Jones M., Fleming S.A. Organic Chemistry
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Index
Note: Footnotes are indicated by n after the page number. Material in figures or tables is indicated by italic page numbers.
I-1
Absolute configuration, 152–55, 172–73, 181
Abstraction, definition, 471
Acenaphthylene, 417
Acetaldehyde (ethanal)
acid-catalyzed hydrogen exchange reactions,
938–39, 970
aldol condensation, 965–66, 970
base-catalyzed hydrogen exchange reaction,
936–38
from biological oxidation of ethanol, 814–15
boiling point, 770
deuterioacetaldehyde, 815
dipole moment, 766
equilibrium between carbonyl and enols forms,
940–41
equilibrium in hydration reactions, 777–80
hydrate formation,965–66
infrared stretching frequency, 888
NMR properties, 889
pK
a
, 936
solubility, 770
structure, 764, 767
Acetals
formation in acid, 786, 791–92, 817, 846–48
glycosides, 1148–52, 1210
hemiacetal intermediate formation in acid,
784–86, 790, 818
hemiketals and ketals, 786n2
as protecting groups for aldehydes and ketones,
788–89
structure, 786, 846
tetrahydropyranyl (THP) ethers as protecting
groups for alcohols, 789–90
See also Carbonyl compounds, addition
reactions; Hemiacetals
Acetamide (ethanamide), 882, 943
Acetamidobenzene (acetanilide), 670, 671
Acetamidomalonic ester, 1183
Acetate ion resonance stabilization, 421
Acetic acid (ethanoic acid)
abbreviation, 421, 1085
acetolysis in intramolecular replacement
reactions, 1085–87
from hydrolysis and decarboxylation of
malonic acid, 961–62
infrared (IR) spectroscopy, 833, 888
physical properties, 830
pK
a
, 1179
structure, 849, 879, 880
uses, 45
Acetic anhydride (ethanoic anhydride), 881, 888
Acetic propionic anhydride (ethanoic propanoic
anhydride)
structure, 881
Acetoacetate synthesis, 959–60, 963, 1014
Acetone (dimethyl ketone, propanone)
aldol condensation, 971–73
base-catalyzed carbonyl–enol equilibrium,
935
boiling point, 770
dipole moment, 766
enolate, structure, 895
equilibrium between carbonyl and enols forms,
940–41
equilibrium in hydration reactions, 777–78, 781
infrared stretching frequency, 888
mass spectrometry, 772
NMR properties, 889
solubility, 240, 770
structure, 768
Acetonitrile (ethanenitrile, methyl cyanide), 883,
887, 889, 943
Acetophenone (methyl phenyl ketone), 769
Acetyl chloride (ethanoyl chloride)
acylation reactions, 670, 1187
infrared stretching frequency, 888
NMR properties, 889
reaction with carbohydrates,1147
structure, 880, 893
Acetylcholine, 217
Acetyl-CoA, 862–63, 997
Acetylene (ethyne)
bonding, 123–25
Lewis structure, 18
molecular formula, 98
structure, 123–24
substituted acetylene synthesis from acetylides,
312–13, 320
welding, 97
See also Alkynes
Acetylide ion, 129–30, 143, 312–13, 320,
517–18
Acetyl salicylic acid (aspirin), 838
Achiral molecules, definition, 150, 150n2
Acid anhydrides. See Anhydrides
Acid–base chemistry
acid chlorides, 886
acidity constant (K
a
), 234
acidity of terminal alkynes, 129–30
acyl compounds, 885–87, 943
alcohols, 232, 233–38
alkanes, 130, 976
alkenes, 130
alkynes, 129–30
amides, 886–87, 943–44
amines, 246–49, 834
amino acids, 1179–81
ammonium ions, 246–48
anhydrides, 886–87
basicity constant (K
b
), 248
carboxylic acids, 834–38
conjugate acids, 234
conjugate bases, 234
esters, 886–87
ethers, 251, 254
heteroaromatic compounds,601–2
methyl anion, 129, 130
nitriles (cyanides), 885–86
overview, 233–35, 320–21
potassium hydroxide reaction with
hydrochloric acid,90, 233–34
pyridine (azabenzene), 601, 620
pyrrole, 601, 621
thiols (mercaptans), 253
water, 234
See also Brønsted acids; Brønsted bases; Lewis
acids; Lewis bases; pK
a
Acid chlorides (acyl chlorides)
acid–base chemistry, 886
addition–elimination reaction, 889–91
AlCl
3
complexes, 643
from carboxylic acids, 643, 853–55, 868,917
conversion to ketenes, 912, 924
Friedel–Crafts acylation, 643–46, 893
general structure, 643, 877
infrared spectra, 888
products of addition–elimination reaction, 890
reaction with lithium aluminum hydride,
891, 922
reaction with organometallic reagents,
891–92
reduction by Rosenmund reduction, 892–93,
923
resonance forms, 885
S
N
Ar reaction of pyridine N-oxides, 678–79
structure, 769
See also Acyl compounds
Acid derivatives, 877
See also Acyl compounds; Carboxylic acids
Acid halides
-bromo acid bromides, 951–52
-bromo acid halides, 951–52
-bromo acids, 950–53, 1182, 1216
nomenclature, 880–81
properties, 880
See also Acid chlorides
Aconitase, 357
cis-Aconitate, 357
Activating agents, 850, 1204–5
Activation energy ( G°)
addition of hydrogen chloride to alkene, 136
additions to alkenes, 136
definition, 136
effect of solvent polarity, 287
energy barrier height effect on reaction rate,
334, 339–40
enthalpy of activation ( H°), 342, 349, 359
mountain pass analogy to energy barriers, 331,
346, 627
and rate constant, 349
S
N
1 reactions, 342–43
S
N
2 reactions, 273–74, 277, 287, 343–46
See also Gibbs free energy ( ); Transition
states
Acyl azides, 918–19, 922
Acyl chlorides. See Acid chlorides
Acyl compounds
acid–base chemistry, 885–87, 943
acyl benzenes from Friedel–Crafts acylation,
644
enolates, 942–44
general formula, 877
infrared spectra, 887–88
mechanism of addition–elimination reaction,
877–78
nomenclature, 879–83
nuclear magnetic resonance spectra, 888–89
nuclear magnetic resonance spectroscopy,
888–89
overview, 877–79, 921–22
physical properties, 884
pK
a
, 943
reaction with lithium aluminum hydride, 891,
900, 922
structures, 884–85
synthesis of other compounds, overview, 890,
922–25
tetrahedral intermediate in
addition–elimination reaction, 877–78,
889
See also specific types
Acyl group, structure, 476, 643
Acylium ion, 643, 645, 646, 704, 772
Adamantanes, 217–19
Adamantylideneadamantane, 416
Adenine, 93, 615, 1149, 1212
Adenosine triphosphate (ATP), 1140
S-Adenosylmethionine, 142, 288, 314, 324,
401–2, 455
Adipic acid (hexanedioic acid), 830, 852
Aflatoxin B
1
, 86, 212
Agarospirol, 211
Ajoene, 252
Alanine, 1175, 1176, 1178, 1189, 1203, 1204
Alcohol dehydrogenase, 400
Alcohols
acid–base properties, 232, 233–38
from acid chlorides, 891, 922
from aldehyde and ketone reactions with
organometallic reagents, 799–802, 817
chemical exchange of OH hydrogens, 733–34,
739
conversion of hydroxide leaving group to water,
235, 281–82, 322, 555
conversion to sulfonates, 281–86, 322, 427, 555
decoupled NMR spectra, 733, 739, 746
deprotonation, 236, 385
1-deuterioethyl alcohol, configuration, 152, 154
hydrogen bonding, 232–33
from lithium aluminum hydride reaction with
acyl compounds, 891, 900, 922
from lithium aluminum hydride reaction with
oxiranes, 429–30, 458
Meerwein–Ponndorf–Verley–Oppenauer
(MPVO) equilibration, 1006–7, 1012
nomenclature, 230–31
oxidation to carbonyl compounds, 802–6, 817
oxidation to carboxylic acids, 805, 817
oxonium ion formation, 235–36
physical properties, 232–33
pK
a
values in water, 236, 249, 316, 834
protonation, 235–36, 281–82
reaction with phosgene, 899
retrosynthetic alcohol synthesis, 807–9
structure, 231–32
synthesis by acid-catalyzed hydration of
alkenes, 139–40, 144, 381–82, 403
synthesis by hydroboration, 398–401, 403
synthesis by oxymercuration, 421–23, 448, 458,
459
synthesis from acyl compounds, 922
synthesis from oxiranes, 429, 458
tetrahydropyranyl (THP) ethers as protecting
