stereochemistry, 302–6
syn elimination, 305–6
Eclipsed conformation, 65–67
Eclipsing strain. See Torsional strain
Edman degradation, 1198–1200, 1202, 1218
Eicosapentaenoic acid (EPA), 865
Electrocyclic reactions
conrotation, 1037–39, 1041, 1042
cyclobutene, opening to a 1,3-butadiene,
1034–40, 1042, 1047
definition, 1032
disrotation, 1037, 1039–40, 1041, 1042
cis-1,3,5-hexatriene and 1,3-cyclohexadiene
interconversion, 1040–41, 1064
HOMO control of reactions, 1036–41
photochemical HOMO, 1039–41, 1044, 1046,
1048, 1058
photochemical reactions, 1035, 1038–40
problem solving techniques, 1071–72
rules for rotary motions,1042
thermal reactions, 1034–38
See also Pericyclic reactions
Electromagnetic spectrum, 707
Electron affinity, 4–5, 15
Electron configurations, overview, 3–6, 8, 10,46
See also Atomic orbitals; Quantum numbers
Electronegativity
common elements, 15
definition, 15, 132
NRM chemical shift of electronegative groups,
723, 725
and polar covalent bonds, 15–16, 132
and resonance forms, 27–28, 373
Electronic spectroscopy, 526
See also Ultraviolet/visible (UV/vis)
spectroscopy
Electron pushing, 23, 24, 25
Electrons, overview, 1,2,44
Electron shells, 4
Electron spin, 7–8, 10
Electron volt (eV), 4n5
Electrophiles, definition, 42, 390, 625
Electrophilic aromatic substitution, 635, 685
See also Substitution reactions of aromatic
compounds
Electrophoresis, 1180–81, 1195
Elimination, unimolecular, conjugate base (E1cB)
reactions, 309–10
Elimination reactions
anti elimination, 305–6, 311, 322
E1cB reactions, 309–10
Hofmann elimination, 308–9, 310–11
overview, 298, 311
Saytzeff elimination, 300, 306, 308, 310, 322
syn elimination, 305–6
See also E1 reactions; E2 reactions
Enamines, 795–96, 818, 821, 963–64, 1146
Enantiomers
absolute configuration, 172–73
chemical differences, 159–63
definition, 151
interconversion of conformational enantiomers,
163–64
optical activity, 152–55, 1128
racemic mixture (racemate), 156–57
reactions with racemic mixtures, 164–69
resolution, 169–72, 1184–85
(R/S) convention, 152–55, 181
separation as diastereomeric salts, 170–72
separation by chromatography, 172, 695–96
visual resolution, 169
Enantiotopic hydrogens, 721, 747–48
Endergonic reactions,335
Endo isomers, definition, 551
Endothermic reactions, 3, 36, 115, 193, 335
Energy barriers. See Activation energy ( G°);
Rotational energy barriers;Transition
states
Enolates
acyl compounds, 942–44
alkylation in the position, 954–64
base-catalyzed hydrogen exchange reaction,
936–38, 944
boron enolates, 1008
comparison of enolate and allyl anions, 934
definition, 934
ester enolate reactions with aldehydes and
ketones (Knoevenagel condensation),
974–76, 1014
ester enolate reaction with esters (Claisen
condensation), 987–92
ketone enolate reaction with esters, 985–87
kinetic enolates, 984
, 985, 986, 1008
¢
INDEX I-11
Enolates (continued)
Michael reaction,976–80
molecular orbitals, 935–36, 955
racemization, 944–46
reactions, summary, 1010–14
reaction with aldehydes, 965–71
reprotonation,934–35, 946
resonance stabilization, 27–28, 373, 933–34,
955
thermodynamic enolates, 1008
See also Aldol condensation; Carbonyl
compounds, reactions at position
Enolpyruvylshikimate-3P, 683
Enols
acid-catalyzed hydrogen exchange reaction,
938–39, 944
conversion to aldehydes, 449, 451
conversion to ketones, 448–50, 652
definition, 448
from enolate reprotonation, 934–35
equilibrium between carbonyl and enols forms,
940–42
Hell–Volhard–Zelinsky (HVZ) reaction,
950–53
keto–enol tautomerization, 939–40, 944, 961,
966
from ketones, 652
from oxymercuration of alkynes,448–49
propanal, 936
racemization, 944–46
reactions, summary, 1010–14
from vinylvoranes, 451
See also Carbonyl compounds, reactions at
position
Enones
cuprate addition, 979
definition, 976
Michael reaction,976–80
thermodynamics of reactions, 978–79
-unsaturated aldehyde and ketone from
crossed aldol dehydration, 982, 1014
-unsaturated aldehyde and ketone in
Horner–Emmons reaction,1009
-unsaturated aldehyde and ketone in
Michael reaction,976–80
-unsaturated carbonyl aldol dehydration
products, 968–69, 971–72, 973–75, 981,
1014
See also Carbonyl compounds; Carbonyl
compounds (overview)
Entgegen (E) isomers, 109, 111, 112–15
See also trans isomers
Enthalpy change
definition, 36, 335, 337
enthalpy of activation ( H°), 342, 349, 359
estimation from bond dissociation energy, 338
relationship to equilibrium constant, 335
relationship to Gibbs free energy
change, 335, 349
sign convention, 3, 37, 40, 193, 195
See also Heat of combustion Heat of
formation
Entropy change
335, 337–39, 349
Enzymes and reaction rates, 357–58
Epimers, 1133
Episulfonium ion, 1088
Epoxidation
of alkenes, 424–25, 459
asymmetric (Sharpless) epoxidation,426
DNA, 616
leaving groups, 424, 427, 429
single-step (concerted) mechanism, 424–25,
459
See also Oxiranes
Epoxides
definition, 317
1,2-diol formation, 426–27
mechanisms for opening in acids and bases,
427–29
reaction with amines, 318
reaction with organometallic reagents, 429–30,
797
regiochemistry of ring opening, 427–29
synthesis, 317, 424, 459
See also Oxiranes
Equatorial hydrogens,191
Equilibrium
equilibrium arrows, 25
overview, 332–33, 358–60
resonance versus equilibrium, 24–25, 29, 44,
372, 404, 617
S
N
1 reactions, 333, 337, 350
S
N
2 reactions, 267–68, 274, 332
in substitution reactions, 268
Equilibrium constant (K), 120, 201–2, 334–37
Erythrose, 1128, 1129
Essential amino acids, 1063, 1077
Esters
acid–base chemistry, 886–87
acid-induced ester hydrolysis, 895, 896
from Baeyer–Villiger reaction, 907–9, 924
base-induced ester hydrolysis, 862, 869, 895,
896–97
-bromo esters, 954
chlorosulfite esters, 284–85, 322, 854, 868
chromate esters, 804
direct alkylation, 963, 1012
enolates, 943
and Fischer esterification, 841–49, 852–53,
869, 896–97, 924
general formula, 877
halogenation, 954
ketone enolate reaction with esters, 985–87
lactone formation by intramolecular Fischer
esterification, 849, 870
lactones (cyclic esters, oxacycloalkanones), 849,
870, 880, 909, 925
methyl ester formation with diazomethane,
848–49, 869
odors and flavors, 876, 878
and organometallic reagents, 898–99
ortho esters, 846–48
polyesters, 852–53
pyrophosphate esters, 555–59
resonance forms, 885
structure, 769
thermal elimination reactions,912–14, 923, 924
transesterification, 896–98, 924, 987
xanthate esters, 914, 923, 925
See also Acyl compounds; -Keto esters
Estradiol, 182
Estrone, 562
Ethane
13
C NMR spectroscopy, 88
carbon–carbon bond strength, 68
combustion, 68
conformational analysis, 65–67
1,2-dideuterioethane, 67–68
dihedral angle, 65–66, 67
eclipsed ethane, 65–67
formation from methyl compounds,64
formation from methyl radicals,68–69, 83, 103
Lewis structure, 18
molecular orbitals, 68, 103
properties, 68
rotational energy barrier, 67, 70, 74–75, 93,
