NDEX
A b initio calculations, for ethene, 180- 182
for hydrogen, 981-982
Abietic acid, 1469
Absolute configuration (see also Chirality), of
amino acids, 877
definition of, 874-877
Fischer projections and, 875-877
of glyceraldehyde, 875
optical rotation and, 874-875
optical rotatory dispersion and, 892-893
of tartaric acid, 876
Absorption spectra (see Infrared, Nmr, Raman,
etc.)
Accelerators of vulcanization, 1429- 1430
Acenaphthene, from coal tar, 1080
Acetaldehyde (see Ethanal)
Acetaldol (see 3-Hydroxybutanal)
Acetals, from alcohols and carbonyl compounds,
62 1-624
equilibrium in formation of (table), 624
as ethers, 667
hydrolysis of, 624
mechanism of formation of, 622-624
protecting groups for carbohyl functions,
715-716
as protecting groups for OH, 652-653
Acetamide (see Ethanamide)
Acetanilide (see N-Phen ylethanamide)
Acetic acid (see Ethanoic acid)
Acetic anhydride (see Ethanoic anhydride)
Acetoacetate decarboxylase, characteristics of, 1285
Acetoacetic acid (see 3-Oxobutanoic acid)
Acetoacetic ester ketone synthesis, 833-834
Acetoacetic ester synthesis (see 3-Oxobutanoic
esters)
Acetoacetic esters (see 3-Oxobutanoate esters)
Acetogenins, 1481- 1482
Acetone (see 2-Propanone)
Acetone cyanohydrin (see 2-Hydroxy-2methylpropanenitrile)
Acetonylacetone, properties and reactions of, 778
Acetophenone (see Phenylethanone)
Acetyl bromide (see Ethanoyl bromide)
Acetyl chloride (see Ethanoyl chloride)
Acetyl coenzyme A (see Ethanoyl coenzyme A)
Acetyl nitrate, 1043
Acetylacetone (see also 2,4-Pentanedione),
properties and reactions of, 737-777
Acetylcholine chloride, 1099
Acetylcholinesterase, serine function in, 1265- 1266
Acetylene (see Ethyne)
Acetylenes (see Alkynes)
N-Acetylglycine, 1222
Acetylketene (see Diketene)
Achiral, definition of, 116
Aci forms of nitro compounds, 1195-1196
Acid anhydrides (see Carboxylic acid anhydrides)
Acid catalysis, of acetal and ketal formation,
622-624
of alcohol dehydrations, 630-632
of alcohol reactivity in S, reactions, 232-234
of aldehyde and ketone halogenations, 742-745
of alkene hydration, 368-371
of alkene polymerizations, 393-395
alkyl halides from alcohols and, 626
of alkylarene rearrangements, 1050
of alkylation of arenes, 1048
of amide hydrolysis, 1182
of amine hydrogen exchanges, 1105-1 106
of amine rearrangements, 11;2
of aromatic substitution, 1041
of carboxylic acid reactions, 805-808
of deuterium exchange of arenes, 1052
of elimination reactions, 25 1
of en01 and keto equilibrium, 828
of enolization, 739
of ester formation, 6 15-6 18
of hemiacetal and hemiketal formation, 622-624
of imine formation, 697-699
of mercuration of arenes, 1058
of nitration, 1042
of nitrile hydrolysis, 1178
of oxacyclopropane ring openings, 664-665
of N-substituted arenamines, 1139- 1140
Acid chlorides (see Acyl chlorides)
Acid halides (see Acyl halides)
Acid strength, correlation with leaving-group
reactivity, 232-233
Acid strengths, of inorganic acids in various
solvents, 370-37 1
Acid-base equilibria, 41-42, equations for,
209-2 11
formulation of, 208-2 11
Acidity, of hydrocarbons (table), 1322
Acids, carboxylic (see Carboxylic acids)
ACP, 1481
Acridine dyes, 1406
Acridine, from coal tar, 1080
Acrolein (see 2-Propenal)
Activated complex (see Transition state)
Activation energy, and bond energies, 96-97
concept of, 82-83
and heat of reaction, 96-98
Acyl azides, amides from, 1177-1 178
tert-butoxycarbonylation of amines with, 1160
in Curtius degradation, 1156
as functional derivatives of carboxylic acids, 818
preparation of (table), 858
Acyl carrier protein, 1481
Acyl chlorides, from carboxylic acids, with
phosphorus chlorides, 809
with thionyl chloride, 809
with Grignard reagents (table), 579, 583-584
Acyl groups, IUPAC rules of nomenclature for, 196
Acyl halides, acyl azides from, 858
in acylation of arenes, 1051-1053
acylation of enolate anions, 835
acylation of ferrocene with, 1506
from acyltetracarbonylferrates, 1516
from acylzirconocenes, 1514
alcohols from, with Grignard reagents, 609
by hydride reduction, 824-825
aldehydes from, by Rosenmund reduction, 728
amides from, 858, 1121-1 122, 1177-1 178
amines from, by Curtius degradation, 1150,
1153, 1156
with amino acids, 1222
anhydrides from, 857
carboxylic acids from, 855
carboxylic esters from, 856
with diazomethane, 692-693, 1200
esterification of, 6 15-6 18
as functional derivatives of carboxylic acids, 8 18
with Grignard reagents, 823-824
l~ydrolysisof, 820
infrared frequencies, 680
IUPAC rules of nomenclature for, 198
ketones from, with alkylcadmiums, 584
from alkylcoppers, 584
with alkylzirconocenes, 1514- 1515
with cadmium alkyls, 73 1
preparation of (table), 557 Ti-)
reduction to aldehydes, 719
Acyl hydrazides, amines from, by Curtius
degradation, 1150, 1156
Acyl nitrates, with arenes, 1043
Acyl nitrenes, in Curtius degradation, 1156
in Hofmann degradation, 1155- 1156
Acyl peroxides, decarboxylation of, radicals
from, 812
Acyl phosphates, in biochemical esterifications,
636-637
Acylation, of amines, 1121- 1122
of arenes, 1051-1053
Acyltetracarbonylferrates, 1516
Acylzirconocenes, preparation and reactions of,
1514-1515
Adamantane, structure of, 701
Addition, definition of, 42
Addition polymerization (see Polymerization,
addition)
Addition reactions, to alkenes (see also
Alkenes), reagents for (tables), 379-380, 389
of carbon-carbon multiple bonds, reactivity in,
358-359
energies of, 358-359
to carbonyl compounds (see Aldehydes,
Esters, etc.)