groups for alcohols, 789–90
thionyl chloride treatment for chloride
formation, 284–85
treatment with phosphorus reagents, 285
trialkylsilyl ethers as protecting groups,
789–90
See also specific types
Aldaric acids, 1144, 1156, 1157
Aldehyde dehydrogenase, 400
Aldehyde hydrogens, 725
Aldehydes
acetals as protecting groups, 788–89
from acid chlorides, 891–92, 923
aldehyde hydrogens, 725
aldol condensation, 965–70
alkylation of enolates, 955–56, 1012
Baeyer–Villiger reaction, 907–9, 924
bisulfite addition, 781, 818
cyanohydrin formation, 781–82, 818, 1139
dials (dialdehydes), 767
enolate formation, 933–42, 965
from enols, 449, 451, 458
formation from ozonolysis, 440–42
halogenation at position, in acid, 946–48,
1013
halogenation at position, in base, 948–50,
1013
hydrate formation,818, 965–66, 1004
from hydroboration of alkynes, 451, 458
infrared (IR) spectroscopy, 770–71
Knoevenagel condensation, 974–76, 1014
nomenclature, 767
nuclear magnetic resonance (NMR)
spectroscopy, 771–72
from oxidation of alcohols, 802–6, 817
oxidation to carboxylic acids, 805, 817
pK
a
values, 933
reaction with enolates, 965–70
reaction with ester enolates, 974–76
reaction with metal hydrides to form alcohols,
801–3, 817
reaction with organometallic reagents to form
alcohols, 800–801, 817
resonance forms, 885
synthesis by Rosenmund reduction,892–93,
923
ultraviolet spectroscopy, 771, 772
Aldohexoses
definition, 1129
epimerization in base, 1141–42
Fischer determination of structure, 1153–60
hemiacetal formation, 1132
- and -pyranose and furanose forms,
1134–35
ratio of furanose and pyranose forms, 1133
structures, 1129, 1153–60
Williamson ether syntheses,1147
See also Aldoses
Aldol condensation
acid-catalyzed aldol dehydration, 968, 1013
aldehyde reaction with enolates, 965–70
aldol structure, 966
base-catalyzed aldol dehydration, 968–69, 1013
comparison of aldol and Claisen condensation,
988–89, 990
crossed (mixed) aldol condensation, 982–87
definition, 966
-hydroxy carbonyl products, 966, 968, 973–74
intramolecular aldol condensations, 980–81,
999
ketone reaction with enolates, 971–74
Knoevenagel condensation, 974–76, 1014
Michael reaction,976–80, 998–99, 1016
problem solving techniques for real-world
synthesis, 1007–9
rate-determining steps in equilibria, 969–70
reverse aldol reactions,973
Robinson annulation, 998–99
thermodynamic factors, 972, 974, 990
-unsaturated carbonyl dehydration
products, 968–69, 971–72, 973–75, 981,
1014
See also Carbonyl compounds, condensation
reactions; Claisen condensation;
Claisen–Schmidt condensation
Aldonic acids, 1144, 1166
Aldopentoses, 1129, 1158–59
Aldoses
anomers, 1134
definition, 1126
Fischer projections, 1127, 1129–30
hemiacetal formation, 1130–34
osazone formation, 1145–46, 1147
oxidation, 1144–45, 1157
reduction, 1130, 1143
Ruff degradation, 1139–40
See also Aldohexoses; Carbohydrates
Aldotetroses, 1129
Aldotriose, 1126
Alkaloids, 170–72, 255–56
Alkanes
acid–base chemistry, 130, 976
biochemistry, 92–93
chemical shift (δ), 722–23
combustion reactions,68, 92
functional group effect on reactivity, 51
heat of formation 116–18, 126
mass spectrometry (MS), 705
molecular formula, 51, 131
naming conventions, 78–81
nomenclature, 78–81
from organometallic reagent destruction by
water, 799–800, 818
(¢H°
f
),
,
¢G°
¢
¢
I-2 INDEX
overview, 51–52, 93–94
pK
a
, 976
straight-chain alkanes, 79, 86–88
synthesis by Clemmensen reduction, 645, 686,
802
synthesis by desulfuration, 253, 257
synthesis by disproportionation reactions,
471–72, 473–74, 506
synthesis by hydrogenation of alkenes and
alkynes, 452, 458
synthesis by Wolff–Kishner reduction, 645,
686, 802
See also specific types
Alkene halogenation. See Halogenation
Alkene hydrohalogenation
conjugated dienes, 369–70, 404, 534–35,
537–41
definition, 365, 414
HX addition to alkynes, 444–47
HX hydration of alkenes,380–84, 404
mechanism for hydrogen bromide addition,
414
radical alkene hydrohalogenation, 485
radical HX hydration of alkenes, 481–87
rearrangements during HX addition, 386–89,
501
See also Alkenes, addition reactions; Alkyl
halides; Halogenation
Alkenes
acid–base chemistry, 130
biological activity, 142–43
bonding, 99–107
cis and trans coupling constant (J
cis
, J
trans
), 732
derivatives, 107–10
dimerization and polymerization, 384–86,
488–89
heat of formation 116–18, 126, 515
heat of hydrogenation, 580
heats of hydrogenation, 413
isomers, 108–10
molecular formula, 98, 130
molecular orbitals, 103–4
nomenclature, 110–12
overview, 98, 142
physical properties, 123
pi orbitals, 98, 104, 125
relative stability of isomers, 116–18
rotational energy barriers, 105–6, 107,
144, 522
stabilizing effect of 2p/2p overlap, 105–6
structure, 99, 105–7
synthesis by alkyne reduction by sodium in
ammonia, 452–55, 458
synthesis by disproportionation reactions,
471–72, 473–74, 506
synthesis by syn hydrogenation of alkynes,
452, 458
synthesis by Wittig reaction, 811–13, 817
from thermal elimination of esters, 912–14,
923
types of carbon–carbon σ bonds in isomers,
116–17
See also Alkenes, addition reactions;
Cycloalkenes
Alkenes, addition reactions
acid-catalyzed hydration reactions, 139–41,
143, 381–82, 403, 773, 775–76
activation energy ( G°), 136
bromine addition to alkenes, 396
Brønsted acids, general case, 131
carbocation intermediate, 132–33, 135–36, 140
dimerization and polymerization, 384–86,
488–89, 1045–46, 1074
HX hydration of alkenes,380–84, 404
hydrogen chloride addition to 2,3-dimethyl-2-
butene, 131–32, 133–36, 365–67, 374
inductive effects, 378–80
mechanism of hydrogen halide addition,
132–36, 138–39, 365–66
overview, 364–65, 402–4, 410, 456–60
oxidation with permanganate or osmium
tetroxide,443–44
oxymercuration, 421–23, 448, 458
ozonolysis, 436–40
problem solving techniques, 110, 139, 141
protonation step, 133, 365–66, 385
radical addition to alkenes, 481–87, 484–86
radical HX hydration of alkenes, 481–87
radical-induced tetrahalide addition to alkenes,
487–89
rate-determining step,365–66
reaction energetics, 135–36
rearrangements during HX addition, 386–89,
501
regiochemistry, 137–39, 141, 366–72
ring formation through addition reactions, 457
transition states, 136
See also Alkene hydrohalogenation; Alkenes;
Alkynes, addition reactions; Epoxidation;
Halogenation; Hydroboration;
Hydrogenation
Alkoxide ion
comparison to carboxylate anion, 834
from deprotonation of alcohols, 236–37, 249,
315, 834, 1081–82
dimethyl sulfate treatment for methyl ether
formation, 285
formation by sodium hydride, 315
oxirane formation, 317, 1083
from reaction of metallic sodium or potassium
with alcohols, 315
from reaction of sodium hydroxide with
alcohols, 315–16
stabilization by alkyl groups in gas phase, 238
stabilization by solvents, 237
Alkylamines, 241, 247, 318, 1181–82
Alkyl compounds, general, 69, 78–81, 141
Alkyl halides
alkyl bromides from Hunsdiecker reaction,
861, 869
bonding, 226, 227
conversion to organometallic reagents, 227–30,
257
cycloalkyl bromide reactivities in S
N
2 reactions,
276
dipole moments, 226
formation by ether cleavage, 282–83
formation with phosphorus reagents, 285
geminal dihalides, 447, 459
Grignard reagent formation, 228–29, 257
HX hydration of alkenes,380–84, 404
hydrocarbon formation,229–30
nomenclature, 225–26