105–6, 188, 273
staggered ethane, 65, 75
structure, 64
structure drawings, 64, 65, 70–71
Ethanol (ethyl alcohol)
alcoholic beverages, 400
chemical exchange of OH hydrogens, 733–34,
739
decoupled NMR spectra, 733, 739, 746
formula, 230
NMR spectroscopy, 733–34, 747–48
physiology, 400
Ethene. See Ethylene
Ethers
acid–base chemistry, 251, 254
from alkoxide treatment with dimethyl sulfate,
285
bromo ethers and chloro ethers, 419, 458
cleavage by haloacids, 282–83
crown ethers, 254–55
cryptands, 255
cyclic ethers, 251, 254–55, 316, 391
and Grignard reagent formation, 228, 251, 254
nomenclature, 250
and organolithium reagent formation, 228
physical properties, 250
polyethers, 254
structure, 249, 251
tetrahydropyranyl (THP) ethers as protecting
groups for alcohols, 789–90
trialkylsilyl ethers as protecting groups, 789–90
Williamson ether synthesis,254, 315–17, 322,
1147, 1150, 1163
See also Thioethers (sulfides)
Ethoxide ion, 236, 299, 301, 315–16, 543
Ethoxyethene (ethyl vinyl ether), 250
Ethyl acetate, 713, 889, 943
Ethyl acetoacetate, 959
Ethylamine, 241
Ethylbenzene (phenylethane), 595,613
Ethyl benzoate, 664–65, 741
M-Ethylbenzoic acid (3-ethylbenzoic acid), 831
Ethyl bromide, 282
Ethyl compounds, structure and properties, 69
Ethyl crotonate, 739
Ethylene (ethene)
bonding, 18, 99–107
common name for ethene, 99, 99n2
electron transitions and energies, 527–29
hydration with sulfuric acid, 383
Lewis structure, 18
molecular orbitals, 103–4
pi orbitals, 104
plant hormone function, 106
protonation, 378–79
rotational energy barrier, 105–6, 107, 144
stabilizing effect of 2p/2p overlap, 105–6
structure, 99, 105–7, 764
torsional strain, 105
See also Alkenes
()
(¢S°),
(¢H°
f
)
(¢H°
c
);
(¢G°)
¢
(¢H°)
,
,
,
,
I-12 INDEX
Ethylene glycol (1,2-ethanediol), 231, 240, 852
Ethylene oxide, 231
1-Ethyl-4-fluorobenzene (p-ethylfluorobenzene),
596
Ethyl iodide (iodoethane), 226, 278, 727–28
Ethyl maleate, 740–41
Ethylmethylamine, 241
Ethylmethylammonium chloride, 242
Ethylmethylketene (2-methyl-1-buten-1-one),
883
Ethylmethylketene (2-methyl-1-propen-1-one),
883
Ethyl 3-methylpentanoate, 879
Ethyl methyl sulfide, 253
3-Ethylpentane, structure, 82
N-Ethylpiperidine, 242
Ethyl propionate (ethyl propanoate),879
Ethyl radical, 471, 473–74
Ethyne. See Acetylene
Ethynyl compounds, 126
Ethynylcyclohexane (cyclohexylacetylene), 127
Eugenol, 582
Exergonic reactions, 335
Exo isomers, definition, 551
Exothermic reactions,3, 36–37, 40, 115, 193, 335
Extinction coefficient, 527
Farnesol,557, 558
Farnesyl pyrophosphate (farnesyl–OPP),556–57,
559
Fats and oils,definition, 862
Fatty acids
cyclopropanated fatty acids, 455
definition, 862
docosahexaenoic acid (DHA), 865
eicosapentaenoic acid (EPA), 865
-linolenic acid (ALA; octadecatrienoic acid),
865
metabolism, 455, 862–63, 996–97
nomenclature, 862
omega-3 fatty acids, 865
saturated fats, 863, 864
unsaturated fats, 863, 864
Ferrocene, 531
Finkelstein reaction, 360
First-order reactions
E1 reactions, 298, 301
rate constant, 289, 341
S
N
1 reactions, 268, 289, 294, 340, 341
substrate and nucleophile in E2 reactions, 301
substrate and nucleophile in S
N
2 reactions, 268,
340
First-order spectrum, 735
Fischer, Emil, 841, 1125–26, 1125n1, 1139,
1153–56
Fischer determination of structures of aldohexoses,
1153–60
Fischer esterification, 841–49, 852–53, 869–70,
896–97, 924, 1187
Fischer projections, 1127–28, 1178
Fluoborate ion, 249–50, 587, 618
Fluoride, 4, 266
Fluorine, 4–5, 14, 17–18, 21, 237
Fluorobenzene,650
1-Fluorobutane, 680
Fluxional structure, 1063
See also Bullvalene
Force constant, 708
Formal charge, 20–22
Formaldehyde (methanal)
bond angles, 764
dipole moment, 766
equilibrium in hydration reactions, 777–81
molecular orbitals, 764
reaction with organometallic reagents to form
primary alcohols, 800, 817
resonance forms, 25
synthesis, 464
in wood products, 765
Formic acid (methanoic acid), 830, 832, 879, 880
Formyl chloride (methanoyl chloride), 880
Fractional crystallization, 695
Fragmentation patterns, 702–6
Franklin, Rosalind, 1213
Free radical reactions. See Radical reactions
Friedel–Crafts acylation, 643–46, 687, 893
Friedel–Crafts alkylation, 639–43, 646, 686
Frost circles
1,3,5,7-cyclooctatetraene, 586
benzene, 584–85
cyclobutadiene, 585
cyclopentadienyl anion, 589
overview, 584–85, 618
tropylium ion, 588
See also Hückel’s rule; Molecular orbitals
D-Fructose, 1130, 1141–42, 1166
Fukui, Kenichi, 531, 1032
Fulvenes,975
Functional groups, 22, 51
Furan, 250, 254, 599–600, 620, 629, 654–55
Furanoses, 1132–33
Furanosides, 1148
Furfural,654
2-Furoic acid, 736–37
Fused compounds, 121, 179–80, 211, 212–13, 592
See also Polynuclear aromatic compounds
GABA ( -aminobutyric acid),400
Gabriel synthesis, 1182–83, 1216
Galactaric acid, 1144
D-Galactose
chain shortening, 1139
in lactose, 1161–64
in melibiose, 1167
oxidation, 1144
reduction, 1143
structure, 1129, 1133, 1160
Garcia, Jerry, 877, 877n1
Garlic (sulfur-containing compounds), 252
Gas chromatography (GC), 697–99, 709
Gas chromatography/infrared spectroscopy
(GC/IR), 699, 709
Gas chromatography/mass spectrometry
(GC/MS), 699
Gas constant (R), 335, 336n2
Gauche interactions, 74, 74n6, 163–64
GC/IR (gas chromatography/infrared
spectroscopy), 699, 709
GC/MS (gas chromatography/mass spectrometry),
699
Gel-filtration chromatography, 1195
Geminal, definition, 447
Geraniol, 557, 558
Geranyl pyrophosphate (geranyl–OPP), 556–57
Gibbs, Josiah Willard, 336n3
Gibbs free energy 120, 334–39, 349
See also Activation energy ( G°)
Globin, 1194
Glucofuranose structure, 1132, 1135
Gluconic acid, 1144, 1162
Glucopyranose structure, 1132–33, 1134–38
D-Glucose
in cellobiose, 1165
in cellulose, 1124, 1168
chemical reactions, 1151–52
epimerization in base, 1141–42
glucofuranose structure, 1132, 1135
glucopyranose structure, 1132–33, 1134–38
hemiacetal formation, 784, 1132
in lactose, 1161–64
Lobry de Bruijn–Alberda van Ekenstein
reaction, 1141–42
in melibiose, 1167
oxidation, 1144
reduction, 1130, 1143
spectroscopy, 1130
structure, 222, 784, 1129, 1136–38, 1153–58
in sucrose, 1166
synthesis, 1138
Glutamic acid, 1176, 1180, 1185
Glutamine, 1176
Glyceraldehyde (2,3-dihydroxypropanal), 1126,
1127, 1128
Glycerol (glycerin), 231, 862
Glycine, 1175, 1176, 1178, 1181, 1184
Glycols (diols), 240
Glycolysis, 1140
Glycoproteins, 1165–66
Glycosides, 1148–52, 1210
Graphite, 115, 219, 603, 604
Grignard, Victor, 228
Grignard reagents
destruction by water, 799–800, 818
deuterolabeled molecule formation, 229–30,
257, 797
ether or tetrahydrofuran (THF) solvents, 228,
251, 254
hydrocarbon formation,229
as Lewis bases,228, 429
mechanism of formation, 228
protonation, 229
reaction with aldehydes and ketones to form
alcohols, 799–802, 817
reaction with CO
2
,840
reaction with esters, 898–99
reaction with oxiranes,429–30, 458