1,4-Additions, to alkadienes, 489-490
Michael type of, 770, 844-845
to unsaturated acids, 840-841
Adenine, adenosine from, 926
as DNA component, 1272-1277
in prebiotic evolution, 1283-1284
in RNA, 1278
Adenosine, in prebiotic evolution, 1283-1284
structure of, 926
Adenosine diphosphate, in coenzyme A, 838
Adenosine phosphate esters, formation and
hydrolysis, 635-637
in biochemical esterifications, 635-637
Adenosine triphosphate, from adenosine
diphosphate, 649
in photosynthesis, 941-943
with vitamin B,,, 1526
Adipic acid (see Hexanedioic acid)
ADP (see Adenosine phosphate esters)
Adrenal cortex hormones, 1473
Adrenalin, 1099
Affinity chromatography, for protein
separations, 1248
Aflatoxin B 1, as carcinogen, 1164
Aflatoxins, 1163
Aglycones, 925-928
Alanine, chiral forms of, 132
properties of, 1208
Alathon, 1432
Alcohols, acetal protecting groups for, 652-653
acetals and ketals from, 621-624
acid-base equilibria of, 41
acidic properties of, 612-613
acidities of (table), 736-738
addition to alkenes, 379
from aldehydes and ketones by reduction
(table), 705-710
aldehydes from, by oxidation, 727
from aldol addition products, 759
alkenes from, 630-632
from alkenes, by hydration, 608-609
by hydroboration, 608
by hydroformylation, 723
alkoxides from, 6 11-6 12
alkyl halides from, with hydrogen halides,
625-627
with phosphorus halides, 627
with thionyl halides, 626-627
from alkylzirconocenes by oxidation, 1514
amines from, 1125-1 126
with amino acids, 1221- 1222
in arene alkylations, 1048
basic properties of, 613-614
biological oxidation of, 644-646
carbon-oxygen bond cleavage of, 625-637
from carbonyl compounds, by borane
reduction, 610
and Grignard reagents, 608-609, 823-824
by hydride reduction, 610, 824
by hydrogenation, 6 11
by Meerwein-Ponndorf-Verley reduction, 6 11
chiral, racemization mechanisms of, 897
chromic acid oxidation of, 640-642
dehydration of, acid catalyzed, 25 1, 632-633
rearrangements in, 632-633
with diazomethane, 1199
electronic spectra of, 605
electrophilic reactions of, halide formation,
625-627
1,2-elimination reactions of, 630-632
ester protecting groups for, 652
esterification of, 615-618
esters from, with acyl halides and
anhydrides, 822
with ketene, 771
from esters, by hydrogenation, 825
by sodium and alcohol reduction, 825
ether protecting groups for, 651-652
ethers from, 655
from Grignard reagents, 577-58 1
from Grignard reagents and oxygen, 586-587
from halides, by S,1 and SN2 displacement,
213-217
hydrogen bonding of, 600-605
hydrogen exchange of, 605
industrial preparation of, 607
infrared spectra of, 602-604
infrared stretching frequencies for, 276-277
IUPAC rules of nomenclature for, 191
ketones from, by oxidation, 730
mass spectra of, 607
in natural products, 599
nucleophilic reactions of, acetal and ketal
formation, 62 1-624
with alkyl halides, 6 14-6 15
ester formation by, 6 15-6 18
from organoboranes, 427-430
from oxacyclopropanes, and Grignard
reagents, 609
by hydride reduction, 610
oxidation of, industrial uses of, 639
types and products of, 638-646
permanganate oxidation of, 643
phosphate esters of, biochemical derivatives
of, 635-637
formation of, 634-635
hydrolysis of, 635-637
physical properties of (table and graph), 73,
600-602
preparative methods for (table), 607-612
protecting groups for OH of, 520-530,
65 1-653
proton exchange in, 3 11-313,
proton nmr spectra of, 605
radical-chain addition to alkenes and
akynes, 389
by reduction of carbonyls, Grignard reagents
and, 582
resolution of chiral forms of, 868-869
sulfate ester formation from, 628-629
sulfonate ester formation from, 629
uses of, 599
as water derivatives, 600
water solubilities of, 73, 600-602
Aldaric acids, 9 12
Aldehyde-ammonia adducts, 700
Aldehydes, acetal formation from, 621-624
from acyl halides, by hydride reduction, 728
by Rosenmund reduction, 728
addition reactions to alkenols and
alkenones, 769
additions to, of alcohols, 694
of carbon nucleophiles, 689-693
of enolate anions, 749-754
general characteristics of (table), 685-689
of Grignard reagents, 577-580
of hydrogen halides, 703-704
of hydrogen sulfite, 695
of nitrogen nucleophiles (table), 697-703
table of examples, 688-689
of thiols, 695
of water, 646-647, 673-674, 694
of ylides, 691-692
from alcohol oxidations, with chromic acid,
640-64 1
by Oppenauer method, 727
with methylsulfinylmethane, 7 18-7 19
with oxygen, 639
alcohols from, by Meerwein-Ponndorf-Verley
reduction, 6 11
with Grignard reagents, 608-609
by reduction, 6 10-61 1
from alcohols, and aluminum alkoxides, 727
and chromic acid, 640, 727
by Meerwein-Ponndorf-Verley, 727
by oxidation, 639-640, 718, 727
from aldehyde derivatives, by hydrolysis, 729
aldol additions of, 749-752, 755-757, 759-761
from 1,2-alkanediols, by oxidation, 7 17, 727
by rearrangement, 720
from alkenes, by carbonylation of alkylboranes,
725-726
by hydroboration and carbonylation, 729
by hydroformylation, 722-723, 729, 1518- 1520
with ozone, 727
from alkyl halides, by methylsulfinylmethane
oxidation, 7 18
from alkynes, by hydration, 729
from amides, by hydride reduction, 728
amines from, 1148, 1154
amino acids from, 1225
with amino acids, deamination of, 1224
decarboxylation of, 1223- 1224
ammonia addition to, 700
azines from, 698
benzoin condensation of, 1324- 1325
bond angles in, 171-172
borane reduction of, 707-708
borohydride reduction of, 705-708
carboxylic acids from, 855
carboxylic esters from, 856
chloroethers from, 704
diazomethane reactions with, 692-693
difluoromethyl derivatives from, 1318
from N,N-dimethylrnethanarnide, and Grignard
reagents, 729
electronic excitation of, 1375-1376
electronic spectra of, 68 1
enamines from, 702
en01 and enolate reactions of, 735-763
enolization of, acid induced, 739
base induced, 736-738
equilibrium for, 736-738, 740-741
by Grignard reagents, 582
in haloform reaction, 746-747
in halogenation, 742-745
in nucleophilic reactions, 749-754
excited states of, 1375-1376
fluorescence and phosphorescence of, 1375-1376
general characteristics of, 671-678
halogenation of, base and acid catalyzed,
742-745
mechanism of, 742-745
hemiacetal formation from, 621-624
hydration of, 647, 673-674
hydrazones from, 698
by hydroformylation, 1518- 1519
from hydroperoxides by rearrangement, 721-722
imines from, 697-699
infrared frequencies, 680-68 1
infrared stretching frequencies for, 276
IUPAC rules of nomenclature for, 192-193
mass spectra of, 684
Meerwein-Ponndorf-Verley reduction of,
709-710
nitriles from, 1185
from nitriles, by hydride reduction, 728, 824
nmr spectra of, 684
from organoboranes, 428-429
oxidation of, Baeyer-Villiger, 7 13-7 14
oxygen, 7 12-7 13
permanganate, 712
peroxycarboxylic acids, 7 13-7 14
silver oxide, 712
oximes from, 698
from ozonization of alkenes, 43 1-433
physical properties of (table), 678-679
polymerization of, 696
preparative methods for (table), 717-729
protecting groups for, 7 15-7 16
proton chemical shifts, of, 3 11
radical-chain addition to alkenes and
alkynes, 389
reactivity of, and bond polarity, 674-678
and electronegative substituents, 678
reduction of, with aluminum alkoxides, 709-710
Cannizzaro reaction, 707-709
Clemmenson, 7 11
by Grignard reagents, 582
with hydrides (table), 705-708
by hydrogenation, 7 10
Wolff-Kishner, 71 1-7 12
semicarbazones from, 698
with sulfur tetrafluoride, 705
from triethoxymethane, and Grignard
reagents, 729
unsaturated (see also Alkenals), addition
reactions of, 768-770
1,4-additions of organometallics to, 585-586
electronic spectra of, 767
spectral properties of, 767-768
Alder, K., and [4+2] cycloadditions, 492
Aldohexoses (see Glucose, Mannose, etc.)