properties, 225
radical HX hydration of alkenes, 481–87
substitution reactions, 267–68
synthesis by addition of hydrogen halides to
alkenes, 132–36, 138–39, 141, 144
synthesis by protonation of alcohol with
haloacid, 142, 144, 282
synthesis by S
N
1 or S
N
2 reactions, 322
tetrahalide formation from alkynes, 448, 459
from thionyl chloride treatment of alcohols,
284–85
vicinal dihalides, 414, 448, 459, 490, 499, 507
See also Alkene hydrohalogenation;
Halogenation
Alkyl shifts, 387–88, 642
Alkynes
acidity of terminal alkynes, 129–30
alkyne radical anions, 453–54
allenes as intermediates in isomerization,
516–18
derivatives and isomers, 126–28
heats of formation and relative stability, 126
molecular formula, 98, 131
nomenclature, 126, 127
physical properties, 129
pi orbitals, 125
in rings, 128
structure and bonding, 123–25, 128
See also Acetylene; Alkynes, addition reactions;
Triple bonds
Alkynes, addition reactions
HX addition to alkynes, 444–47
hydration,448–50
hydroboration, 450–51
hydrogenation, 452
oxymercuration, 448, 459
radical-induced anti-Markovnikov addition,
489–90, 507
reduction by sodium in ammonia (anti-
hydrogenation), 452–55
tetrahalide formation from alkynes, 448, 459
X
2
reagent addition to alkynes, 447–48
See also Alkenes, addition reactions; Alkynes
Alkynyl hydrogens, 724–25
Allene (propadiene), 178, 513–14, 921
Allenes, 178, 513–15, 516–18
See also Cumulated double bonds
D-Allose, 1129, 1138, 1143, 1145, 1160
Allyl alcohol, 231
Allyl anion (allylic anion),27–28, 543–44,
589, 934
Allyl cation (allylic cation)
delocalization of electrons, 27, 369–70
hydrogen chloride addition to 1,3-butadiene,
369–71
molecular orbitals, 369–70
resonance forms, 27, 28, 369–71, 535
resonance-stabilized formation in S
N
1
reactions, 538, 541–42, 564
S
N
1 solvolysis reactions, 541–42
Allyl compounds, 108, 326
Allyl halides, 404, 541–43, 564, 612
Allylic halogenation, 497–501, 507, 543
Allylic hydrogens, chemical shift 724
Allyl iodide (3-iodopropene), 541, 543
Allyl radical, 475, 480, 498–99, 512, 543
Allyl system, 2p orbital overlap, 369–70, 541
-helix, 1191, 1192
position, definition, 763, 933
See also Carbonyl compounds, reactions at
position
D-Altrose,1129, 1138, 1143, 1160
Aluminum alkoxides, 1005–6, 1012
Aluminum bromide (AlBr
3
), 361, 640, 646, 687
(),
()
¢
()
(¢H°
f
),
INDEX I-3
Aluminum chloride (AlCl
3
)
electrophilic substitution of furan and
thiophene, 654
electrophilic substitution of pyridine,653
Friedel–Crafts acylation, 643–44, 687
Friedel–Crafts alkylation, 639–43, 679, 686
Aluminum tri-tert-butoxyhydride, 892
Amide ions, 249, 313, 454, 516–17, 680–81
Amides (carbonyl-nitrogen compounds)
acid–base chemistry, 886–87, 943–44
acid-induced hydrolysis, 902–3, 922
base-induced hydrolysis, 901, 903, 922
from Beckmann rearrangement, 909–11, 923
biochemistry, 878
from carboxylic acids, 850–52, 869
dicyclohexylcarbodiimide (DCC), 850
enolates, 943
formation by dicyclohexylcarbodiimide
(DCC), 850, 856, 869–70, 1205–7, 1209,
1217
general structure, 249n3, 769, 850, 877
Hofmann rearrangement, 919–20, 923
lactams (cyclic amides), 851, 870, 882, 910, 924
nomenclature, 882
polyamides (nylon), 852, 898
reduction by metal hydrides, 903
resonance stabilization, 884–85, 903, 943
structure, 769, 884–85
See also Acyl compounds
Amines
acid–base chemistry, 246–49, 834
N-acylated aromatic amines, 671
alkylamines, 241, 247, 318, 1181–82
alkylation reactions, 317–18
from amide reduction, 903
amine inversion, 243–44, 257
from carbanic acid decarboxylation, 860, 869
chemical exchange of NH hydrogens, 733–34,
739
condensation reactions,1003–4
cyclic amino compounds, 242
decoupled NMR spectra, 733, 739, 746
diamines, 246
from Hofmann rearrangement, 919–20, 923
hydrogen bonding, 245–46, 247–48
intramolecular reactions of endo and exo
bicyclic amines, 1090–92
Mannich reaction, 1003–4, 1013
from nitrile reduction, 906, 923
nomenclature, 240–42
odor, 246
overview, 224
physical properties, 245–46
pK
b
values, 248, 259, 601
polyfunctional amines, 241
primary amines, 240, 241
reaction with epoxides,318
secondary amines, 240, 241
structure, 243–44
synthesis through S
N
2 reactions, 317–18, 322
tertiary amines, 240, 241
Amino acids
abbreviations, 1175, 1176–77
acid–base properties, 1179–81
acylation reactions, 1187
-amino acids, definition, 1175
chromatographic separation and analysis, 1196
D and L configuration, 1178
electrophoresis, 1180–81, 1195
essential amino acids, 1063, 1077
esterification reactions, 1187
Fischer esterification, 1187
Fischer projections, 1178
Gabriel synthesis, 1182–83, 1216
isoelectric point (p I ), 1176–77, 1179–80
kinetic resolution, 1185
from methane and ammonia, 93
nomenclature, 1175–77
overview, 1174, 1215–18
properties, 1176–77
(R) and (S) configuration, 1178
reaction with 2,4-dinitrofluorobenzene, 1196,
1197
reaction with ninhydrin, 1187–89, 1196
reductive animation, 1185–86
resolution, 1184–86
RNA codons for amino acids,1214–15
side chains (R groups), 1175, 1176–77
simple alkylation synthesis, 1181–82, 1216
Strecker synthesis, 1184, 1216
structure, 1178–79
synthesis, 1181–84, 1185–86
zwitterions, 1179–80
Aminoacyl tRNA synthetase, 1214
1-Aminoadamantane, 219
3-Aminobenzoic acid, 670
-Aminobutyric acid (GABA), 400
cis-4-Aminocyclohexanecarboxylic acid, 831
Amino group, 238, 241, 646, 670–71, 672, 686
2-Aminohexanoic acid (norleucine), 1181
2-Aminopropane, 241
2-Aminopyridine, 676–77
Amino terminus, 1189, 1197
3-Amino-2,4,6-tribromobenzoic acid, 670
Ammonia, structure, 17, 240
Ammonium ions
acid–base chemistry, 246–48, 1179
alkylammonium ions, 317
formal charge, 21
Lewis structure, 21
nomenclature, 242
quaternary ammonium ion formation, 318
quaternary nitrogen compounds, 240
Amyl alcohol (1-pentanol), 230, 231, 231n2
Analytical chemistry, overview, 695–97, 750–51
Anchimeric assistance, 1089, 1100
Angle strain, 128, 187, 190, 276, 474
Anhydrides
acid–base chemistry, 886–87
addition–elimination reactions, 894–95
definition, 855
Friedel–Crafts reactions,895
general structure, 877
infrared spectra, 888
nomenclature, 881
structure, 769, 855
synthesis, 855–56, 869, 923
See also Acyl compounds
Aniline (benzenamine or aminobenzene)
azo dye production, 647
bromination, 670
from chlorobenzene reaction with strong base,
680–81
conversion to benzenediazonium chloride,
647–48
conversion to pseudomauvine, 648
nitration, 673
from nitrobenzene reduction,646, 651, 686
reaction with maleic anhydride, 894
from reduction of nitrobenzene, 646
structure, 243, 595
Anilinium ion, 673
Anions, 4
See also Carbanions
Anisaldehyde (4-methoxybenzaldehyde), 768
Anisole (methyl phenyl ether or methoxybenzene)
chlorination, 659
inductive effects, 666–67
meta substitution, 657
ortho substitution, 658, 666–67
para substitution, 657–60, 666–67
structure, 250, 595, 657, 659
Annulenes, 594
Anomeric carbon, 1134
Anomers, 1134–35, 1140
Antarafacial motion, 1055–58
Anthracene, 179, 603, 621, 692
Anthranilic acid,
692
Antibonding molecular orbitals (
antibonding
,
A
),
32–35, 40, 44, 54
Anti elimination, 305–6, 311, 322
Anti-Markovnikov addition
alcohol synthesis, 399–400, 403
definition, 399
hydration of 2-methylpropene, 382
hydroboration/oxidation of alkenes, 399–400,
403
hydroboration/oxidation of alkynes, 451