reaction with -unsaturated ketones, 979
structure, 228
synthesis from alkyl halides, 228–29, 257, 797,
818
Guanidines, 1206
Guanidinium ion, 45
Guanine, 615, 616, 1212
D-Gulose, 1129, 1139, 1156–58, 1159
Gutta percha, 554, 554n3, 557
Gyromagnetic ratio 715–16, 734, 740
Halobenzenes, 667, 674–75, 680, 681, 687
Haloform reaction, 948–50, 1012, 1013
Haloforms, 225, 949, 1012, 1013
Halogenation
aldehydes and ketones,in acid, 946–48, 1013
aldehydes and ketones,in base, 948–50, 1013
alkyne halogenation, 448
allylic halogenation, 497–501, 507, 543
benzene, with FeCl
3
or FeBr
3
, 638
bromination reaction mechanism, 414–17, 419
(),
,
¢
(¢G°),
INDEX I-13
Halogenation (continued)
bromonium ions, 415–21, 424, 426, 536
carboxylic acids, 950–53
chloronium ion, 418
conjugated dienes, 536
cyclohexene, 418–19, 497–500
cyclopentene, 414
esters, 954
geminal dihalides, 447, 459, 490
halohydrins, 418–19, 458
Hell–Volhard–Zelinsky (HVZ) reaction,
950–53, 1013
in nucleophilic solvents, 417–20
stereochemistry, 396, 414–17
substituted aromatic compounds, 638–39, 670
three-membered ring intermediates, 415–16
vicinal dihalides, 414, 448, 459, 490, 499, 507
See also Alkene hydrohalogenation; Alkenes,
addition reactions; Photohalogenation
Halohydrins, 317, 418–19, 458, 1083, 1094
Hammond postulate, 355–57, 377, 496
Harp modification of HVZ reaction, 952–53
Haworth forms, 1136–37
Heat of combustion 194–97
See also Enthalpy change
Heat of formation
alkanes, 116–18, 126
alkenes, 116–18, 126
alkynes, 116–18, 126, 515
allenes, 515
benzene, 581–82
carbocations, 292, 445
cycloalkanes, 194
definition, 115, 193
hydrogen molecule, 37
sign convention, 3, 37, 40, 193
and strain energy, 193–94
See also Enthalpy change
Heat of hydrogenation, 413, 524–25, 580–81, 620,
626–27
Heisenberg, Werner, 2, 2n1, 3n4, 44
Heisenberg uncertainty principle, 2–3, 2n3, 44
Helium, 3, 4, 5, 6, 40–41, 479
-Helix, 1191, 1192
Hell–Volhard–Zelinsky (HVZ) reaction, 950–53,
1013
Helprin, Mark, 624, 624n1
Heme units, 1194
Hemiacetals
acetal formation in acid, 786, 791–92
from carbonyl compounds in acid, 784–86,
790, 818
from carbonyl compounds in alcohol, 783–84,
818
from carbonyl compounds in base, 787
cyclic hemiacetal formation, 783–84, 1083
hemiketals and ketals, 786n2
sugars, 784, 1130–34
tetrahedral intermediate in Fischer
esterification, 842–43
See also Acetals; Carbonyl compounds, addition
reactions
Hemiketals, 786n2
See also Hemiacetals
Hemlock, 170
Hemoglobin, 1194
Heptamethylcyclohexadienyl cation
tetrachloroaluminate salt, 655–56
Heptane, 82
See also Methylhexanes
Heptanoic acid, 803
Heroin, 256
Heteroaromatic compounds
acid–base properties, 601–2
benzo-fused heterocycles, 605
Chichibabin reaction, 676–77, 761
definition, 599
electrophilic substitution of furan and
thiophene, 654–55
electrophilic substitution of pyridine and
pyrrole, 652–54
five-membered aromatic ring structures,
599–600
fused heterocycles, 605
resonance energy, 629
S
N
Ar reactions, 676–79
structures, 598–600
Heterobenzenes, 591, 599
See also Benzene
Heterogeneous catalysis, 411
Heterolytic bond cleavage, 37, 38, 62, 63, 470
Hexachlorobenzene, 597
(E,E)-2,4-Hexadiene, 512
1,3-Hexadiene, 572
1,5-Hexadiene, 475, 524, 1031, 1040–42, 1064
Hexafluoro-2-butyne, 628
Hexahelicene, 179–80, 604
Hexamethylbenzene, 655
Hexamethylenediamine, 852
1,2,3,4,5,6-Hexanehexol, 1143
Hexanes, 149, 150–51, 158, 473–74
See also Cyclohexane; Methylhexanes
2-Hexanone, 984
3-Hexanone, 803
1,3,5-Hexatriene, 529, 578–79, 583, 584, 1040–41,
1064
2,3,4-Hexatriene (1,4-dimethylbutatriene), 516
Hexenes
cis-2-chloro-3-hexene, 111, 394
3-chloro-3-hexene, 444
cis-1,2-dideuterio-1-hexene, 394–95
heat of formation, 116–18
cis-3-hexene, 116
trans-3-hexene, 116
relative stability of isomers, 116–18
types of carbon–carbon bonds in isomers,
116–17
See also Cyclohexene
E-2-Hexen-4-yne (trans-2-hexen-4-yne), 127
Hexoses, definition, 1130
Highest occupied molecular orbital (HOMO)
control of electrocyclic reactions, 1036–41
HOMO–LUMO interactions in cycloaddition
reactions, 1043–48
hydrogen chloride addition to 2,3-dimethyl-2-
butene, 134
interactions in Lewis acid–Lewis base
reactions, 266–267
interactions in S
N
2 reactions, 271–72
overview, 133
photochemical HOMO, 1039–41, 1044, 1046,
1048, 1058
ultraviolet/visible (UV/vis) spectroscopy,
528–29
High-performance liquid chromatography
(HPLC), 697
Histidine, 1176
HMG-CoA reductase, 358
Hoffmann, Roald, 180n6, 531, 1031–32, 1034
See also Woodward–Hoffmann theory
Hofmann, August Wilhelm, 648
Hofmann elimination, 308–9, 310–11
Hofmann rearrangement, 919–20, 923
HOMO. See Highest occupied molecular orbital
(HOMO)
Homogeneous catalysis, 411
Homolytic bond cleavage
bond dissociation energy (BDE), 337,470
butane carbon–carbon bonds, 470–71
definition, 37, 227
ethane carbon–carbon bonds, 469,470
methane, 57, 63
single-barbed (fishhook) arrows convention,
37, 38, 63
Homotopic hydrogens, 721, 748
Homotropilidene, 1066–68
Hooke’s law, 708
Horner–Emmons reaction,1009
Hückel’s rule
and aromaticity, 582–95, 618
degenerate orbital pairs, 584–85, 586, 588–89,
591, 592, 635
overview, 583–84, 618
See also Frost circles
Hund’s rule,9–10
Hunsdiecker reaction, 861, 869
Hunter, Robert, 877, 877n1
HVZ (Hell–Volhard–Zelinsky) reaction, 950–53,
1013
Hybrid orbitals
hybridization, overview, 52–53, 57–60
methyl compounds, 61–62
and NMR chemical shifts, 724–25
sp hybrid orbitals, 53–55
sp
2
hybrid orbitals, 55–56
sp
3
hybrid orbitals, 56–57
See also Atomic orbitals
Hydrates
definition, 773
gem-diols, 776, 781, 783, 790–91
equilibrium constants of carbonyl hydrates,
778, 779
equilibrium in carbonyl compound hydration
reactions, 777–81
formation by carbonyl compound hydration,
773, 775–81, 783, 818
steric destabilization, 778, 780
Hydration
acid-catalyzed hydration of alkenes, 139–41,
143, 381–82, 403, 773, 775–76
alkynes, 448–50
carbonyl compounds, equilibrium in hydration
reactions, 777–81
carbonyl compounds, reaction mechanisms,
773–77
catalyzed hydration of 2,3-dimethyl-2-butene,
139–40
comparison of direct, hydroboration, and
oxymercuration methods, 423
HX addition reactions to alkenes,380–84, 404
oxymercuration, 421–23, 448, 458, 459
radical HX hydration of alkenes, 481–87
Hydrazones, 793, 1145–46
Hydride ions, 62, 264–66
Hydrides
beryllium hydride, 62
s
(¢H°)
(¢H°
f
)
(¢H°)
(¢H°
c
),
I-14 INDEX
NADH as biological hydride source,315
poor leaving group, 1005, 1010
reaction with amides, 900
reaction with esters, 900
reaction with organic halides, 798
reaction with water, 798
reduction of carbonyl compounds to alcohols,
801–3, 817
reduction of nitrile, 906
sodium hydride, 315
See also Lithium aluminum hydride
Hydride shifts
Cannizzaro reaction, 1005, 1012
carbocation rearrangement, 387–88, 392,
401–2, 642
definition, 387