Aldoketenes (see also Ketenes), 771
Aldol addition, alkenones from, 755-757
arnbident nature of, 75 1
in annelation reaction, 1478
cyclic products from, 758
definition and general characteristics of,
749-750
dehydration of products of, 755-757
donor and acceptor in, 753
equilibria in, 75 1-753
mechanism of, 750
methanal and benzenol, 1442
of nitro compounds, 1196
in photosynthesis, 941-943
in steroid syntheses, 1478
synthetic uses of, 757-759
thermodynamics of, 75 1-753
Aldolase, 760, 947-948
Aldonic acids, 912
Aldopentoses (see also Arabinose, Ribose, etc.),
903-908
Aldose-ketose interconversions, 9 18-9 19
Aldoses, structures and occurrence of, 903-908
Aldotetroses, determination of configurations of,
909-9 12
Alduronic acids, 912
Alginates, 937
Alkadienes, cis-trans isomerism of, 114
general characteristics of, 488-489
heats of hydrogenation of (table), 415-416
photochemical cyclization of, 1387- 1389
photochemistry of, 1387- 1389
photoelectron spectra of, 1357-1358
1,2-Alkadienes (also see Allenes), chiral forms of,
508-5 10
R,S-convention for, 884
stereochemistry of, 508-509
1,3-Alkadienes, electrophilic additions to,
bromine by 1,2 and 1,4 modes, 489
hydrogen chloride by 1,2 and 1,4 modes,
489-490
kinetic vs. equilibrium control in, 490
radical addition to, hydrogen bromide in, 491
Alkadiynes, from oxidative coupling of
1-alkynes, 44 1
Alkaloids, biosynthesis of, 1489
definition of, 1097
examples of, 1097
1,2-Alkanedials, reactions of, 774-775
Alkanedioic acids (see Dicarboxylic acids)
I, 1-Alkanediols, stability of, 646-647
l,2-Alkanediols, aldehydes and ketones from, by
oxidation, 717, 727, 730
by rearrangement, 720
preparation of, 647
Alkanediols, from alkene oxidation, 6 11, 643
infrared spectra of, 605
properties of, 646-648
urethane foams kom, 1454- 1455
1,2-Alkanediones, reactions of, 774-775
1,3-Alkanediones, acidities of (table), 736-738
properties and reactions of, 776-777
1,4-Alkanediones, reactions of, 778
Alkanepolyols, properties of, 646-648
Alkanes, acid strengths of, aryl substituted
(table), 1322
additions to alkenes, 380
from aldehydes and ketones by reduction,
71 1-712
from alkenes, by zirconocene chlorohydride
reduction, 1514
alkynyl halides from (table), 548, 588-589
atomic-orbital models of, 162
boiling points of (table), 70-72
bromination of 99, 100-102
chiral, racemization mechanisms for, 897
chlorination of, with tert-butyl hypochlorite,
103-104
light induced, 91-95
with sulfuryl chloride, 102- 103, 108
from coal by Fischer-Tropsch process, 723
combustion of, 74-76
densities of, 70-71
electronic spectra of, 291-292
fluorination of, 99
halogen substitution of (table), 548, 588-589
halogenation of, mechanism and procedures
for, 81-104
selectivity in, 100- 102
heats of combustion of, 76-80
heats of formation of, 86
hydrogen-transfer reactions with carbocations,
397-398
infrared stretching frequencies for,
275-276, 278-280
"iso-" names for, 54
isomerism of, 44-46
isomers of, 45-46
melting points of, 70-72
nitration of, 105, 1187
nmr spectra of, 333-334
"normal," 52
number of isomers of, 45-46
from organoboranes, 427-428
as paraffins, 73-74
physical properties of (table), 70-72
polychlorination of, 100
proton chemical shifts of, 3 10-3 11
reactivity of, general considerations, 73-74
as saturated hydrocarbons, 73-74
substitution on, 81
1,2,3-Alkanetriones, carbon monoxide from, 779
hydration of, 779
Alkanoic acids (see Carboxylic acids)
1,2,3-Alkatrienes, cis-trans isomers of, 5 11
Alkenals, addition reactions of, 585-586, 768-770
1,4-additions of organometallics to, 585-586
dipole moments of, 768
spectral properties of, 767-768
Alkene dismutation, 1520- 1521
Alkene metathesis reaction, 1520- 1521
Alkene oxides (see Oxacycloalkanes)
Alkenes, addition of proton acids to, 367-376
addition reactions of, definition of, 350
hydrogen peroxide, 72 1
addition reactions to (tables), 379-380, 389
from alcohol dehydrations, 630-632
alcohols from, by hydration, 608
by hydroboration, 608
aldehydes and ketones from, by oxidation, 717
aldehydes from, by carbonylation of
alkylboranes, 725-726, 729
by hydroformylation, 722-723, 729, 1518-15 19
with ozone, 727
alkane alkylation of, hydrogen transfer in,
397-398
mechanism for, 397-398
1,2-alkanediols from, with permanganate, 643
from alkynes, by reduction, 1075
allylic bromination of, with N-bromobutanimide,
542-543
l ndex
4 534
I
amides from, 858, 1149, 1178-1 179
mines from, 1149
atomic-orbital models of, 165- 167
bromine addition to, mechanism of,
362-364, 367
stereochemistry of, 362, 365-366
bromine substitution on, with
N-brombutanimide, 103- 104
carbene additions to, 565
carboxylic acids from, 855
characteristics of additions to, 359-361
charge-transfer complexes from, 367
cis isomers, from hydrogenation of alkynes,
413-414
cis-trans isomers of, E,Z-convention for, 886
kinds of, 112-1 13
photochemical isomerization of, 1384- 13.86
common names for, 59-61
coupling with arenediazonium salts, 1136
electronic spectra of, 353
electrophilic additions to, mechanisms of,
359-38 1
orientation in, 373-38 1
reagents for (table), 379-380
epoxidation of, 662
equilibrium control of additions to, 374-376
ethers from, 655
excited states of, reactions of, 1387
from Grignard reagents and carbonyls, 582
halogen-substituted, orientation in additions
to, 380-381
homogeneous hydrogenation of, mechanism of,
1517-1518
hydration of, 366-372
hydroboration of, with alkyl- and dialkylboranes, 423
general characteristics of, 420-424
hydroformylation, 1518- 1519
hydrogen bromide addition to, stereochemistry
of, 368
hydrogen chloride addition to, 367-368
hydrogenation of, catalysts for, 4 11-4 14,
1517-15 19
with diimide, 418-419
heats of (table), 415
homogenous catalysis of, 4 17-418, 1517- 1519
mechanism of, 411-413, 1517-1519
selectivity in, 4 13-414
hydroperoxides from, 72 1
hydroxylation of, reagents for, 434-437
stereochemistry of, 434-436
hypohalous acid additions to, 360, 377-378
infrared spectra of, 35 1-353
infrared stretching frequencies for, 276, 284
isomerization of, organoboranes and, 424-426
ketones from, by oxidation, 730
nmr spectra of, 353
nomenclature of, 59-61
nucleophilic addition to, characteristics of,
384-386
as olefins, 59
from organoboranes, 427
orientation in electrophilic additions to,
373-382
osmium tetroxide reaction with, 434
oxacyclopropanes from, 662
oxidation of, 43 1-437
ozonization of, 43 1-433
peroxidation mechanism of, 456
with peroxycarboxylic acids, 435-436
from phosphate esters, 634
photochemical cycloadditions of, dimerizations, 1389
with ketones, 1389
[2 21 type, 503
photochem~calisomerization of, 1384-1386
photoelectron spectra of, 1357- 1358
physical properties of (table), 35 1-352
pi (n) bonds in, 165-167
pi (n) complexes from, 367
polymerization of, anionic mechanism for,
392-393
cationic mechanism for, 393-395
coordination mechanism for, 396-397, 1446
general characteristics of, 390-397, 1420,
1446- 1453
monomers for (table), 39 1, 1432- 1433
radical-chain mechanism for, 395-396,
1446- 1449, 1452- 1453
uses of products of (table), 391,
1432-1433
proton chemical shifts of, 310-3 11
radical-chain addition to, hydrogen bromide in,
386-389
orientation in, 386-389
reagents for (table), 389
stereochemistry of, 388
Raman spectra of, 284-286
reduction of, comparisons of procedures
(table), 428
with zirconocene chlorohydride, 1514
resonance structures for, 176
Ritter reaction of, 1149, 1178-1 179
rotation about the double bond of, 167,
1384- 1386
spin-spin splittings in, 320, 325-326
sulfate esters from, 369-371
sulfuric acid addition to, 369-37 1
thermodynamic control of additions to,
374-376
triplet states of, geometry of, 1385
with zirconocene chlorohydride, 1512-1 514
Alkenic hydrogens, definition of, 60
Alkenols, alkenones from, by chromic acid oxidation, 642