radical HBr addition to alkenes, 481–82,
484–86
radical HBr addition to alkynes, 489–90, 507
See also Markovnikov addition
Antimony hexafluoride anion, 679–80
Antimony pentafluoride, 679–80
Apomorphine, 408
Aprotic solvents, 238–39, 240, 280
D-Arabinose, 1129, 1153–56, 1158
Arenes, 598
Arginine, 1177, 1177, 1180, 1202
Argon, 4, 6
Arndt–Eistert reaction, 917
Aromatic character, definition, 582
Aromatic compounds
Birch reduction, 608–9, 618
chemical shift 725
coupling constant ( J), 732
Diels–Alder reaction, 628–31
hydrogenation, 626–27, 686
paracyclophanes, 628–29
reverse Diels–Alder reactions,554
structural features, 582–83
substitution reactions, 606–8
See also Hückel’s rule; Substitution reactions of
aromatic compounds; specific types
Aromaticity, definition, 582
See also Hückel’s rule
Arrow formalism, 23, 26
Aryl, 598
Asparagine, 1176
Aspartame, 1164
Aspartic acid, 1176
Atomic number, 5
Atomic orbitals
1s orbital, shape, 10–11
2p orbitals, shape, 12–13
2s orbital, shape, 12
definition, 3
(),
££
I-4 INDEX
electron density, 10, 11–12, 32–33
electron shells, 4
in first 10 elements, 13
nodes, 11–12
probability of finding electron in a volume of
space 6, 10, 11–12
relationship to quantum numbers, 6–8
See also Electron configurations; Hybrid
orbitals; Wave functions
Atomic weights, 701
Atoms
atomic number, 5
atomic structure, 4–6
Bohr model, 2
definition, 2
history of atomic models, 2
mass number, 5
strange atoms, problem solving, 46
Auden,Wystan Hugh, 468, 468n1, 1081, 1081n1
Aufbau principle, 8–9
Axial hydrogens, 191
Azabicyclooctane, 277–78
2-Azacyclobutanone ( -lactam), 882
2-Azacyclohexanone ( -lactam), 882
Azetidine (azacyclobutane), 242
Azides, 436, 918–19, 922
Aziridine (azacyclopropane),242, 464–65
Azobisisobutyronitrile (AIBN), 476
Azo compounds, 476, 507, 647, 651, 689
Babies and quantum mechanics, 42–43
Baeyer–Villiger reaction, 907–9, 924
Bakkenolide-A, 211
Barbaralane, 1068
Base pairs, 288, 615, 1212–13, 1214
Base peak, 702
(beta) cleavage, 472, 473, 474
Beckmann rearrangement, 909–11, 923, 924
Beer–Lambert law, 527
Benzaldehyde (benzenecarboxaldehyde)
Cannizzaro reaction, 1004–5
Claisen–Schmidt reaction, 983–85, 1008
hydrate formation,965–66
Meerwein–Ponndorf–Verley–Oppenauer
(MPVO) equilibration, 1005
mixed aldol condensation with tert-butyl
methyl ketone, 983–84
structure, 595, 768, 983, 1004
Benzamide, 882
Benz[a]pyrene,605, 615, 616
Benzene
and bisulfate anion, 633
catalytic halogenation with FeCl
3
or FeBr
3
,
638
catalytic hydrogenation, 580, 627
chemical properties, 572
conversion to cyclohexane, 580–81, 626–27,
686
and 1,3,5-cyclohexatriene, 572, 573–75,
580–81, 629
delocalization energy, 581–82, 607, 614, 626
destabilization to lower activation energy,
628–29
deuteration, 606–8, 618, 632–34
Dewar forms, 576–78, 617, 1043
Diels–Alder reaction, 628–29
energy barriers to substitution reactions, 606,
627–28
Frost circle, 584–85
heat of formation, 581–82
heat of hydrogenation, 580–81, 626–27
Kekulé forms, 575–77
methylation reactions, 641, 655–56
molecular orbitals, 578–79
nucleophilic addition to benzenes (S
N
Ar
reaction), 674–76
resonance (overlap of 2p orbitals), 575–78
resonance stabilization, quantitative evaluation,
580–82, 629
structure, 179, 573–75, 582–83
substitution reactions, resistance to, 606–8,
631–32
See also 1,3,5-Cyclohexatriene;
Heterobenzenes; Substituted benzenes
Benzenediazonium chloride, 647, 648, 650
Benzenediazonium ion, 648, 650
Benzenesulfonic acid, 636–37, 686
Benzenethiol (phenyl mercaptan, thiophenol), 252
Benzenol. See Phenol
Benzhydryl group, 611
Benzofuran, 605
Benzoic acid (benzenecarboxylic acid)
anhydride formation, 881
oxidation of alkylbenzenes, 613–14, 618
physical properties, 830
pK
a
, 760
structure, 595, 882
Benzoic anhydride, 881
Benzoic butyric anhydride (benzoic butanoic
anhydride), 881
Benzoin condensation, 1028
Benzothiophene, 605
3,4-Benzphenanthrene, structure, 179
Benzvalene (tricyclo[3.1.0.0
2,6
]hex-3-ene), 573,
574
See also Benzene
Benzyl alcohol, 231, 595, 1004
Benzylamine, 241
N-Benzylaziridine, 242
Benzyl cation, 611, 703–4
Benzyl chloride,structure, 595, 611
Benzylethylmethylamine, 241
Benzylic compounds
definition, 595, 596
hydrogen abstraction at position, 613
oxidation to benzoic acid, 613–14, 618
reactivity of benzyl group, 610
similarity of benzyl and allyl groups, 610
S
N
1 substitution reactions, 610–11, 618
S
N
2 substitution reactions, 612, 618
4-Benzylmorpholine (N-benzylmorpholine), 242
Benzyl radical, 480, 612–13, 618
Benzyne, 680–82
Beryllium hydride, 54–55
Bicyclic compounds
bridged bicyclic molecules, 121, 211, 214–16
from Diels–Alder reaction, 551–54
fused bicyclic molecules, definition, 121, 211
fused bicyclic molecules, structure, 212–13
intramolecular reactions of endo and exo
bicyclic amines, 1090–92
neighboring group effect, 1090–93
nomenclature, 214–15, 551–52
structure of ring compounds, 211–17
See also Ring compounds
Bicyclo[4.2.2]deca-2,4,7,9-tetraene, 707
Bicyclo[2.2.1]heptane (norbornyl system), 186,
306, 1099n2, 1100
Bicyclo[3.3.1]non-1-ene, 122–23
Bicyclo[2.2.2]octane, 361
Bicyclo[3.2.1]octane, 215, 361
Bicyclo[3.3.0]octane, 361
Bicyclo[1.1.1]pentane, 216
-Bicyclopropenyl, 573, 574
See also Benzene
Bierce, Ambrose, 695, 695n1
Bimolecular elimination reactions.See E2 reactions
Binding sites, 1193
Biphenyl (phenylbenzene), 179, 595, 688
Birch reduction, 608–9, 618
Bisulfite addition to carbonyl compounds, 781,
782, 818
Blocking groups, 671
Bohr, Niels, 2, 2n1, 3n4
Bohr model of atom, 2
Boltzman distribution, 340
Bombykol, 534
Bond dissociation energy (BDE)
average bond dissociation energies, 39
bond energy of H
2
molecule, 39–40
butane, 188
1-butene, 475
cyclopropane, 188, 474
definition, 37
1,5-hexadiene, 475
homolytic bond cleavage, 337, 470
hydrocarbons, 477
hydrogen molecule, 37
methane, 57
propane, 475
Bonding molecular orbitals (
bonding
,
B
), 32–35,
44
Borane
alkylborane formation, 391, 394
borane–tetrahydrofuran complex, 391
dialkylboranes, 397, 450
diborane, 390–91
as Lewis acid, 92, 390–91
sp
2
hybridization, 55–56, 92
trialkylboranes, 397, 398, 399
vinylboranes, 450–51
See also Hydroboration
Borodin, Alexander,966n2
Boron, 55–56
Boron enolates, 1008
Boron trifluoride, 251, 264–65, 390
See also Hydroboration
Bredt, Julius, 121–22
Bredt’s rule, 121–22
Bridged bicyclic molecules, 121, 211, 214–16
See also Bicyclic compounds; Fused
compounds; Ring compounds
Bridgehead position, 121–22, 212, 213–16
Broad-band decoupling, 740
-Bromo acids, 950–53, 1182, 1216
Bromobenzene, 595
1-Bromobutane, 738
3-Bromobutanoic acid (3-bromobutyric acid), 831
1-Bromo-2-chlorocyclopropane, 204
2-Bromo-4-chloro-6-fluoroaniline, 597
1-Bromo-1-chloropropene, 111
4-Bromo-2-chlorotoluene, 597
4-Bromo-2,5-dichlorophenol,597
Bromoethane, 702
1-Bromo-3-ethyl-2-nitrobenzene, 597
Bromoform, 431
Bromohydrins, 463, 1083, 1094
££
3,3¿
()
(
2
),
INDEX I-5
2-Bromo-3-hydroxypropanal, 154
2-Bromo-2-methylbutane, 299
Bromonitrobenzene, 672
Bromonium ions, 415–21, 424, 426, 536, 1094–95,
1101–2
Bromophenol, 671
1-Bromopropene, 489
2-Bromopropene, 489
3-Bromopyrrolidine, 242
N-Bromosuccinimide (NBS), 500–501, 507, 543,
613, 618
2-Bromotoluene (o-bromotoluene), 596
Bronowski, Jacob, 1174, 1174n1
Brønsted acids, definition, 42, 90, 233