Magid’s third rule, 1007
Meerwein–Ponndorf–Verley–Oppenauer
(MPVO) equilibration, 1006–7, 1012
NAD
reduction by hydride transfer from
ethanol, 814–15
radical rearrangement, 502
Hydroboration
alcohol synthesis, 398–401
alkylborane formation, 391, 394
alkynes, 450–51
concerted mechanism, 391–95
definition, 390
dialkylboranes, 397
2,3-dimethyl-2-butene, 397
regiochemistry, 392–93, 399–400
steric factors, 392, 397
syn addition, 394–95
trialkylboranes, 397, 398, 399
See also Alkenes, addition reactions; Borane;
Boron trifluoride
Hydrocarbon cracking, 473–74
See also Pyrolysis
Hydrocarbons
bond dissociation energies, 477
definition, 51
formation from alkyl halides, 229
from Kolbe electrolysis, 860, 861, 870
solubility, 240
synthesis by reduction with Raney nickel, 253,
257
synthesis from organometallic reagents,229,
257
Hydrogen
aldehyde hydrogens, 725
bond dissociation energy (BDE), 37
bond energy of H
2
molecule, 39–40
bond strength in H
2
, 36–41, 57
electron configuration, 6, 10, 14
energy as function of distance between nuclei,
31
enthalpy of formation, 37
hydrogen abstraction, definition, 471
Lewis structure, 14
molecular orbitals, 30–35, 31–35
orbital interaction diagrams, 33–34
Hydrogenation
alkynes, 452
benzene, heat of hydrogenation, 580–81
benzene catalytic hydrogenation, 580, 627
benzene conversion to cyclohexane, 580–81,
626–27, 686
cycloalkenes, 412
definition, 410, 411
diimide, 411
energetics, 413–14
heats of hydrogenation, 413
Lindlar catalyst, 452, 458
palladium catalysts, 411, 452, 458
steric factors, 412
Wilkinson’s catalyst (rhodium), 411
See also Alkenes, addition reactions; Alkynes,
addition reactions
Hydrogen bonding
alcohols, 232–33
amines, 245–46, 247–48
carboxylic acids, 832, 833
definition, 232, 257
-dicarbonyl (1,3-dicarbonyl) compounds,
941, 942
and NMR chemical shifts, 726
nucleic acids, 288, 615, 1212–13
peptides and proteins, 1190–91, 1192, 1194
protic solvents, 238–39, 256, 280
solvents, 238–39, 256, 280
Hydrogen bromide
addition to 1,3-butadiene, 406, 534–35
addition to cis-2-butene, 406
anti-Markovnikov radical addition to alkenes,
481–82, 484–86, 506
mechanism for addition to alkenes, 414
Hydrogen chloride
addition to 1,3-butadiene, 369–71, 534–35,
537–39
addition to 2,3-dimethyl-2-butene, 131–32,
133–36, 365–67, 374
addition to 2-methyl-1-butene, 374–75
addition to 3-methyl-1-butene, 386–87
addition to 2-pentene, 375
addition to vinyl chloride, 367, 372
dipole moment, 132
Hydrogen cyanide, 93
Hydrogen fluoride, 14
Hydrogen iodide, 380–81, 406
Hydrogen nuclear magnetic resonance
spectroscopy (
1
H NMR)
acyl compounds, 888–89
hydrogens or carbons, 714–15, 723, 725
hydrogens or carbons, 714–15, 723, 725
complicated spectra, 735–39
cyclohexane, 746–47
decoupled spectra, 739
deshielding, 720, 723–24, 725, 771
diastereotopic hydrogens, 721–22, 731, 749
4,4-dimethyl-2-pentanone, 718
enantiotopic hydrogens, 721, 747–48
energy difference between spin states, 714–16,
720
first-order spectra, 735, 737–38
flipping a nuclear spin, 714–15, 720
homotopic hydrogens, 721, 748
integral, 718–20, 729
magnetic resonance imaging (MRI), 713
n 1 rule, 727–29, 735–36
NMR measurements, overview, 717–18
overview, 88, 90, 94
tetramethylsilane (TMS) standard, 716–17,
720–21
See also Chemical shift Nuclear magnetic
resonance spectroscopy (NMR);
Spin–spin coupling
Hydrogen peroxide, 398, 424, 441, 602
Hydrophilic groups, 866, 1192
Hydrophobic groups, 866, 1192
Hydroquinone (p-dihydroxybenzene), 484, 597
Hydroxybenzene. See Phenol
-Hydroxy carbonyl compounds, 966, 968,
973–74, 982–83, 1003
See also Aldol condensation; Carbonyl
compounds; Carbonyl compounds
(overview)
7-Hydroxy-5-decanone, 984
5-Hydroxy-4,5-dimethyl-3-hexane, 982
5-Hydroxyhexanal, 1131
Hydroxyl group
as activating group in aromatic compounds,
669–70, 671
hydrogen bonding, 238
leaving group of alcohols, conversion to water,
235, 281–82, 322, 555
naming conventions, 111
protecting hydroxyl groups, 789
protonation in carboxylic acids, 837–38
See also Alcohols; Carbohydrates; Neighboring
group effect; Phenols
3-Hydroxy-3-methylcycloheptane, 981
2-Hydroxy-6-methyltetrahydropyran, 1131
(E)-4-Hydroxy-2-pentenoic acid, 831
Hyperconjugation, 293–94, 377–78, 478–79
D-Idose, 1129, 1139, 1159
Imidazole, 621
Imides, 882
Imines (Schiff bases)
equilibrium with enamines, 796, 1146
formation from carbonyl compounds, 790–94,
818
formation from nitriles, 904–6, 924
formation of substituted imines, 793
Iminium ions, 795–96, 903, 964, 1003–4, 1013
Indene, 406
Indole, 605
Induced dipole, 87
Inductive effects, definition, 379
Infrared (IR) spectroscopy
acyl compounds, 887–88
carbonyl compounds, 770–71
carboxylic acids, 833
characteristic IR absorptions, 709–13
infrared absorptions of functional groups,
710–11
IR spectra of organic molecules, 709, 712
IR spectrometers, 708–9
overview, 696, 707–8, 734
See also specific compounds
Inhibitors, 484
Initiation of chain reactions, 482, 483
Integral, 718–20, 729
Intermediates
allenes in alkyne isomerization, 516–18
benzyne, 681–82
carbocations in alkene addition reactions,
132–33, 135–36, 140
comparison to transition state, 186
cycloalkynes, 128
definition, 62, 186
dienes in alkyne isomerization, 516–18
hemiacetal intermediate formation in acid,
784–86, 790, 818
methyl ions and radicals, 62
three-membered ring halogenation, 415–16
See also Tetrahedral intermediate in
addition–elimination reactions
(),
(¢H°)
INDEX I-15
Intramolecular reactions. See Neighboring group
effect
Inversion of configuration
mechanisms, 270–71, 350
phosphorus reagents, 285
S
N
1 reactions, 291–92, 297
S
N
2 reactions, 269, 270–75, 284, 288, 297
Iodoform, 949
Iodomethane (methyl iodide), 226
2-Iodo-2-methylpropane (tert-butyl iodide). See
tert-Butyl iodide
2-Iodopropane (isopropyl iodide), 226
2-Iodopropene, 446, 447
3-Iodopropene (allyl iodide), 543
Ion-exchange chromatography, 1195
Ionic bonds, 5–6, 15
Ionization potential, 4, 5
Ions, definition, 4
Ipso attack, 677–78
Isobutane, 73, 75
Isobutene (2-methylpropene, isobutylene)
boiling point, 770
dimerization, 384–85
dimerization and polymerization, 385–86
hydration reactions, 382, 390
regiochemistry of addition reaction, 137
solubility, 240
structure, 109
See also Butene
Isobutyl alcohol (2-methyl-1-propanol), 230
Isobutyl chloride (1-chloro-2-methylpropane), 494
Isobutyl compounds, 75
Isobutyraldehyde (2-methylpropanal), 464, 767
Isocitrate, 357
Isocyanates, 918–21, 923, 924, 1206
Isoelectric point (pI ), 1176–77, 1179–80
Isoleucine, 1176
Isomers
cis isomers, 84, 85, 144
conformational isomers, 70, 177
definition, 69–70
diastereomers, 165–67, 169–72, 177, 208–9
drawing isomers, 82–83
entgegen (E) isomers, definition, 109
overview, 176–77
problem solving techniques, 82
relative stability of alkane isomers, 116–18
stereoisomers, definition, 148, 176