properties of, 648-65 1
Alkenones, addition reactions of, 768-770
1,4-additions of organometallics to, 585-586
from alkenols, by chromic acid oxidation, 642
electronic spectra of, 68 1
infrared frequencies of, 68 1
spectral properties of, 68 1, 767-768
Alkenyl groups, nomenclature of, 59-60
Alkenyl halides, coupling with metals, 572-573
+
organometallic compounds from, 572-573
physical properties of (table), 537-538
preparation of (table), 548, 588
reactivity of (table), 589
Alkenyloxyarenes, preparation of, 1297-1298
rearrangement of, 1298
Alkoxyarenes, cleavage of, 1295
preparation of, 1294
Alkyd resins, 1439- 1440
Alkyl cyanides (see Nitriles)
Alkyl halides, from alcohols, 625-627
alkylation of arenes with, 1056
from alkylzirconocenes, 1514
amines from, 1125-1 127, 1148
azides from, 1202
with benzenolate anions, 1294
from carboxylic acids, silver salts with bromine,
813-814
carboxylic acids from, 854
carboxylic esters from, 856
chiral, racemization mechanisms of, 896
conformations of, and nmr spectra, 1345-1347
coupling and disproportiona60n with metals,
572-573
electrophilic catalysis of S, reactions of, 234
elimination reactions of, mechanisms, reagents
and stereochemistry for, 240-25 1
ethers from, 655, 1294
Grignard reagents from, 57 1-575
from Grignard reagents and halogens, 586-587
methylsulfinylmethane oxidation of, 7 18
nitrile alkylation with, 1185
nitriles from, 1184-1 185
nitro compounds from, 1187, 1190- 1191
nmr shifts of, 308-310
nomenclature of, 56
nucleophilic reactions of, with alcohols, 614-615
mechanisms, reagents and stereochemistry of,
213-239
Williamson ether synthesis and, 6 14-6 15
organomagnesium compounds from, 576-577
organometallic compounds from, 572-573
b y halogen-metal exchange with halides,
573-574
physical properties of (table), 537-538
reactions of, 539-54 1
reactivities of (table), 539, 589
reactivity in SN1 and S,2 reactions, 224-230
reduction of, with tin hydrides, 109
silver ion catalysis of S, reactions of, 234
S,2 displacements of, with enamines, 764-765
with enolate anions, 762-763
with sulfur-stabilized carbanions, 765-766
syntheses for (table), 541, 587-589
with tetracarbonylferrate, 1516
Alkyl phosphates (see Phosphate esters)
Alkyl radicals, names for, 53
Alkyl shifts, with alkyl transition metal compounds, 1510-1516, 1518-1520,
1522-1526
Alkyl sulfate esters, from alcohols, 628-629
Alkyl sulfates, in alcohol dehydrations, 630-63 1
as detergents, 628
preparation of, 629
Alkyl sulfonate esters, from alcohols, 628-629
Alkylation, of carbanions and enolate anions,
761-766
of alkenes, mechanism and uses of, 397-398
of arenes, kinetic vs. equilibrium control in, 1066
of nitriles, 1185
Alkylbenzenes, by acylation and reduction of
arenes, 1052- 1053
from arene alkylations, 1047- 1050
detergents from, 1056- 1057
industrial syntheses based on, 1083
ipso nitration of, 1067-1068
from petroleum, 1079- 1083
rearrangement of, 1050
Alkylboranes, alcohols from by oxidation, 427-430
aldehydes from, with alkenes, 729
alkanes from, 427-428
amines from, 427, 430-43 1
carbonylation of, 724-726
reduction of carboxylic acids with, 810-81 1
Alkylcadmium compounds, from Grignard
reagents, 584
ketone synthesis with, 584
Alkylcopper compounds, 1,4-addition of alkenones
and alkenals, 585-586
ketone synthesis with, 584
from lithium compounds, 584
Alkylmercury halides, from alkylzirconocenes, 1514
Alkyltetracarbonylferrates, preparation and
reactions of, 1516
Alkylzirconocenes, preparation and reactions of,
1512-1515
Alkynes, acidity of I-alkynes, alkynide salts from,
437-440
in ammonia solutions, 438
gas phase vs. solution, 437-438
solvation effects and, 438-439
synthetic reactions derived from, 440-441
aldehydes from, by hydration, 729
by l~ydroboration-oxidation, 427-429
alkenes from 414, 1075
from alkynide-salt nucleophilic reactions,
440-44 1
atomic-orbital model for, 167-168
from azides, 1202
carbene additions to, 565
coupling reactions of, 44 1
electronic spectra of, 356
electrophilic addition to, bromine in, 282
characteristics of, 382-384
hydrogen fluoride in, 382
reactivity compared to alkenes in, 382
water in, 383-384
with Grignard reagents, 578
heats of hydrogenation of tiable), 4 15-4 16
hydroboration of, 422-423
hydrogenation of, Lindlar catalyst for, 414
stereochemistry of, 413-414
infrared spectra of, 356
infrared stretching frequencies for, 276
from isomerization of 1,2-alkadienes, 512-513
ketones from, by hydroboration-oxidation,
427-429
mass spectra of, 356-357
nomenclature of, 6 1-62
nucleophilic addition to, methanol in, 385
organometallics from, 574
oxidative coupling of, 441
physical properties (table), 351-352
proton chemical shifts of, 3 11
radical-chain addition of HBr, stereochemistry
of, 390
radical-chain additions to (table), 389-390
reduction to alkenes, 414, 1075
Alkynide anions, formation of, 437-441
as nucleophiles, 440-44 1
Alkynyl groups, nomenclature of, 62
Alkynyl halides, physical properties of (table),
537-538
preparation of (table), 548, 588-589
reactivity of (table), 549, 589
S,2 reactions of, 550
Allene (see 1,2-Propadiene)
Allenes, cycloadducts of, 502-503
general reactions of, 5 12-5 13
hydration of, 5 12
isomerization of, 5 12-5 13
stability of, 5 12-5 13
D-Allose, structure and configuration, 905
Allyl aryl ether rearrangement, 1298
Allyl bromide (see 3-Bromopropene)
Allylic halides, preparation of (table), 541-544, 588
reactivities of (table), 544-546, 589
rearrangements in reactions of, 545
Allylmagnesium bromide, nmr spectrum of, 1524
Allylnickel complexes, chemistry of, 1525- 1524
Alpha helix, peptides and, 1251-1252
D-Altrose, structure and configuration, 905
Aluminum alkoxides, aldehydes from, with
alcohols, 727
ketones from, 730
Aluminum bromide, as catalyst of bromine
addition, 16
Aluminum chloride, in acylation of arenes,
1051-1053
in alkylation of arenes, 1047-1050
ketone complexes of, 1052
Aluminum isopropoxide, in Meerwein-PonndorfVerley reduction, 6 11
Aluminum, in Ziegler polymerization, 1444
Ambrette seed, oil of, 1468
Ameripol, 1433
Amides, from acid derivatives (table), 1176-1 178
acidity of, 1175-1 176
from acyl halides, 1177- 1178
aldehydes from, by hydride reduction, 708, 728
from alkenes, 1178
as m i n e protecting group, 1159
amines from, by hydride reduction, 824-825
by Hofmann degradation, 1150, 1153,
1155-1 156
by hydrolysis, 1154
by reduction, 824-825, 1147, 1154
from amines, with acyl halides and
anhydrides, 822
and carboxylic acid derivatives, 1121-1 122,
1176-1 177
with ketene, 771
from azides, 1177- 1178
basicity of, 1176
from Beckmann rearrangement, 1180-1 181
from carbonate esters, 1177
carboxylic acids from, 854, 1177-1 178
cis-trans isomers of, 1171-1 173
coupling reactions for, with N,N-dicyclohexylcarbodiimide, 1240- 1241
in peptide synthesis, 1240- 1241
dipole moments of, 1168
from esters, 1177-1 178
geometry of, 1167-1 168
with Grignard reagents (table), 579, 823-824
hydrogen bonding of, 1168
hydrolysis of, 820-82 1, 1182- 1183
infrared spectra of, 680, 1170-1 171
IUPAC rules of nomenclature for, 199, 1169
from ketones, by Haller-Bauer cleavage, 747
nitration of, 1188- 1190
nitriles from, 1185
from nitriles, 1178-1 179
N-nitroso compounds from, 1183, 1163
with nitrous acid, 1183
nmr spectra of, 1172- 1175
from oximes, 1180- 1181
in peptide structures, 1227-1228
from phenyl esters, 1177-1 178
physical properties of, 1168
planarity of, 1168
polarity of, 1168
polymers of, 1181, 1441, 1456-1457
preparation of (table), 858, 1121-1 122,
1176-1181, 1236-1247
radical-chain addition to alkenes and
alkynes, 389
reactions of (summary), 1183
reduction to aldehydes, 708, 727
reduction to amines, 824-825, 1146- 1147
resolution of chiral forms of, 868
from Ritter reaction, 1149, 1178- 1179