See also Acid–base chemistry
Brønsted bases
alkenes in addition reactions,132, 143
definition, 42, 90, 233, 298–99
relationship to nucleophilicity, 278–80
See also Acid–base chemistry
Brosylate (p-bromobenzenesulfonate), 1085–86
Brown, H. C., 390, 398, 1116n4
Brucine, 171
Buckminsterfullerene, 604
Bullvalene, 1068–71
1,2-Butadiene, 516–17
1,3-Butadiene (methylallene)
addition of Br
2
and Cl
2
, 536, 564
bond lengths, 522
from electrocyclic opening of cyclobutene,
1034–40, 1042, 1047
electron transitions and energies, 528–29
heat of hydrogenation, 524–25
hydrogen bromide addition to,406, 534–35
hydrogen chloride addition to, 369–71,
534–35, 537–39
hydrogen iodide addition to, 406
interconversion of s-trans and s-cis
conformations, 523–24, 546
molecular orbitals, 520–21
paired electron spins, 28
physical consequences of conjugation, 521–25
resonance forms, 26–27, 28, 519, 521, 535
structure, 110, 512
thermodynamic and kinetic control of addition
reactions, 537–41
See also Conjugated dienes; Dienes
Butanal (butyraldehyde), 767, 779, 933, 984
Butane
anti form, 74
bond dissociation energy, 188
conformational analysis, 73–75
dihedral angle, 74
gauche form, 74, 75, 163–64, 200
gauche interactions, 74, 74n6, 163–64
isobutane, 73, 75
photohalogenation, 494–95
2,2,3-trimethylbutane, 83
Butanedial, 767
meso-2,3-Butanediol, 444
1-Butanethiol (butyl mercaptan), 252, 809
Butanoic acid (butyric acid), 830, 836, 849, 879,
880
Butanone (ethyl methyl ketone, 2-butanone), 464,
768
Butene
1-butene, bond dissociation energy, 475
1-butene, heat of hydrogenation, 524
1-butene, structure, 109, 110
cis-2-butene, conversion to 2,3-dibromobutane,
1093–96
cis-2-butene, hydrogenation, 580
cis-2-butene, structure, 109, 144, 148, 177, 444
trans-2-butene, structure, 109, 144, 148, 177
butene radical, mass spectrometry (MS), 705–6
See also Isobutene
trans-2-Buten-1-ol, 111
Butlerov, Alexandr M., 574n2
Butyl alcohol (1-butanol), 230, 705–6
Butylated hydroxy anisole (BHA), 484
Butylated hydroxy toluene (BHT), 484
Butylbenzene (1-phenylbutane), 644, 645
Butyl compounds, 75–76, 494–95
See also specific compounds
Butylethylmethylpropylammonium iodide, 242
sec-Butyl alcohol (2-butanol), 152, 154
, 162, 230
sec-Butyl radical,471, 472
tert-Butyl alcohol (2-methyl-2-propanol)
from addition of water to 2-methylpropene,
382, 390
from tert-butyl bromide, 289
from tert-butyl iodide solvolysis, 333, 348
pK
a
, 987
reaction with hydrogen iodide, 343
solvation, 237, 238
structure, 141, 230
tert-Butylamine, 241
tert-Butylbenzene, 614, 643
tert-Butyl bromide, 289, 294–95, 301–2
tert-Butyl butyrate (tert-butyl butananoate), 879
tert-Butyl chloride (2-chloro-2-methylpropane),
494, 640, 702, 703
tert-Butylcyclohexane, 202–4
tert-Butyl cyclopentyl sulfide, 253
tert-Butyl iodide (2-iodo-2-methylpropane)
activation energy of ionization reaction,
343–44, 346–47
energy versus reaction progress diagram,in
water, 343
reaction mechanism in S
N
1 reaction, 350–51
S
N
1 solvolysis reaction in water, 333, 343–44,
346–51, 383
structure, 226
transition states in S
N
1 reaction, 333, 343,
346–49
1-tert-Butyl-4-methylcyclohexane, 749
tert-Butyl methyl ether (2-methoxy-2-
methylpropane, MTBE),250, 316, 324,
719
tert-Butyl methyl ketone, 983–84
1-Butyne, 126, 127, 516–18
2-Butyne, 126, 128, 516–18
Butyryl fluoride (butanoyl fluoride), 879
Cadaverine (1,5-pentanediamine), 246
Cahn–Ingold–Prelog priority system, 111, 112–15,
152–55
Calicheamicin, 214, 980
Camphor, 558
Canavanine, 1177
Cannizzaro reaction, 1004–5, 1012
Cantharidin, 568
Caraway [(S)-()-carvone], 163
Carbamates, 860, 919, 924, 1205
Carbamic acids, 860, 869, 920
Carbanions
allyl anion, 27–28
2-butyne resonance-stabilized carbanion, 516
definition, 62
enolate anion, 27, 28, 373
radical anions, 453–54, 609
stability order, 311
structure and hybridization, 64
See also Methyl anion
Carbenes
concerted reactions of,432, 434
definition, 431
from diazo compounds, 431, 436
dihalocarbenes, 431
diradicals, 434, 435
formation of cyclopropanes, 431, 432
ketocarbenes, 915–16
reaction with alkenes, 431–32
singlet carbenes, 433–34, 436, 458
stereospecificity, 432
triplet carbenes, 433–36, 468
See also Cyclopropane
Carbenium ion, 62n4
Carbinolamines, 790–91, 794–95, 819–21,
1184
Carbocations
additions to alkenes, 132–33, 135–36, 140
definition, 62
delocalization of electrons, 27
deprotonation, 385
heat of formation 292, 445
hyperconjugation, 293–94, 377–78, 478–79
instability of methyl and primary carbocations,
293, 376
resonance and carbocation stability, 374–78
resonance and regiochemistry in addition
reactions of alkenes, 366–72
simple carbocations, 141
stability in superacid, 679–80
stability order, 138, 139, 141, 292–93, 376,
478
structure and hybridization, 64, 477
transition states, 376–77
vinyl carbocations, 444–45
Carbodiimides, 516, 1206–7, 1218
See also Dicyclohexylcarbodiimide (DCC)
Carbohydrates
anomeric carbon, 1134
anomers, 1134–35, 1140
chain lengthening, 1138–39
configurational carbon, 1127, 1128, 1129
D configuration, 1128
definition, 1125
disaccharides, 1161–68
epimerization in base, 1141–42
epimers, definition, 1133
ester formation, 1147–51
exotic laboratory syntheses, 1125n3
Fischer determination of structures of
aldohexoses, 1153–60
Fischer projections, conventions, 1127–28
furanoses, 1132–33
furanosides, 1148
glycolysis, 1140
glycosides, 1148–52, 1210
Haworth forms, 1136–37
hemiacetal formation, 784, 1130–34
ketoses, 1128, 1141
keto sugars, 1130
Kiliani–Fischer synthesis, 1138–40, 1153–54,
1160
L configuration, 1128
(¢H°
f
),
I-6 INDEX
Lobry de Bruijn–Alberda van Ekenstein
reaction, 1141–42
manipulation of alcohol groups in -
D-
glucopyranoside, 1152
modern carbohydrate chemistry, 1151–52
monosaccharides, definition, 1161
mutarotation, 1140–41
nomenclature and structure, 1126–38
nonreducing sugars, 1166
osazone formation, 1145–46, 1147, 1158, 1159
overview, 1125–26
oxidation, 1144–45
polysaccharide, 1161, 1166, 1168
protecting groups, 1151–52
- and -pyranose and furanose forms of
aldohexoses, 1134–35
pyranoses, 1132–33
pyranosides, 1148
ratio of furanose and pyranose forms of
aldohexoses, 1133
reducing sugars, 1133, 1145, 1166
reduction, 1130, 1134, 1143
rotation of plane-polarized light, () or ()
convention, 1128
Ruff degradation, 1139–40
starch, 1161, 1168
synthesis, 1138–40
See also Aldoses; specific types
Carbon, 9–10, 700, 740
Carbonate ion, 45
Carbonates from phosgene reaction with alcohols,
899, 924
Carbon dioxide, 15–16
Carbon disulfide, 914
Carbonic acid, 859–60
Carbonium ion, 62n4
Carbon monoxide, 47
Carbon nuclear magnetic resonance spectroscopy
(
13
C NMR), 88–90, 94, 740–42
Carbon tetrachloride, 16, 417, 419, 487, 490–93,
500
Carbonyl compounds (overview)
carbonyl group conversion into methylene
group, 645, 686
definition, 438
dipole moments, 766
equilibrium between carbonyl and enols forms,
940–42
formation during ozonolysis,438–39, 440–42
infrared (IR) spectroscopy, 770–71
keto–enol tautomerization, 939–40, 944, 961,
966
mass spectrometry, 704, 772
meta substitution reactions of aromatic
compounds, 664–65
nomenclature, 767–69
nuclear magnetic resonance (NMR)
spectroscopy, 725, 771–72, 888–89
oxidation to carbonyl compounds, 802–6
ozone, role in synthesis, 441