structural isomers, definition, 73, 174, 176
trans isomers, 84, 85, 144
zusammen (Z) isomers, definition, 109
See also Enantiomers
Isopentane, 76, 77–78
Isoprene (2-methyl-1,3-butadiene)
gutta percha, 554, 554n3, 557
head and tail attachment, 557
polyisoprene, 554, 557
steroid biosynthesis, 559
structure, 512, 554, 557, 565
terpene formation, 557–58
Isoprene rule, 558
Isopropyl alcohol (2-propanol),230
4-Isopropylbenzaldehyde, 803
Isopropylbenzene (cumene or 2-phenylpropane),
595, 639–40, 641–42
Isopropyl bromide, 276, 314
Isopropyl chloride, 138
Isopropyl compounds, structure, 73, 276
1-Isopropyl-1-methylcyclohexane, 205
1-Isopropyl-2-methylcyclohexane, 208–10
Isopropyl-4-methylphenol, 669
Isopropyl phenyl ketone (2-methyl-1-phenyl-1-
propanone), 769
p-Isopropyltoluene,669
Isoquinoline, 602, 761
Isothiocyanates, 921, 1198–99, 1206, 1218
1-Isothiocyanato-(4R
)-(methylsulfinyl)butane, 921
Isotope effect, 273n3, 1109
Isotopes and their abundances in nature, 700
Karplus curve, 731–32
Kauzmann, Walter, 42–43, 51, 51n1
Kekulé forms, 575–77
Kekulé von Stradonitz, Friedrich August, 574,
574n2
Ketals. See Acetals
Ketene (ethenone), 883, 888, 921
Ketenes
from acid chlorides, 912, 924
from Arndt–Eistert reaction,917
bonding, 887–88
formation by Wolff rearrangement, 916–18,
924
infrared spectra, 888
nomenclature, 883
reactions, 907, 922, 1206
structure, 515–16, 877, 1206
See also Cumulated double bonds
-Keto acids, decarboxylation, 858–59, 870,
959–60
Ketocarbenes, 915–16
Keto–enol tautomerization, 939–40, 944, 961, 966
-Keto esters
from Claisen condensation,987–89, 991, 992,
997, 1013
cyclic -keto esters, 992–93
in fatty acid metabolism, 997
hydrolysis and decarboxylation, 959–62, 963,
1014
in reverse Claisen condensations, 992, 997
in synthesis of ketones, 959–62, 963, 1014
See also Esters
-Ketoglutaric acid, 1185
Ketones
acetals as protecting groups, 788–89
from acid chlorides, 891–92, 912, 924
acyl benzenes, 644
aldol condensation, 971–74
alkylation of enolates, 955–56, 1012
Baeyer–Villiger reaction, 907–9, 924
Beckmann rearrangement, 909–11, 923
from carboxylic acids, 856–57, 858–59, 870
diazo ketones, 915–18, 924
diones (diketones), 768
enolates, 933–42
formation from nitriles, 905, 924
formation from ozonides, 440–42, 459
from Friedel–Crafts acylation, 644, 687, 893,
924
haloform reaction of methyl ketones,948–50,
1012, 1013
halogenation at position, in acid, 946–48,
1013
halogenation at position, in base, 948–50,
1013
from hydration of alkynes, 448–50, 451, 459
infrared (IR) spectroscopy, 770–71
from -keto acid decarboxylation, 858–59, 870
Knoevenagel condensation, 974–76, 1014
nomenclature, 767–69
from oxidation of alcohols, 803, 804–6, 818
pK
a
values, 933
production from enols, 448–50
reaction with ester enolates, 974–76
reaction with metal hydrides to form alcohols,
801–3, 817
reaction with organometallic reagents to form
alcohols, 801, 817
resonance forms, 885
synthesis from -keto esters, 959–62, 963,
1014
transformation into enolates, 652
ultraviolet spectroscopy, 771, 772
Ketoses, 1128, 1141
Keto sugars, 1130
Ketotriose, 1128
Kharasch, M. S., 482, 482n2
Kiliani–Fischer synthesis, 1138–40, 1153–54,
1160
Kilojoule (kJ), 4n5
Kinetic control, 353, 359, 537–41
Kinetic enolates, 984, 985, 986, 1008
Kinetic resolution, 1185
Kinetics
definition, 351
energy barrier height effect on reaction rate,
334, 339–40
Hammond postulate, 355–57, 377
mountain pass analogy to energy barriers, 331,
346, 627
overview, 339–40
rate constant (k), 268, 289, 341, 349
rate-determining step,294–95, 350–51, 359
temperature effect on reaction rate, 340
thermodynamics versus kinetics effect on rates,
351–57, 359–60
Kishi, Yoshito, 1009
Knoevenagel condensation, 974–76, 1014
See also Aldol condensation
Koenigs–Knorr reaction, 1149
Kolbe electrolysis, 860, 861, 870
Kroto, H. W., 603–4
Lactams (cyclic amides), 851, 870, 873, 882, 910,
924
Lactase, 1164, 1164n6, 1165, 1166
Lactate dehydrogenase, 1192
Lactones (cyclic esters, oxacycloalkanones)
cyanogen bromide cleavage of peptides,
1200–1201
Fischer esterification, 849, 870
-lactones, 849, 880, 1084–85
nomenclature, 849, 880
synthesis, 849, 909, 925, 1081–82
Lactose, 1161–64, 1164n6
Ladenburg, Albert, 574
Ladenburg benzene
(tetracyclo[2.2.0.0
2,6
.0
3,5
]hexane or
prismane), 216, 573–74
Lanosterol, 561
LDA. See Lithium diisopropylamide (LDA)
Lead, 650
Lead dioxide, 650n3
Leaving groups
ammonia, 902
in benzene halogenation, 638
effect on S
N
1 reactions, 281, 295, 343, 347
I-16 INDEX
epoxidation reactions, 424, 427, 429
ether cleavage by haloacids, 282–83
in formation of dinitrogen trioxide,647
good and poor leaving groups and conjugate
acids, 235, 281
hydroxide conversion to water, 235, 281–82,
322, 555
and inversion of configuration, 270–71
nitrite, 647
nitrogen (N
2
), 848
pyrophosphates, 555–59
in S
N
2 reactions, 262, 267–68, 281, 343–44, 350
in S
N
Ar reactions, 677–78
sulfonate reactions,281–86, 322, 427, 555, 1085
tosylates, 283–84, 305, 555, 798, 1093
Le Châtelier, Henri Louis, 336n3
Le Châtelier’s principle, 336, 336n3
Lehn, Jean-Marie, 254
Lehrer,Thomas, 224, 224n1
Leucine, 1176, 1203, 1204, 1205
Levorotatory, 156
Lewis,Gilbert Newton,14, 42
Lewis acids
borane, 92
boron trifluoride, 264–65, 390
definition, 42, 265
as electrophiles, 42, 390, 625
HOMO–LUMO interactions, 266–67
methyl cation, 91, 264–65
molecular orbital stabilization, 42, 91–92, 265,
321
overview, 264–65
See also Acid–base chemistry
Lewis bases
definition, 42, 265
Grignard reagents, 228, 429
HOMO–LUMO interactions, 266–67
leaving group in substitution reactions, 267
molecular orbital stabilization, 42, 91, 265, 321
as nucleophiles, 42, 267
nucleophilicity, 278–81, 463, 605
organolithium reagents, 229, 429
overview, 264–65
Lewis structures
ammonia, 17
ammonium ion, 21
construction, 14, 16–22
conventions for drawing, 16–17, 44
double and triple bonds, 18–19
ethane, 18
ethene or ethylene, 18
ethyne or acetylene, 18
fluorine, 14
formal charge, 20–22
hydrogen,14
hydrogen fluoride,14
methane, 17
methyl anion, 21
nitromethane, 23
nonbonding electrons, 14, 17, 19
See also Covalent bonds
Limonene, 121, 558
Lindlar catalyst, 452, 458
A-Linolenic acid (ALA; octadecatrienoic acid), 865
Lipscomb, William, 217
Lithium aluminum hydride (LiAlH
4
, LAH)
alcohol synthesis from acid chlorides, 891, 922
alcohol synthesis from epoxides, 429–30, 458
alcohol synthesis from esters, 900
primary alcohol synthesis from carboxylic
acids, 858, 869
reaction with amides, 900
reaction with organic halides, 798
reaction with water, 798
See also Organolithium reagents
Lithium benzoate, 832
Lithium diisopropylamide (LDA)
alkylation of carboxylic acids, 957, 1012
alkylation of esters, 963
alkylation of ketones, 956
Claisen–Schmidt condensation (crossed aldol
condensation), 984–85, 1008