solvent properties of, 1168
stabilization energy of, 1159, 1168
synthesis of, from acid derivatives (table),
1176-1 178
types of, 1169
Amidol, 1311
Amine oxides, alkenes from, 1143
azanols from, 1143
chiral forms of, 1143
preparation of, 1143
Amine salts, IUPAC rules of nomenclature
of, 1102
Amines, acid-base equilibria of, 41
acidities of, 1095, 1120
acidities of salts of, 1112
acylation of, 1121- 1122
alcohol comparisons with, 1095-1096
from alcohols, 1125- 1126
aldehyde additions of, 697-699, 702
alkylation of, 1125-1 127
from alkylation of amines and ammonia, 1149
amides from, 771, 822, 1121-1 122
from amides, by hydrolysis, 1154
m i n e function as leaving group, 1096
arnine oxides from, 1143
from ammonia and alkyl halides, 1125-1 126
base constants of (tables), 1101, 1111- 1118
basicities of, alkanamines and, 1095- 1096,
1112-1113
arenamines and (table), 1113-1 116
azarenes and, 1117-1 118
cycloalkanamines and, 1112-1 113
from Beckmann rearrangement, 1149
with benzenesulfonyl chloride, 1122- 1123
benzoylation of, as protecting group, 1159
benzyloxycarbonylation of, as protecting group,
1159-1160
tert-butoxycarbonylation of, as protecting group,
1159-1160
carcinogenic, 1161- 1162
chiral forms of, 1109- 1110
chiral, as resolving agents, 866-867
from Curtius degradation, 1150, 1156
electronic spectra of, 1105
enarnines from, 1122
enamines with aldehydes and ketones, 702
ethanoylation of, as protecting group, 1159
from Gabriel synthesis, 1148
Hinsberg test for, 1123
from Hofmann degradation, 1150, 1155
hydrogen bonding of, 1103
imines from, 1122
infrared spectra of, 277, 1104
inversion of, 1109- 1110
IUPAC rules of nomenclature of, 200-201,
1100-1 102
ketone additions of, 697-699, 702
mass spectra of, 1106- 1108
metal salts of, benzyne generation with, 1120
enolate salt generation with, 1120
nomenclature of, 1120
as nucleophiles, 1126- 1127
preparation of, 1120
from nitriles, by hydride reduction, 824-825
nitro compounds from, by oxidation, 1144
with nitrous acid, diazonium salts from,
1129-1 133
differentiation by, 1129
nitrogen as leaving group in, 1096
N-nitrosamines from, 1129-1 130, 1136
nmr spectra of, chemical shifts in, 1105
and hydrogen exchange, 1105
nitrogen- 14 relaxation effects on, 1106
as nucleophiles, 1096, 1121-1 129
odors of, 1103
oxidation of, 1141-1145
phenylmethoxycarbonylation of, as protecting
group, 1159- 1160
physical properties of (table), 1101-1 103
preparation of, by alkylation of amines,
1125-1 126
from amides, 824-825, 1146-1 147, 1150,
1154-1 156
Gabriel synthesis for, 1127
from nitriles, 1146- 1147
from nitro compounds, 1146-1 147, 1151
by sulfonamide synthesis, 1127
protecting groups for, acylation for, 1158- 1160
alkylation for, 1157-1 158
protonation for, 1157
sulfonylation for, 1161
table of, 1236-1239
pro ton exchange in, 3 11-3 13
protonation of, as protecting group, 1157
from reduction, amides, 1146-1 147, 1154-1 155
azides, 1146, 1150
imines, 1146, 1148, 1154
nitriles, 1146- 1147
of nitro compounds, 1146- 1147, 1151
oximes, 1146, 1148
from reductive alkylation, of aldehydes and
ketones, 1148, 1154
from Ritter reaction, 1149, 1179
Schiff bases from, 1122
from Schmidt degradation, 1150, 1156
stereochemistry of, 1108-1 110
sulfonamides from, 1122- 1123
sulfonylation of, as protecting group, 1161
synthetic routes to (table), 1145- 1156
triphenylmethylation of, as protecting
group, 1158
vitamins as, 1099
water solubility of (table), 1101, 1103
Amino-acid sequencing of peptides, 1229-1234
Amino acids, abbreviations for, 1207-1210
acid-base properties of, 1212-1215
acidic type, 1207
with aldehydes, 1223-1225
from amination of halo acids, 1225
analysis of, fluorescamine, 1217- 1218
ion-exchange chromatography, 1219
ninhydrin, 1216-1218, 1221
paper chromatography and, 1218- 1219
thin-layer chromatography, 1219
azarene types, 1207-1210
azlactones from, 1222
basic type, 1207
chiral, 1207
configurations, D,L conventions for, 132
configurations of, naturally occurring, 1207
deamination of, 1223- 1224
decarboxylation of, 1223- 1224
diketopiperazines from, 1222
dip-olar forms of, 1212- 1215
electronic spectra of, 1216
from enolate anion alkylations, 1225- 1226
equilibria of, 1210-1215
esters from, 1221-1222
fluorescamine, reaction, 1217
imines from, 1223- 1224
infrared spectra of, 1215
ion-exchange chromatography, 1219- 1220
isoelectric points of (table), 1208-1210, 1212
isolation of, 1227
malonic ester syntheses of, 1225-1226
mass spectra of, 1216
melting points of, 1215
metabolism of, 1224- 1225
from Michael additions, 1226
ninhydrin reaction, 1216-1217
with nitrous acid, 1223
nonprotein examples, 1211
paper chromatography, 1218-12 19
in peptides, conventions for, 1228
peptide bond of, 1228
physical properties (table), 1208-12 10, 1215
p K values of (table), 1208-12 10
protecting groups for, in peptide syntheses,
1236- 1247
as protein constituents (table), 1206-1210
purification of, 1227
with pyridoxal phosphate, 1224-1225
reactions of, 1221- 1225
resolution of, 1227
and tRNA, 1281-1282
solubility characteristics of (table),
1208-1210, 1215
Strecker synthesis for, 1225
substituent groups on, 1207
sulfur containing, 1207-1209
synthesis of, 1225- 1227
thin-layer chromatography of, 1219
Aminoacyl-tRNA, 1281-1282
4-Aminobenzenesulfonamide, 1123-1 124
4-Aminobenzenol, from phenylazanol, 1140
as photographic developer, 1311
physical properties of, 1290
4-Aminobutanoic acid, and nerve impulses, 1211
l-Aminoethanol, 700
Aminophenols (see Aminobenzenols)
Aminophenylethanoic acid, synthesis of, 1225
4-Aminostilbene, as carcinogen, 1162
Ammonia, bond angles of, 163, 168
physical properties of, 19, 239, 1101
in prebiotic evolution, 1282-1284
Ammonium polysulfide, nitro group reduction
with, 1151
AMP (see Adenosine phosphate esters)
Amphetamine, 867, 1098
Arnygdalin, 926, 1327
Amylase, 935
Amylopectin, 934-935
Amylose, 934
Anaesthetics, 1099
Analgesic drugs, 1098, 1328
Androsterone, structure and occurrence, 1473
Angle strain, Bredt's rule and, 484
and carbonyl reactivity, 677-678
in cycloalkanes, 448-449, 462-467
in cycloalkenes, 474-476
in cycloalkynes, 475-476
in polycycloalkanes, 482-485
Aniline (see Benzenamine)
Aniline Black, 1145, 1406
Anionic polymerization, of alkenes, 392-393
Anisole (see Methoxybenzene)
Annelation reaction, 1477- 1478
[IgIAnnulene, nmr spectrum of, ring current
effects on, 1034-1035, 1088
Annulenes, "bond fixation" in, 1090
bond lengths of, 1090
equilibration of, 1088
nmr spectra of, 1035, 1088
nomenclature of, 1087
substitutions of, 1088
Anomers (see also individual sugars), of
D-glucose, 9 14-9 18
Antarafacial elimination, definition of, 245-246
Anthocyanins, as flower pigments, 925, 1403
Anthracene, bromination of, 1072
from coal tar, 1080
Diels-Alder additions to, 1077
electronic spectra of, 1033
physical properties of, 1027
reduction of, 1074
stabilization energy of, 985
9,lO-Anthracenedione, as dye component, 1407
Anthr aquinone, 1407, 1409
Anti conformation, definition of, 124
Antibiotics, 1097- 1099
Antibonding orbital, definition of, 156
Anticodons, of tRNA, 1279-1282
Antihistamine, 1328
Antirachitic hormone, 1472
Apoprotein, 1256
Aprotic solvents, 238
D-Arabinose, structure and configuration, 904
L-Arabinose, properties and occurrence of, 907
Arenamines, from amides, by hydrolysis, 1154
arenols from, 1293
from aryl halides, with activating groups,
1128, 1152
by benzyne mechanism, 1120, 1128, 1152
basicities of, Harnmett correlation of, 1334
table of, 1113-1 116
from Beckmann rearrangement, 1153
from benzidine rearrangement, 1153
from Bucherer reaction, 1295- 1296
as carcinogens, 1161- 1162, 1164
from Curtius degradation, 1153, 1156
from Hofmann degradation, 1153, 1155
from nitro compounds, 1193
nitro compounds from, 1187- 1191
N-nitroso, rearrangements of, 1139-1 140