physical properties, 770
(pi) bonding, 764–66
resonance of carbonyl group, 766
stability of substituted carbonyl groups,
777–80
steric destabilization, 778
steric destabilization of hydrates, 778, 780
structure of carbon–oxygen double bond, 763,
764–66
ultraviolet spectroscopy, 771, 772
See also Carbonyl compounds, addition
reactions; Carbonyl compounds,
condensation reactions; Carbonyl
compounds, reactions at position; -
Dicarbonyl (1,3-dicarbonyl) compounds;
Enones; -Hydroxy carbonyl compounds
Carbonyl compounds, addition reactions
acetal formation, 783–89, 817
alkane formation by Clemmensen reduction,
645, 686, 802
bisulfite addition, 781, 782, 818
cyanohydrin formation, 781–82, 818, 1139
enamine formation, 795–96, 818, 821, 963
equilibrium in addition reactions, 777–81
hydration,773–77
imine formation, 790–94, 818
overview, 763–64, 816–19
reaction with organometallic reagents to form
alcohols, 799–802, 817
simple reversible additions, 773–77
substituted imine formation, 793
Wittig reaction, 811–13, 817
Wolff–Kishner reduction, 645, 686, 802
See also Acetals; Carbonyl compounds
(overview); Hemiacetals
Carbonyl compounds, condensation reactions
amines, 1003–4
benzoin condensation, 1028
Cannizzaro reaction, 1004–5, 1012
Claisen–Schmidt condensation, 983–85, 1008
combination of condensation reactions,
998–1001
crossed (mixed) Claisen condensation, 993–95
Dieckmann condensation, 992–93
Horner–Emmons reaction,1009
Knoevenagel condensation, 974–76, 1014
Mannich reaction, 1003–4, 1013
Meerwein–Ponndorf–Verley–Oppenauer
(MPVO) equilibration, 1005–7, 1012,
1014
Michael reaction,976–80, 998–99, 1016
problem solving techniques, 999–1001,
1007–9, 1014–17
reverse aldol reactions,973
Robinson annulation, 998–99
-unsaturated aldehyde and ketone from
aldol dehydration,968–69, 971–72,
973–75, 981, 1014
-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
See also Aldol condensation; Carbonyl
compounds; Carbonyl compounds
(overview); Carbonyl compounds,
reactions at position; Claisen
condensation
Carbonyl compounds, reactions at position
acidity of double hydrogens,958, 986, 989,
993
alkylation in the position, 954–64
position, definition, 763, 933
-bromo acid bromides, 951–52, 1182, 1216
-bromo acid halides, 951–52
-bromo acids, 950–53
chemical reactions, overview, 932–33, 1010–17
hydrogen abstraction in benzylic compounds,
613
keto–enol tautomerization, 939–40, 944, 961,
966
NMR spectra of hydrogens or carbons,
714–15, 723, 725
overview, 932–33, 1010–17
-unsaturated aldehyde and ketone from
aldol dehydration,968–69, 971–72,
973–75, 981, 1014
-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
See also Carbonyl compounds (overview);
Carbonyl compounds, condensation
reactions; Carbonyl compounds,
overview; Enolates; Enols
-Carbonyldiimidazole, 873
Carboranes, 217
Carboxylate anion
ammonium salts, 850, 852, 1179, 1183–84
comparison to alkoxide ion, 834
definition, 832
as displacing agent in S
N
2 reactions, 848
electrochemical oxidation (Kolbe electrolysis),
860, 861, 870
electrostatic stabilization, 835
metal salts, 832
methyl ester formation with diazomethane,
848–49
neighboring group effect on -carboxylate
reaction with methyl alcohol, 1083–85
nucleophilic addition to carboxylate anion,
836–37
resonance stabilization, 834–35
Carboxylate salts, 832, 850, 852, 1179, 1183–84
Carboxylic acids
acid anhydride formation, 855–56
acid–base chemistry, 834–38
acid chloride formation, 853–55, 868
acidities of substituted carboxylic acids, 836
alkylation, 957
amide formation, 850–52, 869
ammonium salts, 850, 852, 1179, 1183–84
decarboxylation, 858–60, 870
definition, 424
dianion formation, 836, 837, 857–58, 957
dimers, 832, 833, 860, 870
from esters, 869, 895–98, 897, 912–14
and Fischer esterification, 841–49, 852–53,
869, 896–97, 924
formation from ozonolysis, 441–42, 458, 839,
869
general formula, 829, 877
halogenation, 950–53
Hell–Volhard–Zelinsky (HVZ) reaction,
950–53
Hunsdiecker reaction, 861, 869
hydrogen bonds, 832, 833
from hydrolysis and decarboxylation of
diesters, 961–62
from hydrolysis of acid chlorides, 890
from hydrolysis of acyl compounds, 877
from hydrolysis of amides,901–2, 922
from hydrolysis of nitriles, 904–5
infrared spectra, 833
N,N¿
,
,
,
,
,
,
,
,
INDEX I-7
Carboxylic acids (continued)
-keto acids, decarboxylation, 858–59, 870,
959–60
Kolbe electrolysis, 860, 861, 870
lactone formation by intramolecular Fischer
esterification, 849, 870
NMR spectroscopy, 833–34
nomenclature, 830–32
from organometallic reagent reaction with
CO
2
, 840–41
overview, 829
peracids, 424
pK
a
, 834, 836
properties, 830
protonation of carbonyl group and hydroxyl
groups, 837–38
reaction with metal hydrides, 858
reaction with organolithium reagents, 856–57,
870
s-trans and s-cis conformations, 832–33
structure, 769, 832–33
synthesis by oxidative routes,839–40, 868–69
See also Acyl compounds
Carboxypeptidases, 1197–98
Carboxy terminus, 1189
Carcinogenesis and carcinogens, 262, 431, 571,
605, 614–16
Carvone, (R/S) enantiomers, 163
Caryedes brasiliensis, 1177
Catalysts
acid-catalyzed hydration of alkenes, 139–41,
143, 381
benzene hydrogenation,627
chiral catalysts, 426
definition, 140
ferric chloride or bromide for halogenation of
benzene, 638
heterogeneous catalysis, 411
homogeneous catalysis, 411
Lindlar catalyst, 452, 458
palladium on charcoal, 411
Wilkinson’s catalyst (rhodium), 411
Catechol (o-dihydroxybenzene),597
Cationic polymerization,385–86
Cations, definition, 4
Cbz (benzyl chloroformate), 1205, 1207–8, 1217
Cellobiose, 1165
Cellulose, 1168
Cephalosporin C, 532
Chain reactions, 468, 482, 483
Chair cyclohexane, overview, 190–92, 220
Chemical shift
alkanes, 722–23
allylic hydrogens, 724
aromaticity, 725
definition, 718
delocalization, 725
deshielding, 720, 723–24, 725
effect of magnetic field strength, 716–17, 718,
722, 735, 738
electronegative groups,723, 725
hybridization, 724–25
hydrogens attached to oxygen or nitrogen, 726
overview, 720–22
of various carbons (
13
C NMR), 741
of various hydrogens (
1
H NMR), 720
See also Hydrogen nuclear magnetic resonance
spectroscopy (
1
H NMR); Nuclear
magnetic resonance spectroscopy (NMR)
Chichibabin reaction, 676–77, 761
Chiral, definition, 148, 151
Chirality, 148–51, 150, 150n2, 177–80, 181
2-Chloro-2,3-dimethylbutane, 131, 304, 365, 388
trans-1-Chloro-2-butene, 534
M-Chlorobenzaldehyde, 779
Chlorobenzene, 638, 650, 667–68, 680–81
2-Chlorobutane, 80, 165–67
Chlorobutanoic acid, 836
2-Chloro-1-butanol, 230
3-Chloro-1-butene, 534
Chlorocyclopropane, 173–74
2-Chloro-2,3-dimethylbutane, 131, 304, 365, 388
2-Chloro-3,3-dimethylbutane, 388
Chlorodinitrobenzene, 674
2,4-Chlorodinitrobenzene, 674
Chloroethane, 702
Chloroethyne (chloroacetylene), 126
Chlorofluoromethane, 721
3-Chloro-4-fluoro-2-pentanol, 230
Chloroform (trichloromethane), 16, 431, 490–91,
493
cis-2-Chloro-3-hexene, 111, 394
3-Chloro-3-hexene, 444
3-Chloro-2-hydroxypropanal, 767
2-Chloro-2-methylbutane, 138, 386
2-Chloro-3-methylbutane, 386
1-Chloro-2-methyl-1-butene, 113
Chloronitrobenzene, 668, 668, 674–75, 675
Chloronium ion, 418
trans-4-Chloro-2-pentene, 111
2-Chloropropanoic acid, 737
2-Chloro-1-propanol, 748–49
1-Chloropropene,108
2-Chloropropene,108, 446, 447
3-Chloropropene (allyl chloride), 108