crossed aldol condensation of esters and
ketones, 986
and deprotonation, 944, 984
and enolate formation, 944, 954, 957, 963, 984
Lobry de Bruijn–Alberda van Ekenstein reaction,
1141–42
Lone-pair electrons, 14, 62
Long-range coupling, 731, 736
Loschmidt, Johann Josef, 574, 574n2
Lowest unoccupied molecular orbital (LUMO)
fluoride, 266
HOMO–LUMO interactions in cycloaddition
reactions, 1043–48
HOMO–LUMO interactions in S
N
2 reactions,
271–72
hydrogen chloride addition to 2,3-dimethyl-
2-butene, 134
interactions in Lewis acid–Lewis base
reactions, 266–67
interactions in S
N
2 reactions, 271–72
overview, 133
ultraviolet/visible (UV/vis) spectroscopy,
528–29
LSD (lysergic acid diethylamide), 1026
LUMO. See Lowest unoccupied molecular orbital
(LUMO)
Lycopodine, 214
Lysine, 1177, 1180, 1202
D-Lyxose, 1129, 1139, 1159, 1170
M 1 peak, 700–701
M 2 peak, 706
Magid’s second rule, 999
Magid’s third rule, 1007
Magnetic fields
applied magnetic field (B
0
) in NMR, 714–15,
720, 724, 725, 726, 727
effect of field strength on chemical shift
716–17, 718, 722, 735, 738
induced magnetic field (B
i
) in NMR, 720, 724,
725, 726
mass spectrometry, 700, 702
Magnetic resonance imaging (MRI), 88, 713
See also Hydrogen nuclear magnetic resonance
spectroscopy (
1
H NMR); Nuclear
magnetic resonance spectroscopy (NMR)
Maitotoxin, 745
Maleic acid, 830, 881
Maleic anhydride, 875, 881, 894
Malic acid, 274
Malonic acid (diethyl malonate or propanedioic
acid), 830, 961–62
Malonic ester synthesis, 961
Maltose, 1161, 1170, 1172
Manganese dioxide, 806
Mannich reaction, 1003–4, 1013
D-Mannopyranose, 1141, 1142
D-Mannose, 1129, 1141–42, 1146, 1147, 1153–58
Markovnikov addition, 376, 379–84, 394, 399–400
See also Anti-Markovnikov addition
Markovnikov’s rule, 375, 375n2, 380, 399
Mass number, 5
Mass spectrometry (MS)
acetone, 772
acylium ion, 704
alkanes, 705
base peak, 702
benzyl cation, 703–4
bicyclo[4.2.2]deca-2,4,7,9-tetraene, 707
bromine, 706, 750
bromoethane, 702
1-butanol, 705–6
butene radical, 705–6
tert-butyl chloride, 702, 703
carbonyl compounds, 704, 772
chlorine, 702, 706, 750
chloroethane, 702
cyclohexane, 700–701, 702
daughter ions, 702
3,4-dihydro-2H-pyran, 700, 701, 702
fragmentation patterns, 702–6
history and background, 696
isotope peaks, 700–701
isotopes and their abundances in nature, 700
M 1 peak, 700–701
M 2 peak, 706
mass spectrometers, 699–701
mass-to-charge ratio (m/z), 700
molecular ion, definition, 700
MS measurements, 701–9
parent ion (p), 702
radical cation formation, 699
toluene, 702–3
Meerwein–Ponndorf–Verley–Oppenauer (MPVO)
equilibration, 1005–7, 1012, 1014
Meisenheimer complex, 675
Menthol, 558
Menthyl chloride, 328–29
Mercaptans. See Thiols
Mercaptides, 253, 267, 313
Mercuric acetate, 421–22
Mercurinium ion, 423
Merrifield, R. Bruce, 1208, 1210
Meso compounds, 168–69
Messenger RNA (mRNA), 1214–15
Meta (m-) substitution, definition, 596, 656
See also Substitution reactions of aromatic
compounds
Methanamine (methylamine), 241
Methane
13
C NMR spectroscopy, 88
biochemistry, 92–93
bond angles, 52, 57, 58
bond dissociation energy (BDE), 57
bond strength, 57
clathrates (methane hydrate), 58–59
combustion, 68, 342
heat of formation, 115
homolytic bond cleavage, 57, 63
Lewis structure, 17
molecular orbitals, 57
photohalogenation, 490–93
sp
3
hybrid orbitals, 56–57
structure, 51
unhybridized model, 58–59
(),
INDEX I-17
Methanethiol (methyl mercaptan), 252
Methanol (methyl alcohol), 230
Methide ion. See Methyl anion
Methine group, 75
Methionine, 106, 1176, 1182, 1200–1201
Methoxide ion, 236, 238, 307, 315, 316
Methoxyethane (ethyl methyl ether), 250
Methoxymethane (dimethyl ether), 250, 314
2-Methoxypropane, 732
N-Methylacetamide, 888
Methyl acetate, 888, 898
Methyl acetate (methyl ethanoate)
infrared stretching frequency, 888
structure, 879
Methylamine (methanamine, aminomethane), 241,
243, 318
Methyl anion
acid–base chemistry, 129, 130
formal charge, 21
formation, 62
Lewis structure, 21
sp
3
hybrid orbitals, 63
structure, 63, 477
N-Methylazacyclooctane
(heptamethylenemethylamine), 242
Methyl bromide, 223, 493, 507
2-Methyl-1,3-butadiene. See Isoprene
3-Methyl-1,2-butadiene, 514
3-Methylbutanamide, 882
Methyl butanoate, 737–38
3-Methylbutanoic acid, 882, 918
2-Methyl-2-butanol, 389
2-Methyl-1-butene, 299–300, 374–75
2-Methyl-2-butene
addition of hydrogen chloride (HCl), 138
from 2-bromo-2-methylbutane, 299–300
hydroboration, 397
protonation, 354, 356
protonation and carbocation formation,
354–56
stereochemistry, 144
structure, 138, 144
3-Methyl-1-butene, 386–87
3-Methyl-3-buten-1-ol, 555
3-Methyl-2-buten-1-ol pyrophosphate,556
3-Methyl-3-buten-1-ol pyrophosphate
(isopentenyl pyrophosphate), 555–56
Methyl cation
formation, 62
as Lewis acid, 91, 264–65
sp
2
hybrid orbitals, 63, 133, 377, 477
structure, 63, 133, 477
See also Carbocations
Methyl chloride, 91, 490–93
Methyl compounds, 60–62, 275
Methyl cyanide (acetonitrile), 345–46
(E)-1-Methylcycloheptene, 118
(Z)-1-Methylcycloheptene, 118
2-Methyl-1,3-cyclohexadiene, 110
Methylcyclohexane, 194–201
2-Methylcyclohexanone, 955–56
1-Methylcyclohexene, 110
3-Methylcyclohexene, 110
1-Methylcyclopentene, 394
Methyl diazoacetate, 431
Methylene chloride, 490–93, 721
Methylenecyclohexane, 407, 812–13
3-Methylenecyclohexene, 546
Methylene group, 72, 109
Methylene molecule, 49, 55
Methyl
D-glucopyranoside, 1147, 1149, 1151, 1152
3-Methyl-1,3-heptadiene, 110, 112
Methylhexanes
2-methylhexane, 82
3-methylhexane, absolute configuration,
152–53, 154, 176
3-methylhexane, chirality, 151, 160–61
3-methylhexane, optical activity, 156, 157, 158
3-methylhexane, stereochemistry, 149
structures, 82
Methyl iodide, 340, 344–46
Methylketene (1-propen-1-one), 883
2-Methylpentanal, 767
3-Methylpentane, 149, 150–51, 158
3-Methylpentanoic acid, 879
3-Methyl-2-pentanone (sec-butyl methyl ketone),
768
4-Methyl-3-penten-2-one (mesityl oxide), 971
4-Methylphenol, 669
3-Methylpiperidine, 242
2-Methylpropane, 494–95
Methyl propanoate, 713
Methyl radical
bonding models, 99–103
formation, 63, 469–70
hybrid orbitals, 99–101
methyl ions and radicals as reactive
intermediates, 62
molecular orbitals, 101
structure, 63–64, 100–101
10-Methylstearate, 142–43, 401–2
2-Methyltetrahydrofuran, 1087
Methyl vinyl ether, 378–80
Mevalonic acid, 358
Micelles, 866, 867
Michael reaction,976–80, 998–99, 1016
See also Aldol condensation
Microscopic reversibility, 346, 359
Molecular ion, 700
Molecular orbitals
alkenes, 103–4
allyl cation (allylic cation), 369–70
antibonding molecular orbitals (
antibonding
,
A
), 32–35, 44
antibonding sigma orbitals 54
background, 30–31
benzene, 578–79
beryllium hydride, 54–55
bonding molecular orbitals (
bonding
,
B
),
32–35, 44
1,3-butadiene (methylallene), 520–21
conjugated dienes, 520–21
cyclobutadiene, 585