with nitrous acid, diazonium salts from, 1133
N-nitrosamines from, 1136
ring nitroso substitution in, 1136
oxidation of, 1144- 1145
from phenols, 1295- 1296
as polymerization inhibitors, 1449
protecting groups for, 1157-1 161
quinones from, 1145
from reduction, of nitro compounds, 1151
resonance in, and base strengths of, 1113- 1115
ring substitution reactions of, 1128-1 129
from Schmidt degradation, 1153, 1156
N-substituted, rearrangements of, 1139-1 140
Arene polyols, 1303- 1305
Arenediazonium salts (see Benzenediazonium
salts)
Arenes (see also Benzene, Methylbenzene,
Naphthalene, etc.), acid strengths of alkyl
(table), 1322
alkyl substituted, from coal tar and petroleum,
1079-1081
from arenediazonium salts, 1134, 1138
charge-transfer complexes of, 1192- 1193
in chlorination of alkanes, selectivity effects, 102
from coal tar, 1079-1083
cycloaddition reactions of, 1077
electronic spectra of, benzene chromophore
and, 1030-1034
benzenoid band in, 1032- 1033
halides from, 1044- 1046
halogen addition to, 1076
and Hammett equation, 1329-1337
hydrogen exchange of, 1057
hydrogenation of, 4 14
infrared spectra of, 276, 1027-1029
IUPAC rules of nomenclature for, 1024-1026
ketones from, 1051-1053
nitration of, 1041-1043, 1058-1072, 1187-1190
nrnr spectra of, ring currents and, 1034-1035
spin-spin splittings in, 1036-1037
nomenclature of, 62-64
oxidation of, with oxygen and vanadium
catalysts, 1077-1078
from petroleum by catalytic reforming,
1079-1081
physical properties of (table), 1026-1027
picrates of, 1192
proton chemical shifts of, 3 11
reactivity correlations of, 1329- 1337
reduction of, Birch procedure for, 1074- 1075
by hydrogenation, 1022- 1024
with sodium in alcohol, 1073-1074
side-chain derivatives of, 1316-1328
side-chain halogenation of, 546-547, 1046,
1317-1318
side-chain substituted, 1287, 1327-1328
spectral properties of, 1027- 1036
toxicity of, 1026
Arenols {see also Phenols), properties of (table),
1288-1291
Arginine, properties, 1209
Arndt-Eistert synthesis, 1200
Aromatic character, and benzene, 10, 173-174,
957-968
of dibenzenechromium, 1507
of ferrocene, 1504- 1507
of nonbenzenoid cyclic polyenes, 98 1-995,
1084-1089, 1090
Aromatic halides (see Aryl halides)
Aromatic hydrocarbons, production and uses of
(tables), 1079-1083
Aromatic substitution (see Electrophilic or
Nucleophilic aromatic substitution)
Aryl azides, from arenediazonium salts, 1139
Aryl ethers, cleavage of, 1295
preparation of, 1294
Aryl halides, from arene halogenations, 1039,
1044- 1046, 1070- 1072
from arenols, 1295
from benzenediazonium salts, 1134-1 136
benzyne from, 1120
nitriles from, 1184- 1185
nucleophilic substitution of, radical mechanism
for, 573
organomagnesium compounds from, 576-577
organometallic compounds from, by
halogen-metal exchange, 574
with metals, 572-573
physical properties of (table), 537-538
preparation of (table), 55 1-552, 589
uses of, 561
Aryl nitro compounds (see Nitrobenzene)
Arylmethanes, acid strengths of (table), 1322
Arynes (see also Benzyne), from aryl halides,
558-559
Ascaridole, 1466
L-Ascorbic acid, properties of, 650
structure of, 938
Asparagine, codon for, 1282
hydrolysis of, 1229
properties, 1209
Aspartic acid, ionization equilibria of, 1214
properties, 1209
Asphalt, 74
Aspirin, 1328
Asymmetric synthesis, in aldol addition, 893-894
in biological reactions, 894
principles of, 893-894
Atactic polymers, 1430-1435
Atomic energy states, 268-269
Atomic-orbital models, ab initio calculations with,
179-182
of alkanes, 162
alkyne-alkane acidity and, 439-440
for benzene, 172- 175, 967-968
of carbonyl bonds, 675
of E2 transition state, 247
of ethane, 162
of ethene, 165-167
of ethyne, 167-168
of hydrogen, 962-963
of methanol, 164-165
for methide anion, 169
for methyl carbocation, 169
for methyl radical, 169- 170
of 1,2-propadiene, 508-509
for 2-propenyl radical, 178-178
for S, transition states of, 221, 223
Atomic orbitals, bond formation with, 155- 157,
960-966
for carbon, 154-155
designations for, 151-152
electron pairing in, 153- 154
electron probabilities and, 151-152
energies of, 151-153
ground-state electronic configurations of,
153-155
hybrid, sp-type, 159, 167-168
sp2-type, 160-161, 165-166
sp3-type, 160, 162
hybridization of, 159- 161
hydrogenlike, 151-152
order of filling, 153-155
overlap of, in bond formation, 155-161, 962-966
and bond strengths, 159-160
phases of, 156
pi (T)overlap, 165-167
promotion of electrons in, 158-160, 163-164
quantum numbers of, 151-152
shapes of, 151-152
sigma (o) overlap, 156-165
tau (7) bonds with, 165-167
for unshared electrons, 162-165, 168-172
valence state configurations, 158-160, 163, 168
Atomic weights, determination of, 4
ATP (see Adenosine phosphate esters)
Atropine, 1097
Autoxidation, of benzenecarbaldehyde, 7 12-7 13
of ethers, 658-659
of (1-methylethyl)benzene, 72 1
Autumn crocus, 1316
Auxochromes, definition of, 1030
substituent effects of, 1402-1404
Avogadro, A., 4
Axial positions (see Cyclohexane)
Azabenzene, in alkyl halide formation, 627
base strength of, 1117-1 118
from coal tar, 1080
physical properties of, 239, 1101
stabilization energy of, 985
in sulfonate ester formation, 629
Azabenzene-chromic acid, alcohol oxidation
with, 642
Azacycloalkanes, nomenclature systems for,
659-66 1
1-Aza-2-cycloheptanone, from cyclohexanone
oxime, 1181
polymer from, 1181, 1433, 1441
Azacyclohexane, physical properties of, 1101
Azacyclohexanes, inversion rates of, 1110
Aza-2,4-cyclopentadienes, from
1,4-alkanediones, 778
1-Aza-2-cyclopentanone, solvent properties
of, 1168
Azacyclopropanes, inversion rates of, 1110
1-Azanaphthalene, base strength of, 1118
from coal tar, 1080
Azane oxides (see also Amine oxides), 1143
Azanols, in arnine oxidations, 1143- 1144
Azanyl hydrogen sulfate, organoborane reactions,
427, 430-43 1
Azarenes, base strengths of, 1117- 1118
from diarylethanediones, 1326
Azeotropes, definition of, 258
Azides, from alkyl halides, 1202
m i n e s from, 1146, 1148, 1150, 1153, 1156, 1202
from arenediazonium salts, 1139
explosive properties of, 1202
from hydrazines, 1197, 1202
reduction of, 1202
Azine (see Azabenzene)
Azine dyes, 1406
Azines, from aldehydes and ketones, 698
Azlactones, from amino acids, 1222
Azo compounds, from arenediazonium
couplings, 1137
from hydrazines, 1197
initiation of polymerization with, 1447
preparation of, 1194, 1198
radical decomposition of, 1198
Azobenzene, as dye component, 1407
preparation of, 1194
reduction of, 1194
thermal decomposition of, 1198
Azobisisobutyronitrile, initiation of polymerization
with, 1447
Azomethine dyes, 1414
Azonia nomenclature, 1102
Azoxybenzene, from nitrobenzene, 1194
Azulene, basicity of, 1085
polarity of, 1084
rearrangement of, 1084
stabilization energy of, 985
substitution reactions of, 1084
Bachmann, W. E., and equilenin synthesis, 1495
Back bonding, 1509-15 10
Back-side approach, 2 19-223
Bactericides, aryl halides for, 56 1
Baeyer, A., and strain in cycloalkanes, 463-465
Baeyer-Villiger oxidation, of aldehydes and
ketones, 712-713
Bakelite resins, 1442-1443
Ball-and-stick models, of carbon compounds,
34-35
of cis-trans isomers, 112- 114
of conformations, 122-123, 449-452
Paterno and, 3
Bartlett, P. D., and carbocation hydrogen-transfer
reactions, 397-398
Barton, D. H. R., and conformational analysis,
124, 450
Base catalysis, of aldehyde and ketone
halogenations, 742-745
of aldol additions, 749-754
of aldose-ketose interconversions, 9 18-9 19
of chiral ketone racemization, 896
of dehydration of aldols, 755-756
of en01 and keto equilibria, 828
of enolization, 736-738
of hydrogen cyanide to aldehydes and ketones,
689-690
of nitrile hydrolysis, 1178
of unsaturated alkanoic acid rearrangements, 841
Base strengths, standard expressions for, 1111-1 112
Bay, oil of, 1462, 1464
9-BBN, from 1,5-cyclooctadiene, 423