Chlorosulfite esters, 284–85, 322, 854, 868
Cholanthrene, 605
Cholestanol, 221
Cholesterol
biosynthesis, 358
cholesterol benzoate, 497
low-density lipoprotein (LDL) cholesterol,
358
structure, 121, 216, 532, 562
synthesis, 358, 532
Chorismate, 683–84, 1063, 1078
Chorismate mutase, 683, 1063, 1078
Chromate esters, 804
Chromatography
column chromatography, 172, 697
enantiomer separation, 172, 695–96
gas chromatography (GC), 697–99, 709
gas chromatography/infrared spectroscopy
(GC/IR), 699, 709
gas chromatography/mass spectrometry
(GC/MS), 699
GC/IR (gas chromatography/infrared
spectroscopy), 699, 709
GC/MS (gas chromatography/mass
spectrometry), 699
gel-filtration chromatography, 1195
high-performance liquid chromatography
(HPLC), 697
ion-exchange chromatography, 1195
overview, 695, 697
separation of enantiomers, 172, 695–96
Chromium trioxide, 803, 804–5
Chymotrypsin, 1202
trans-Cinnamaldehyde [(E)-3-phenyl-2-propenal],
768
cis isomers, 84, 85,144
Citrate, 357
Civet cats (Viverra civetta and Viverra zibetha),
769
Civetone, 769
Claisen, Ludwig, 987–88, 1008, 1063n5
Claisen condensation
amide base use, 986
comparison of aldol and Claisen
condensations, 988–89,
990
crossed (or mixed) Claisen condensations,
993–95, 1013
Dieckmann condensation, 992–93
forward and reverse reactions in fatty acid
metabolism, 996–97
and full equivalent of base, 986, 989, 991, 992
intermolecular Claisen condensations, 992–93
ketone enolate reaction with esters, 985–87
kinetic enolates, 986, 1008
mechanism, 985
overview, 985–88, 991,992
removal of double hydrogens, 985, 986, 989,
991, 994
reverse Claisen condensations, 924, 992
thermodynamic factors, 988–89, 990,992
See also Aldol condensation; Carbonyl
compounds, condensation reactions;
-Keto esters
Claisen rearrangement, 1063, 1077–78
Claisen–Schmidt condensation, 983–85, 1008
See also Carbonyl compounds, condensation
reactions
Clemmensen reduction, 645, 686, 802
Coates’cation, 1117
Cocaine, 256
Coenzyme, definition, 814
Combustion, 68, 92, 144
See also Heat of combustion
Concerted reactions
comparison to nonconcerted, stepwise
reactions, 1033
definition, 389, 396, 1031
epoxidation, 424–25
hydroboration, 391–95
overview, 1032–34
ozonolysis, 437
rearrangements of acyl compounds, 914–20
See also Diels–Alder reaction; Pericyclic
reactions; S
N
2 reactions
Configurational carbon, 1127, 1128, 1129
Conformation, definition, 65
Conformational analysis
butane, 73–75
cyclohexane, 197–99
definition, 73
ethane, 65–67
methylcyclohexane, 194–201
propane, 72
Conformational diastereomers, 177, 208–9
Conformational enantiomers, 164
Conformational isomers, 70, 177
Coniine, 170
Conjugate acid, 234
Conjugate base, 234
Conjugated dienes
addition reactions, 534–36, 563, 564
bond lengths, 522
(¢H°
c
)
()
I-8 INDEX
chemical properties of acyclic and cyclic dienes,
572
definition, 512
halogenation, 536
heats of hydrogenation, 524–25
hydrohalogenation, 369–70, 404, 534–35,
537–41
interconversion of s-trans and s-cis
conformations, 523–24, 545–46
molecular orbitals, 520–21
physical consequences of conjugation, 521–25
resonance forms, 519, 521
thermodynamic and kinetic control of addition
reactions, 537–41
ultraviolet/visible (UV/vis) spectroscopy,
528–32
See also 1,3-Butadiene (methylallene);
Diels–Alder reaction; Dienes
Conjugated double bonds, definition, 512
Conrotation, 1037–39, 1041, 1042
Conrotatory motion, definition, 1037
Cope elimination, 914, 923
Cope rearrangement
bullvalene, 1068–71
chorismate rearrangement to prephenate,
1063, 1078
definition, 1059
degenerate reaction,1059
3,4-dimethyl-1,5-hexadiene, 1062–63
1,2-divinylcyclopropane, 1064–65, 1067
cis-1,3,5-hexatriene and 1,3-cyclohexadiene
interconversion, 1064
homotropilidene, 1066–68
labeling experiments, 1059–60
photochemical rearrangement, 1061
thermal rearrangement, 1060
transition state, 1060–62
See also Sigmatropic shift reactions
Cortisone, 212, 562
Coupling constant ( J),718, 728, 731–32
See also Spin–spin coupling
Covalent bonds, overview, 6, 13, 14–16
See also Lewis structures
Cram, Donald J., 254, 1096, 1116n4
Crick, Francis H. C., 1213
Crossed (mixed) aldol condensation, 982–87
See also Aldol condensation
Crossed (mixed) Claisen condensation, 993–95,
1013
See also Claisen condensation
trans-Crotyl alcohol, 231
Crown ethers, 254–55
Cryptands, 255
Cubane, 216
Cumene (isopropylbenzene or 2-phenylpropane),
595, 639–40, 641–42
Cumulated double bonds
carbodiimides, 516, 1206–7, 1218
cumulated alkenes (cumulenes), 512, 515–16
isocyanates, 918–21, 923, 924, 1206
isothiocyanates, 921, 1198–99, 1206, 1218
See also Allenes; Ketenes
Curl, R. F., 603–4
Curtius rearrangement, 918–19, 920, 924
Curved arrow formalism, 23, 24, 44, 263–64
Cyanide addition to carbonyl compounds, 781–82,
818
Cyanobenzenes, 686, 719
Cyanogen bromide (BrCN), 1200–1201
Cyanohydrin formation, 781–82, 818, 1139
Cyclamates, 1164
Cyclic alkanes. See Cycloalkanes
Cyclic hydrogen (H
3
,H
3
), 102, 217, 1103
Cycloaddition reactions
definition, 1032, 1043
Diels–Alder reaction, 1033, 1043–45, 1047–48
HOMO–LUMO interactions, 1043–48
photochemical alkene dimerization, 1045–46,
1074
problem solving techniques, 1072
rules for cycloaddition reactions, 1047
See also Pericyclic reactions
Cycloalkanes
1,2-dimethylcyclopropane, 84–85, 148,
205–7
alkylcyclohexanes, axial–equatorial energy
differences, 202–4, 277
bicyclopentyl, 85
1,2-dimethylcyclopropane, 208
disubstituted ring compounds, structure,
204–10
formation of ring compounds, 83
heat of formation 194
heats of combustion 196–97
molecular formula, 51, 83, 98, 130
monosubstituted cyclohexanes, structure,
194–204
naming conventions, 84
polycyclic compounds, 85–86
properties, 84, 86–88
stereochemical analysis, 173–76
strain, 187–93
strain calculation from heat of combustion
194–97
strain calculation from heat of formation
193–94
See also Ring compounds
Cycloalkenes
bicyclic compounds from Diels–Alder reaction,
551–54
bridgehead alkenes, 121–23
heat of hydrogenation, 580
hydrogenation, 412
molecular formula, 131
naming conventions, 110
natural products, 121
physical properties, 123
polycyclic compounds, 121
stability of cis double bonds, 119–20
structures, 118–23
structures of cyclic polyenes, 118
twisting of trans double bonds, 119–20
See also Alkenes
Cycloalkynes, 128
Cyclobutadiene, 118, 572, 573, 583–84, 585–86
Cyclobutane, 98, 188–89
Cyclobutene, opening to a 1,3-butadiene, 1034–40,
1042, 1047
Cyclodecane, 193
Cyclodecapentaenes, 592–94, 621
1,3,5-Cycloheptatriene (tropilidine)
bromination, 620
hydride transfer, 587, 618
orbitals, 583, 584, 588
pK
a
, 591
structure, 118, 573, 583, 587–88
Cycloheptatrienyl anion, 587–88, 590–91
Cycloheptatrienylium ion (tropylium ion), 587–89,
590, 618
Cycloheptyne, 128
1,3-Cyclohexadiene, 118, 512, 572, 580–81,
1040–41, 1064
1,4-Cyclohexadiene, 118, 512, 564, 608–9, 617,
618
1,3-Cyclohexadienone, 942
See also Phenol
Cyclohexadienyl cation
from benzene, 606–9, 631–33, 635
conversion back to aromaticity, 634, 635, 639
in Friedel–Crafts acylation, 643, 646
in Friedel–Crafts alkylation, 640
in halogenation reactions,638
in meta substitution of anisole, 657, 658
in nitration reactions,638
in ortho substitution of anisole, 658
overview of role as intermediate, 626, 685, 688