definition, 3, 30
degenerate orbitals, 584–85, 586, 588–89, 591,
592, 635
empty orbitals, 34, 34n8, 40
ethane, 68, 103
ethylene, 103–4
ethylene (ethene), 103–4
hydrogen molecule, 31–35
low-energy orbitals and bond stability, 35,
36–41
methane, 57
methyl radical, 101
nodes, 32
nonbonding orbitals, 32–33
orbital interaction diagrams, 33–34
orthogonal orbitals, 34
rules for constructing, 34–35, 44–45
See also Frost circles
Molozonides, 437
Monosaccharides, definition, 1161
Morphine, 121, 255, 256, 408
Morpholine, 242
MPVO. See Meerwein–Ponndorf–
Verley–Oppenauer (MPVO)
equilibration
Murexine, 605
Muscarine, 184
Mustard gas [bis(2-chloroethyl)thioether], 1089
Mycobacterium tuberculosis, 143
Mylar, 852
Myristic acid and myristates,862, 863, 997
n 1 rule, 727–29, 735–36
NADH (reduced nicotinamide adenine
dinucleotide), 358, 814, 1140, 1185, 1186,
1216
NAD
(nicotinamide adenine dinucleotide), 679,
813–15, 1185
NADPH, 996
Naming conventions. See Nomenclature
Napalm, 1089
Naphthalene, 179, 592, 602, 605, 622
Narbomycin, 182
Natural products, definition, 86
N-Bromosuccinimide (NBS), 500–501, 507, 543,
613, 618, 953
Neighboring group effect
acetolysis in intramolecular replacement
reactions, 1085–87
anchimeric assistance, 1089, 1100
aromatic neighboring groups, 1096–99
bicyclic systems, 1090–93
cis-2-butene, conversion to 2,3-dibromobutane,
1093–96
carbon–carbon double bonds as intramolecular
nucleophiles, 1099–1108
-carboxylate reaction with methyl alcohol,
1083–85
Coates’cation, 1117
cyclic hemiacetal formation, 783–84, 1083
halogens, 1093–96
heteroatoms with nonbonding electrons,
1083–96
intramolecular reactions of endo and exo
bicyclic amines, 1090–92
intramolecular S
N
2 reactions, 316–17, 917,
1081–88, 1091, 1095, 1101
isotope effect, 1109
3-methyl-2-butyl tosylate reaction with acetic
acid, 1108–9
7-norbornenyl tosylates reaction with acetic
acid, 1099–1108
overview, 1081–83, 1118
oxirane formation from halohydrins, 1083
oxygen in intramolecular displacement
reactions, 1085–87
3-phenyl-2-butyl tosylate conversion to
3-phenyl-2-butyl acetate, 1096–99
problem solving clues, 1082, 1089
single bonds as neighboring groups, 1108–16
solvolysis reaction of exo- and endo-2-
norbornyl tosylate, 1110–16
sulfur compounds, 1085–86, 1088–89
unexpectedly rapid rate as clue, 1088–89,
1099–1100, 1103–4, 1106–8, 1109–13
££
(*),
£
£
I-18 INDEX
unexpected or backward stereochemical results
as clue, 1083–85, 1089–91, 1093–94,
1095, 1097, 1111–14
unusual rearrangement reactions as clue,
1086–87, 1089, 1108, 1111, 1113
Neomenthyl chloride, 328–29
Neon,3,4,6
Neopentane, 76, 77
Neopentyl alcohol, 389
Neopentyl iodide (1-iodo-2,2-dimethylpropane),
389
Neutral methyl. See Methyl radical
Newman, Melvin S., 65
Newman projections, 65–66, 94
Nicol prisms, 157–59
Ninhydrin, 1187–89, 1196
Nitrate ion, 45
Nitration of aromatic compounds, 637–38, 664,
668–69, 673, 687
Nitrenes, 918–19
Nitric acid, 806, 809
Nitriles (cyanides)
acid–base chemistry, 885–86
acid-induced hydrolysis, 904–6
base-induced hydrolysis, 905
enol-like conjugated bases, 942
infrared spectra, 888
and metal hydrides, 906
nomenclature, 883
and organometallic reagents, 905–6
reactions, 904–6, 923
structure, 877, 887
synthesis, 911, 925
Nitroacetamidobenzene, 670
Nitrobenzene
1,3,5-trinitrobenzene, 668
bromonitrobenzene, 672
chlorodinitrobenzene, 674, 675
chloronitrobenzene, 668
dinitrobenzene, 663, 668
inductive effects, 666
meta substitution, 663–64
from nitration of benzene, 621, 637, 687
nucleophilic substitution reactions of
nitrobenzenes, 674–76
para substitution, 664
reduction to aniline, 646, 651, 686
Nitro group
conversion to amino group, 646, 672, 686
effect on electrophilic aromatic substitution,
664, 666, 669, 679
as a functional group, 22
in Meisenheimer complex, 675
in nucleophilic aromatic substitution, 674–75,
679, 680
positive charge on nitrogen,663–64
Nitromethane, 22–25, 28, 45, 239
Nitrones, 436
Nitronium ion,621, 637–38
4-Nitrophenol (p-nitrophenol), 596
Nitrosamines, 647
N-Nitrosoaniline, 647–48
N-Nitroso-N-methylurea, 875
Nitrotoluene,669
Nitrous oxide, 436
NMR. See Nuclear magnetic resonance
spectroscopy (NMR)
Noble gases, 3–6
Nodes, 6, 11–12, 32
Nomenclature
acid halides, 880–81
acyl compounds, 879–83
alcohols, 230–31
aldehydes, 767
alkanes, 78–81
alkenes, 110–12
alkyl compounds, 78–81
alkyl halides, 225–26
alkynes, 126, 127
amides, 882
amines, 240–42
amino acids, 1175–77
ammonium ions, 242
anhydrides, 881
bicyclic compounds, 214–15, 551–52
Cahn–Ingold–Prelog priority system, 111,
112–15
carbohydrates, 1126–38
carbonyl compounds, 767–69
carboxylic acids, 830–32
common prefixes, 81
cycloalkanes, 84
cycloalkenes, 110
ethers, 250
fatty acids, 862
hydroxyl group, 111
International Union of Pure and Applied
Chemistry (IUPAC) system,78–81
ketenes, 883
ketones, 767–69
lactones, 849, 880
lactones (cyclic esters), 880
nitriles, 883
thioethers (sulfides), 252–53
thiols (mercaptans), 252
Nonbonding electron in Lewis structures, 14, 17,
19
Nonbonding orbitals, 32–33
Nonreducing sugars, 1166
Nonsteroidal antiinflammatory drugs (NSAIDs),
688
Norbornyl system
norbornane (bicyclo[2.2.1]heptane), 186, 306,
1099n2, 1100
7-norbornenyl tosylates reaction with acetic
acid, 1099–1108, 1099n2
solvolysis reaction of exo- and endo-2-
norbornyl tosylate, 1110–16
Nuclear magnetic resonance spectroscopy (NMR)
applied magnetic field (B
0
), 714–15, 720, 724,
725, 726, 727
carbon nuclear magnetic resonance
spectroscopy (
13
C NMR), 88–90, 94,
740–42
convention for reporting NMR signals, 742
decoupling, 733, 739, 740–41, 746
DEPT (distortionless enhancement with
polarization transfer), 741
dynamic NMR, 746–49
energy difference between spin states, 714–16,
720
flipping a nuclear spin, 714–15, 720
gyromagnetic ratio 715–16, 734, 740
history and background, 526, 696, 696n2, 716
induced magnetic field (B
i
), 720, 724, 725, 726
magnetic resonance imaging (MRI),713
NMR spectrum, definition, 88
nuclear spin (I), 88, 714–15, 727–28
overview, 88–90, 713–17
ppm scale, 716–17
problem solving techniques, 89, 889
protein structure determination, 1192n3
tetramethylsilane (TMS) standard, 716–17,
720–21
See also Chemical shift Hydrogen nuclear
magnetic resonance spectroscopy (
1
H
NMR); Spin–spin coupling
Nucleic acids
alkylation of DNA, 288, 615–16
base pairs, 288, 615, 1212–13, 1214
bases, 288, 614–15
DNA double helix, 598, 1213
DNA replication, 1213
DNA structure and composition, 614–16,
1149, 1211–13
enzymatic epoxidation, 616
hydrogen bonding, 288, 615, 1212–13
messenger RNA (mRNA), 1214–15
mutation, 288–89, 615–16
nucleosides, 1210–11
nucleotides, 614–15, 1211–12, 1213, 1214
(pi) stacking in DNA, 598, 615
and polyaromatic hydrocarbons, 614–16
RNA codons for amino acids,1214–15
RNA structure and composition,93, 614–15,
1149, 1214