Beckmann rearrangement, amides from, 1149,
1153, 1180-1181
arnines from, 1149, 1153
Beer-Lambert law, 291, 293
Benadryl, 1328
Benzal chloride (see Dichloromethylbenzene)
Benzal fluoride (see Difluoromethylbenzene)
Benzaldehyde (see Benzenecarbaldehyde)
Benzedrine, 1098
Benzenamine, from aryl halides, 557-558, 1128
azo compounds from, 1194
'
basicity, electronic effects on, 1 113-1 116
Hammett correlation of, 1334
1,4-benzenedione from, 1145
bromination of, 1128
from bromobenzene, 557-558
electronic absorptions of, 1030- 1033, 1402- 1403
hydrogenation of, 1073
from nitrobenzene, 1193
oxidation of, 1144- 1145
physical properties of, 1101
stabilization energy of, 986
substituted, basicities of (table), 1114-1 116
Benzenamines, from aryl halides, 557-558, 1128
Benzene, acylation of, 1051-1053
alkyl substituted, nitration of, 1042-1043
alkylation of, 1047- 1050
atomic-orbital model of, 172-1 74, 968-969
benzenol from, 1291- 1293
Birch reduction of, 1074- 1075
bond lengths in, 987
bromination of, 1044-1045
bromine addition to, 967-968
bromine substitution of, 552, 1044-1045
charge-transfer complexes of, 1192-1 193
chlorine addition to, 1076
chlorobenzene from, 1291
chloromethylation of, 1054, 1319
chlorosulfonation of, 1056
chromium derivative of, 1506- 1507
as chromophore, 1402
1,4-cyclohexadiene from, 1074- 1075
delocalization energy of, 173- 176
derivatives of, IUPAC rules of nomenclature
for, 1024- 1026
spectral properties of, 1027-1037
deuterated, preparation of, 1057
Dewar resonance structures for, 175-176
electrophilic substitutions of (table), 1037- 1040
fluorescence and phosphorescence of, 1375
Friedel-Crafts alkylation of, 1047- 1050
general reactions of, 967-968
geometry of, 173, 966
GVB treatment of, 983-984
halogen additions to, 1046
heat of combustion of, 174, 967
heat of hydrogenation of, 967
hexachloride of, 1066
and 1,3,5-hexatriene, 967-968
hydrogen exchange of, 1057
hydrogenation of, 967-968, 1072- 1073
industrial syntheses based on, 1082
iodination of, 1044-1045
Kekuli: and, 10
ketones from by acylation, 1051- 1053
mercuration of, 1058
molecular-orbital treatment of, 969-97 1
nitration of, 1041
with nitric acid, 967-968
nomenclature of, 62-64
oxidation of, with oxygen and vanadium
catalysts, 1077- 1078
with ozone, 967-968, 1078
from petroleum, 1079- 1083
photoelectron spectra of, 1357
physical properties of, 239, 1027
radical anion of, 1075
representations of, 974
resonance treatment of, 173-177, 972-974
sandwich compound of, 1506- 1507
stability of, 173-175
stabilization energy of, 967-968, 985
structure of, 10- 11, 966-967
structure problem presented by, 9- 11
substituted, orientation effects in, 1058-1068
substituting agents for, 1037-1058
sulfonation of, 1055-1057
with tetracyanoethene, 968
valence-bond treatment of, 972-975
Benzenecarbaldehyde, aldol addition of, with
2-propanone, 756
autoxidation of, 712-713
benzoin from, 1324
from chloromethylbenzene, 1318
from dichloromethylbenzene, 1318
difluoromethylbenzene from, 1318
electronic absorptions of, 1030- 1031
glycosides of, 926, 1327
Hammett reactivity correlations with, 1334
physical properties of, 679
with sulfur tetrafluoride, 1318
Benzenecarboxylic acid, from oxidation of
methylbenzene, 1317
physical properties of, 792
substituted, acidities of (table), 1327-1333
from trichloromethylbenzene, 1318
1,4-Benzenediamine,arenecarboxamide polymers
from, 1456-1457
base strength of, 1115
ladder polymers from, 1456- 1457
from phenyldiazane, 1140
l,2-Benzenediarnines, quinoxalines from, 1326
1,4-Benzenediamines, as color developers,
1413-1414
Benzenediazonium salts, aryl azides from, 1138
azo compounds from, 1137
Index
copper catalysis of reactions of, 1134-1136
coupling to biaryls, 1138
coupling with alkenes, 1135-1 136
cyanoarenes from, 1134
decomposition of, 1133
diazo coupling of, 1137- 1138
diazotate salts from, 1139
hydrazines from, 1138
with hypophosphorous acid, 1189- 1190
iodide reaction with, 1136
with I -naphthalenol, 1300
nitriles from, 1185
nitro compounds from, 1191
phenyl cations from, 1133, 1135
phenyl radicals from, 1135- 1136
preparation of, 1133
reactions of (table), 1138-1 139
reduction of, 1134, 1138, 1189- 1190
triazenes from, 1137
1,2-Benzenedicarbonitrile,copper phthalocyanine
from, 1408
1,2-Benzenedicarboxyhydrazide,1127
1,2-Benzenedicarboximide, acidity of, 1176
hydrazine cleavage of, 1127
hydrolysis of, 1127
in Gabriel m i n e synthesis, 1127
synthesis of, 850
1,2-Benzenedicarboxylicacid, anhydride from, 847
properties and uses of, 849
1,3-Benzenedicarboxylicacid, polyesters from, 1440
1,4-Benzenedicarboxylicacid, 1,4-di(trifluoromethyl) benzene from, 1318
epoxy resins from, 1444-1445
polyesters from, 1438
polymers from, 1433, 1456- I457
properties and uses of, 849
with sulfur tetrafluoride, 1318
1,2-Benzenedicarboxylicanhydride, from
naphthalene oxidation, 1078
polyesters from, 1439-1441
uses of, 1078
1,2-Benzenediol, 1,2-benzenedione from, 1303
from 1,2-dichlorobenzene, 1303
physical properties of, 1289
1,3-Benzenediol, from 1,3-benzenedisulfonic
acid, 1304
physical properties of, 1289
1,4-Benzenediol, 1,4-benzenedione from, 1303
from 1,4-benzenedione, 1306- 1307
electrode potential of, 1306
as photographic developer, 1310-13 11
physical properties of, 1289
as polymerization inhibitor, 1449
substituted, from 1,4-benzenedione additions,
1311-13 12
1,2-Benzenedione, from 1,2-benzenediol, 1303
as quinone, 1305
1,4-Benzenedione, additions to, of
1,3-butadiene, 1312
of ethanoic anhydride, 1311-1312
of hydrogen chloride, 1311-13 12
from benzenamine, 1145, 1303
from 1,4-benzenediol, 1303
1,4-benzenediol from, 1303
from benzenol, 1300- 1301
complex with 1,4-benzenediol, 1307
electrode potential of, 1306
with hydroquinone, 1307
in photographic development, 1311
quinhydrone from, 1307
reduction of, 1306- 1308
semiquinone from, 1307
1,3-Benzenedisulfonicacid, 1,3-benzenediol
from, 1304
Benzenesulfonic acid, from benzene, 1055, 1291
benzenol from, 1291
preparation of, 1055-1056
Benzenesulfonyl chloride, m i n e protecting groups
from, 1161
benzenesulfonic acid from, 1056
in Hinsberg test for arnines, 1123
preparation of, 1056
sulfonamides from, 1122- 1123
sulfonate esters from, 629
1,2,4,5-Benzenetetracarboxylicacid, ladder
polymers from, 1456
polyimides from, 1456
1,2,4,5-Benzenetetracarboxylicdianhydride,
polyesters from, 1440
1,2,3-Benzenetriol,from
2,3,4-trihydroxybenzenecarboxylicacid, 1304
1,2,5-Benzenetriol, ethanoate ester, 1312
1,3,5-Benzenetriol, from
2,4,6-trinitrobenzenecarboxylicacid, 1304
Benzenol, acidity of (table), 736-738, 1293-1294
aldol type reactions of, 1300
Bakelite resins from, 1442- 1443
from benzene, 1291-1292
from benzenediazonium salts, 1133, 1136
14-benzenedione from, 1300- 1301
from benzenesulfonic acid, 1291
bromination of, 1296- 1297
carboxylation of, 1297- 1298
from chlorobenzene, 557, 1291
from coal tar, 1081, 1291
with diazomethane, 1294
with dichlorocarbene, 1299
electronic absorptions of, 1030- 1032, 1402- 1403
as enol, 651
esters from, 1294
ethers from, 1294
hydrogenation of, 1073
from hydroperoxide rearrangement, 721-722
2-hydroxybenzenecarbaldehyde from, 1299
2-hydroxybenzenecarboxylic acid from,
1298- 1299
from isopropylbenzene, 1293
IUPAC rules of nomenclature for, 191
Kolbe-Schmitt reaction of, 1298-1299
with methanal, 1300, 1442-1443
from methylbenzene, 1292- 1293
oxidation to quinone, 1300- 1301
physical properties of, 1289, 1291
quinone from, 1300-1301
radical from, 1301
sodium salt, electronic absorptions of, 1032
stabilization energy of, 986, 1293
Benzhydrol (see Diphenylmethanol)
Benzhydryl derivatives (see Diphenylmethyl
derivatives)
Benzidine, as carcinogen, 1162
from hydrazobenzene, 1140
rearrangement of, 1140
Benzil, as 1,2-dione, 774-775
formation of, 1325