in sulfonation reactions,636–37
Cyclohexane
from benzene hydrogenation, 580–81, 626–27,
686
chair–twist equilibrium, 199
conformational analysis, 197–99
1,1-disubstituted cyclohexanes, 205
1,2-disubstituted cyclohexanes, 205–10
drawing chair form, 190–92, 220
equatorial–axial conformation equilibrium,
201–3, 205, 206
full-boat conformation, 198
half-chair conformation, 197–98
mass spectrometry (MS), 700–701, 702
monosubstituted cyclohexanes, structure,
194–204
nuclear magnetic resonance spectroscopy
(NMR), 746–47
ring flip, 192, 198–99, 746–47
rotational energy barrier, 198–99, 747
stereochemistry, 190–92, 197–99
steric interactions in S
N
2 reactions, 276–77
strain, 190–92
twist (twist-boat) conformation, 197, 198, 199
undecadeuteriocyclohexane (cyclohexane-d
11
),
746
van der Waals strain, 198
Cyclohexanecarboxaldehyde, 767
1,4-Cyclohexanedione, 768
Cyclohexanethiol, 252
Cyclohexanone, 709, 771, 812
1,3,5-Cyclohexatriene, 572, 573–75, 580–81, 629
See also Benzene
Cyclohexene
allylic halogenation, 497–500
from Diels–Alder reaction, 513, 544–48, 550,
554, 563–64
halogenation, 418–19, 497–500
hydrogenation, 580, 626
temperature effect on stability, 338
See also Hexenes
Cyclohexylamine (cyclohexanamine,
aminocyclohexane), 241
1,2-Cyclononadiene, 514
Cyclononyne, 128
1,4-Cyclooctadiene, 512
1,3,5,7-Cyclooctatetraene, 118, 573, 581, 583, 586,
620
cis-Cyclooctene, 120
trans-Cyclooctene, 120, 178
(¢H°
f
),
(¢H°
c
),
(¢H°
c
),
(¢H°
f
),
INDEX I-9
Cyclooctyne, 128
Cyclopentadiene (1,3-cyclopentadiene)
Diels–Alder reactions, 551, 553
fulvene formation, 975
pK
a
, 589, 591, 601, 975
structure, 118, 875
Cyclopentadienyl anion, 589–90, 591, 599, 618
Cyclopentane, 83, 85, 186, 190, 414, 416
Cyclopentanol (cyclopentyl alcohol), 230
Cyclopentene, 119–20, 414
3-Cyclopentylpropyne (propargylcyclopentane),
127
Cyclopropanated fatty acids, 455
Cyclopropane
angle strain, 187, 474
aziridine (azacyclopropane),242, 464–65
bent orbitals, 187
bond dissociation energy, 188, 474
cyclopropanated fatty acid formation, 455
cyclopropyl bromide, 276
pyrethroids, 456
structure, 51
torsional strain, 187–88, 474
total strain estimates, 188, 194
See also Carbenes; Cycloalkanes
Cyclopropenes, 455–56
Cyclopropenium ion, 592
Cyclopropenylidene, 456
Cysteine, 1176, 1178, 1190, 1216
Cytosine, 615, 1212
Dacron, 852
Dalton, John, 2
Daughter ions, 702
Debye, Petrus Josephus Wilhelmus, 15
(E)-1,5-Decadiene, 512
Decalin, 212–14
Decarboxylation
alcohol formation from bicarbonate esters, 869
carbamic acid, 860, 869, 920
carboxylic acids, 858–60, 870
-dicarbonyl compounds, 959–62, 1014
diesters, 961–62
Hunsdiecker reaction, 861, 869
-keto acids, 858–59, 870, 959–60
-keto esters, 959–62, 963, 1014
malonic acid, 858–59, 961–62
monoesters of carbonic acid, 859–60
Decoupling of NMR spectra, 733, 739, 740–41,
746
Degenerate reactions,1031, 1048–49, 1059
Degree of unsaturation 130–31, 751
Dehydroquinate, 683
Dehydroshikimate, 683
Delocalization of electrons
allyl cation, 27, 369–70
allyl radical, 475, 480, 498–99, 543
benzyl radical,480, 612
carbocations, 27
delocalization energy, 581–82, 607, 614, 626
NMR chemical shift, 725
radical formation, 475–76, 480, 498
stabilizing effect in resonance forms, 27, 102
Democritus, 2
Denaturing, 1193–94
Deoxyribonucleic acid (DNA)
alkylation, 288, 615–16
alkylation reactions and mutations,288–89
base pairs, 288, 615, 1212–13, 1214
bases, 288, 614–15
double helix, 598, 1213
enzymatic epoxidation, 616
hydrogen bonding, 288, 615, 1212–13
mutation, 288–89, 615–16
(pi) stacking, 598, 615
and polyaromatic hydrocarbons, 614–16
replication, 1213
S
N
2 reactions, 262, 288–89
structure and composition, 614–16, 1149,
1211–13
See also Nucleic acids
Deoxyribonucleosides, 1211
Deoxyribose, 288, 1211, 1212, 1214
DEPT (distortionless enhancement with
polarization transfer), 741
Deshielding, 720, 723–24, 725
Detergents, 866–67
Deuteriobenzene, 607–8, 618, 632–34, 687
Deuteriochloroform, 717
1-Deuterioethyl alcohol, 152, 154
Deuterium
abundance, 701
aldol condensation, 970
deuterated hydrocarbons, 229, 257
deuteride exchange reactions, 606, 936–39,
944, 949–50, 1013
deuteride shift, 402
mass, 113
and NMR spectroscopy, 717, 733–34, 746
resonance in deuterium-labeled compounds,
475, 539–40, 606
sodium borodeuteride, 423
and syn addition, 394–95, 412
transfer in S
N
2 reactions, 288
Dewar, James, 574
Dewar benzene (bicyclo[2.2.0]hexa-2,5-diene),
573–74, 578, 617, 1043
See also Benzene
Dewar forms, 576–78, 617
Dextrorotatory, 156
Diacetone alcohol (4-hydroxy-4-methyl-
2-pentanone), 971
Dials, 767
Diamantane, 218, 219
Diamond, 218–19
Diastereomers, 165–67, 169–72, 177, 208–9
Diastereotopic hydrogens, 721–22, 731, 749
Diazo compounds, 431, 436, 620
See also Carbenes
Diazocyclopentadiene, 431, 620
Diazofluorene, 431
Diazo ketones, 915–18, 924
Diazomethane, 431, 848, 875, 915
Diazonium ions, 329, 647–51, 686, 687
Diazotic acid, 648
Dibenz[a,h]anthracene, 605
Dibenzo[c,g]phenanthrene, structure, 179
Diborane, 390–91
2,3-Dibromobutane, 1093–95
trans-1,2-Dibromocyclopentane, 414, 416
1,2-Dibromo-3,3-dimethylbutane, 415
cis-1,1-Dibromo-2,3-dimethylcyclopropane, 432
-Dicarbonyl (1,3-dicarbonyl) compounds
alkylation, 958, 963
equilibrium between carbonyl and enols forms,
941–42, 958–59, 974, 985–86
hydrogen bonding, 941, 942
hydrolysis and decarboxylation, 959–62, 1014
intramolecular hydrogen bonds, 942
pK
a
, 958
structure, 941
See also Carbonyl compounds; Carbonyl
compounds (overview)
1,3-Dichlorobenzene (m-dichlorobenzene), 596
2,3-Dichlorobutane, 176–77
Dichlorocuprate ion, 650
Dichlorocyclopropane, 174–76, 204
1,2-Dichlorofluoroethane,721
3,5-Dichlorohexanoic acid, 831
1,3-Dichloro-2-methoxypropane,732
1,2-Dichloropropane,446
2,2-Dichloropropane,446, 447
Dicyanobenzenes, 719
Dicyclohexylcarbodiimide (DCC), 850, 856,
869–70, 1205–7, 1209, 1217
Dicyclohexylurea (DCU), 1206
Dicyclopentylamine, 241
Dicyclopropyl disulfide, 253
Dieckmann condensation, 992–93
Diels–Alder reaction
aromatic compounds, 628–31
benzene, 628–29
bicyclic compound synthesis, 551–54
concerted reaction, 547–49, 1033, 1043–45,
1047–48
cycloaddition reaction, 1033, 1043–45,
1047–48
cyclohexene production, 513, 544–48, 550,
554, 563–64
dienophile, definition, 544
endo and exo products, 551–52, 567
furans, 629
orbital overlap and interactions, 544–45, 552,
1043–45
overview and background,544, 563, 564
photochemical Diels–Alder reaction, 1044–45
polycyclic products, 552–53
pyrrole, 630
reaction mechanism, 547–49
retention of stereochemistry, 548–49
reverse Diels–Alder reactions,554, 564,
630–31
s-cis conformation, 545–46, 550
thermal Diels–Alder reaction, 1043–44
thermochemistry, 545
Dienes
allenes, 178, 513–15
as intermediates in alkyne isomerization,
516–18
overview, 512–13
unconjugated dienes, 512, 519, 524–25, 528
See also 1,3-Butadiene (methylallene);
Conjugated dienes
Dienophile, definition, 544
N,N-Diethylpropanamide, 882
Diethyl tartrate, 426
Dihedral angle, 65–66, 67, 72, 74, 731
Dihelium (He
2
), 40–41, 479
Dihydrobullvalene,1068
Dihydropyran (3,4-dihydro-2H-pyran), 700,701,
702, 789
1,3-Dihydroxyacetone, 1128
Diimide, 411
Diisobutylaluminum hydride (DIBAL-H),
900–901, 923
2,3-Dimethyl-1-butene, 367
3,3-Dimethyl-1-butene, 388, 392, 415, 501–2
(Æ),
I-10 INDEX