transfer RNA (tRNA), 1215
Nucleophiles
effect of solvent polarity, 279–81
effect on S
N
2 reactions, 277–81
Lewis bases,42, 267, 278–81, 463, 605
nitrogen, 317–18
oxygen, 315–17
pyridine as nucleophile, 602
relative nucleophilicity of common species, 279
sulfur compounds, 313–14
Nucleophilic aromatic substitution. See S
N
Ar
reactions
Nucleophilicity, 278–81, 463, 605
Nucleosides, 1210–11
Nucleotides, 614–15, 1211–12, 1213, 1214
Nucleus, 2
Nylon (polyamide), 852, 898
Ockham, William of, 590n3
Ockham’s razor, 590
Octanes, 195–96
trans,cis,trans-2,4,6-Octatriene, 1041
1-Octene, 380, 753
2-Octene, 753
Octet rule, 4
Off-resonance decoupling, 740–41
Oils, definition, 862
Olah, George A., 680
Oleate, 142–43
Olefins, 123
See also Alkenes
Oleum, 636
Opsin, 533
Optical activity, overview, 155–59
Orbital interaction diagrams, 33–34
Orbitals, overview, 3, 4
See also Atomic orbitals; Molecular orbitals;
Wave functions
Organic foods, 312
Organocuprates, 430, 458, 797–98, 893, 924
()
();
(),
INDEX I-19
Organolithium reagents
aluminum tri-tert-butoxyhydride, 892
amide formation with alkyllithium reagents,
249
butyllithium, 1001–2
destruction by water, 799–800, 818
deuterolabeled molecule formation, 229–30,
257, 797
dithiane alkylation, 1001–2
ether or tetrahydrofuran (THF) solvents, 228
hydrocarbon formation,229
as Lewis bases,229, 429
lithium triethylborohydride, 798
protonation, 229
reaction with acid chlorides, 891
reaction with aldehydes and ketones to form
alcohols, 799–802, 817
reaction with carboxylic acids, 856–57, 870
reaction with esters, 899
reaction with oxiranes,429–30, 458
S
N
Ar reaction, 677
structure, 229
synthesis from alkyl halides, 228, 229, 257,
797, 818
See also Lithium aluminum hydride
Organometallic reagents
from alkyl halides, 227–29, 256, 797
as carbanion equivalents, 429
definition, 227–28
destruction by water, 799–800, 818
hydrocarbon synthesis, 229, 257
lithium aluminum hydride, 429–30, 458
overview, 227–30, 797–99
reaction with acid chlorides, 891–92
reaction with aldehydes and ketones to form
alcohols, 799–802, 817
reaction with CO
2
, 840–41
reaction with D
2
O, 229–30, 797
reaction with epoxides,429–30, 797
reaction with oxiranes,429–30
See also Grignard reagents; Organolithium
reagents
Ortho esters, 846–48
Orthogonal orbitals, 34
Ortho (o-) substitution, definition, 596, 656
See also Substitution reactions of aromatic
compounds
Osazones, 1145–46, 1147, 1158, 1159
Osmium tetroxide,443–44
Oxabenzene, 599
2-Oxacyclobutanone,849
2-Oxacycloheptanone, 880
2-Oxacyclohexanone, 849
Oxacyclopentanone,849, 880
Oxacyclopropanone, 849
Oxalyl chloride, 928
Oxaphosphetanes, 811–12
Oximes, 793, 909–10, 911
Oxiranes
definition, 317
1,2-diol formation, 426–27
ethylene oxide, 231
mechanisms for opening in acids and bases,
427–29
reaction with organometallic reagents, 429–30,
458
regiochemistry of ring opening, 427–29
single-step epoxidation, 424–25, 459
synthesis by asymmetric (Sharpless)
epoxidation, 426
synthesis by Williamson ether synthesis, 317
synthesis from halohydrins,317, 1083
See also Epoxidation; Epoxides
3-Oxohexanal, 768
Oxonium ions, 140, 235–36, 248–49, 314
2-Oxopropanal (pyruvic aldehyde), 768
Oxygen, 315–17, 484
Oxymercuration, 421–23, 448, 458, 459
Ozone, 46, 437, 441
Ozone depletion, 467
Ozonides, 437–42, 459
Ozonolysis, 437–42
P-450 monooxygenase,616
Paige, Leroy Robert “Satchel,” 262, 262n1
Paired spin, 8
See also Electron spin
Palmitic acid and palmitates, 862–63, 997
Palytoxin, 1009
[n]Paracyclophane, 628–29
Parallel spins, 10
Para (p-) substitution, definition, 596, 656
See also Substitution reactions of aromatic
compounds
Parent ion (p), 702
Pascal’s triangle,729
Patulin,532
Pauli, Wolfgang, 8
Pauli principle,8, 34
Pedersen, Charles J., 254
Penicillin V, 531
1,3-Pentadiene, 539–40, 1048–52
1,4-Pentadiene, 512, 519, 524
2,3-Pentadiene (1,3-dimethylallene), 513, 514
Pentanal, 767
Pentane, 76–77, 82, 87–88, 95
2,4-Pentanedione, 768
Pentanoic acid (valeric acid), 830, 849
, 880
1-Pentanol. See Amyl alcohol
2-Pentanone, 771, 1008
Pentanoyl chloride, 880
Pentoses, definition, 1127, 1130
Pentyl compounds,77
Peptide and protein synthesis
automatic procedure using Merrifield machine,
1208–10
biological synthesis from RNA, 1214–15
Cbz (benzyl chloroformate), 1205, 1207–8,
1217
conversion of carboxy end into ester, 1205
dicyclohexylcarbodiimide (DCC), 1205–7,
1209, 1217
protecting groups, 1205, 1207–10
RNA codons for amino acids,1214–15
tBoc (di-tert-butyl dicarbonate),1205–10
undesirable reactions, overview, 1202–4
Peptides
-helix, 1191, 1192
amino terminus, 1189, 1197
carboxy terminus, 1189
chromatographic separation,1195–96
cleavage by carboxypeptidases, 1197–98
cleavage by chymotrypsin, 1202
cleavage by cyanogen bromide (BrCN),
1200–1201
cleavage by trypsin, 1202
definition, 1175
denaturing, 1193–94
dicyclohexylcarbodiimide (DCC), 1205–7,
1209, 1217
disulfide bridges, 1190, 1193, 1194–95, 1216
Edman degradation, 1198–1200, 1202, 1218
hydrogen bonds, 1190–91, 1192, 1194
nitrogen-to-carbon link, 224
nomenclature, 1189
peptide bond, definition, 1175, 1195
-pleated sheets, 1191
primary structure, 1190
random coil, 1191
reaction with 2,4-dinitrofluorobenzene, 1196,
1197
Sanger degradation, 1196–97, 1202
secondary structure, 1191–92, 1193
structure, 1189–94
tertiary structure, 1192–94
See also Peptide and protein synthesis
Peracids, 424
Pericyclic reactions
definition, 1031
how to work orbital symmetry problems,
1071–73
overview, 1031–32, 1073–74
See also Concerted reactions; Cycloaddition
reactions; Electrocyclic reactions;
Sigmatropic shift reactions
Periodic acid, 807, 1151
Perkin, William Henry, 648
Peroxidate ion, 399
Peroxides
acyl peroxides, 476
alkyl peroxides, 253, 476
anti-Markovnikov HBr addition to alkenes,
482, 485, 506
carboxyl radicals from acyl peroxides, 476
hydrogen peroxide reaction with boranes, 398,
451
instability, 253
oxidation of ozonides, 441
radical production from alkyl peroxides, 476
structure, 253, 424
weak O–O bond, 476, 482, 483
Phenanthrene, structure, 179, 603
Phenanthro[3,4-c]phenanthrene (hexahelicene),
179, 180
Phenol (benzenol or hydroxybenzene), 231, 595,
670, 942
Phenols, 649, 652, 670, 687
Phenonium ion, 1098, 1110
Phenoxide, 652
Phenylalanine
from aspartame hydrolysis, 1164
biosynthesis, 682–84, 1063
structure, 1175, 1176, 1180, 1183
synthesis, 1183
Phenyl cation, 650, 675
Phenyl formate (phenyl methanoate), 879
Phenylhydrazones,
793, 1126, 1145–46
Phenylisothiocyanate, 1198–99
Phenylketene (2-phenylethen-1-one), 883
N-Phenylmaleimide, 894
Phenyl (Ph), 595, 596
Phenyl propyl ketone (butyrophenone),644
Phenylpyruvate, 684
Phenyl radical, 650
Phenylthiohydantoins, 1199, 1200, 1218
Pheromones, 534
Phosgene, 880, 899,
924
Phosphonium ion, 811
Phosphorus pentachloride, 322, 853, 868
I-20 INDEX