quinoxalines from, 1326
rearrangement of, 775, 1325-1326
Benzilic acid rearrangement, of diarylethanediones,
775, 1326
Benzocaine, 1328
Benzoic acid (see Benzenecarboxylic acid)
Benzoin, formation of, 1324-1325
oxidation to benzil, 1325
Benzoin condensation, 1324- 1325
Benzophenone (see Diphenylmethanone)
Benzopinacol, 1382- 1383
Benzoquinone (see 1,4-Benzenediol)
Benzotrichloride (see Trichloromethylbenzene)
Benzotrifluoride (see Trifluoromethylbenzene)
Benzoyl chloride (see Benzenecarbonyl chloride)
Benzoyl nitrate, 1043
Benzoyl peroxide, initiation of polymerization
with, 1447
Benzyl alcohol (see Phenylmethanol)
Benzyl bromide (see Bromomethylbenzene)
Benzyl chloride (see Chloromethylbenzene)
Benzyl halides (see Phenylmethyl halides)
Benzyloxycarbonyl groups, as protecting group for
mines, 1159- 1160, 1237- 1239
Benzylpenicillin (see Penicillin G)
Benzyne, from amine salts, with aryl halides, 1120
from 2-benzenediazoniumcarboxylate, 559
cycloadditions of, 559
1,3-cyclopentadiene addition, 576
as intermediate in aryl halide reactions, 557-559
nucleophilic additions to, 558-559
from organometallic reactions, 575
Bercaw, J. E., and nitrogen fixation by
zirconocene, 1508
Bergamot, oil of, 1468
Bernal, J. D., and structures of steroids, 1476-1477
Beryllium hydride, bonding in, 157- 159
properties of, 19
BHC, 1076
Biacetyl, 774
Biaryls, from arenediazonium salt couplings, 1138
chiral forms of, 5 10-5 11
Bicyclo[l.l.O]butane, from 1,3-butadiene, 1389
physical properties and strain energy of
(table), 483
Bicyclo[4.4.0]decane (see Decalin)
Bicyclo[2.2.1]-2,4-heptadiene(see Norbornadiene)
Bicyclot2.2.llheptane, exo-endo isomerism of
derivatives of, 497
synthesis of, 526-527
Bile acids, 1475- 1477
Bimolecular reactions, 2 16
Bioluminescence, 1397- 1399
Biosynthesis, of alkaloids, 1489
of aromatic rings, 1481-1482
of cephalosporins, 1492
of cholesterol, 1486-1488
of fatty acids, 1480-1481
of penicillins, 1492
of prostaglandins, 1493- 1494
of terpenes, 1483-1485
Biotin, in fatty acid synthesis, 1483
Biphenyl, electronic absoprtions of, 1031
from Grignard coupling, 1505
quinone of, 1306
stabilization energy of, 985
4,4'-Biphenyldione, as quinone, 1306
Biphenylene, stabilization energy of, 985
Biphenyls, chiral forms of, 5 10-5 1 1
Biradical intermediates, in [2 21 cycloadditions,
1014-1017
Birch, A. J., and acetogenin hypothesis, 1481-1482
and reduction of arenes, 1074-1075
Bisabolene, 1468
Bis(cyclooctatetraene)uranium, 1508
Bis(pentenylnickel), 1508
Bisphenol A, epoxy resins from, 1444- 1445
polyesters from, 1439
Bisulfate (see Hydrogen sulfate)
Bisulfite (see Hydrogen sulfite)
Bloch, K., and fatty acid biosynthesis, 1480
Block polymers, 1452, 1454-1455
Bohr frequency condition, 269
Bombykol, structure and activity of, 141
in simple compounds,
Bond angles, C-C-C
34-36
in carbocylic rings, 448, 462-465, 484
and electronic repulsions, 157-164, 169-172
Bond energies (see also Bond-dissociation
energies), accuracy of, 79-80, 465
average values of, 78-80
and chlorination of methane, 85
of cycloalkanes, 465
definition of, 76-79
and reactivity, 96-97
resonance effect on, 177-178
tables of, 77, 92, 674
Bond formation, with atomic orbitals, 155- 157
by pi (n) overlap, 165-167
by sigma (o) overlap, 156-165
Bond lengths, and bond energies, 960-961
of carbon-carbon bonds, 36-37
of carbon-chlorine bonds, 37
of carbon-hydrogen bonds, 37
and double-bond character, 987
and hybridization (table), 987-988
Bond strengths, correlation with leaving group
reactivity, 232-233
Bond-dissociation energies, definition of, 93
table of, 92
Borane, reduction of carbonyl compounds with
(table), 707-708
Borane reductions, alcohols from, 6 10
+
Boranes, additions to alkenes, 380, 420-429
carbonylation of, 724-726
oxidation of, 427-43 1
Boron hydrides (see Hydroboration)
Boron trifluoride, ether complexes of, 656
Bragg, W. and L., and x-ray diffraction structure
determinations, 1249
Bredt's rule, and polycycloalkenes, 484
Bridgehead double bonds, Bredt's rule and, 484
Bright scarlet, 1407
Bromination, of alkanes, selectivity in, 101-102
of arenes, 1044-1045, 1070-1072
of hydrocarbons, with N-bromobutanimide,
103-104
Bromine, addition to ethyne, 382
additions to alkenes, 360-367, 379
aluminum bromide catalysis of addition of, 16
azide of, addition to alkenes, 379
radical-chain addition to alkenes and
alkynes, 389
N-Bromoamides, in Hofmann degradation,
1155-1 156
Bromobenzene, amination of, 557-558
from benzene and bromine, 552
physical properties of, 538
N-Bromobutanimide (NBS, N-bromosuccinimide),
in additions to alkenes, 379
allylic bromination of alkenes with, 542-543
bromination of hydrocarbons with, 103-104
and hydrogen fluoride, in additions to
alkenes, 379
with methylbenzene, 1317
Bromocyclohexane, conformational equilibria
of, 454, 457
Bromoethane, hydrolysis of, 12
structure of, 3-6
Bromoform, 746
Bromomethane, electronic spectrum of, 289
SN2 reactivity and nucleophile structure
(table), 235
(Bromomethyl)benzene, from methylbenzene and
tert-butyl hypobromite, 106
from methylbenzene and
bromotrichloromethane, 104
l-Bromo-2-methylpropane, from hydrogen
bromide and 2-methylpropene, 374-376
2-Bromo-2-methylpropane, from hydrogen
bromide and 2-methylpropene, 374-376
Bromonium ions, in bromine additions to alkenes,
365-366
from l-bromo-2-fluoroethane, 366
l-Bromo-2-phenyl-l-propene, photochemical
isomerization of cis-trans isomers of, 1386
2-Bromopropane, E2 reaction of, 241
SN2 reaction of, 241
3-Bromopropene, from propene and
N-bromobutanimide, 104
N-Bromosuccinimide (see N-Bromobutanimide)
Bromotrichloromethane, radical-chain addition to
alkenes and alkynes, 389
Br$nsted, J. N., and acid-base theory, 208
Brown, C., 5
Brown, H. C., and hydroboration, 421
Brucine, 867, 1097
Bucherer reaction, 1295-1296
Bullvalene, 1089- 1090
Burgstahler, A. W., and cantharidin synthesis,
1497-1498
1,3-Butadiene, with l,4-benzenedione, 1312
bond distances in, 37
bromine addition by 1,2 and 1,4 modes, 489
chlorine addition to, 1441
cis-trans isomers of polymer of, 505
copolymerization of, with ethenylbenzene
(styrene), 506
with propenenitrile (acrylonitrile), 506
[4 41 cycloaddition of, 1004
dimerization of, 1004
electrocyclic reactions of, 1005-10 14
electronic spectrum of, molecular-orbital
treatment of, 980-98 1
transitions of, 289-29 1
ethene addition to, 492
heat of hydrogenation of, 415
1,6-hexanediaminefrom, 1441
homopolymerization of, 504-505
hydrogen bromide addition to, by radical
mechanism, 49 1
hydrogen chloride addition to, by 1,2 and 1,4
modes, 490, 542
iron tricarbonyl complex of, 1523
molecular-orbital treatment of, 475-477
molecular orbitals of, 976
nickel complexes of, 1523
photochemical additions and cycloadditions
of, 1388
photochemical reactions of, 1388- 1389
rotational conformations of, 495
s-cis-trans isomers of, 495
stabilization energy of, 986
sulfur dioxide cycloadduct, 500-501
tetrduoroethene cycloadducts of, 502, 1014-1017
valence-bond treatment of, 977
1,3-Butadiyne, from oxidative coupling of
ethyne, 441
Butanal, electronic absorption of, 795
by hydroformylation of propene, 722-723
physical properties of, 679
Butane, bond distances in, 37
conformational energies of, 123-125
conformations of, 123- 125
heat of combustion of, 79
rotational barrier of, 123-124
Butanedioic acid, anhydride from, 847
in citric acid cycle, 951-954
properties and uses of, 847
Butanedioic anhydride, polyesters from, 1440
2,3-Butanedione, from photolysis of
2-propanone, 1379
physical properties of, 679
Butanimide, acidity of, 850-85 1
N-bromo derivative of (see N-Bromobutanimide)
+
Index
resonance in, 850-85 1
synthesis of, 850
Butanoic acid, electronic absorption of, 795
physical properties of, 792
I-Butanol, industrial preparation of, 759
2-Butanone, alkylation of, 763
halogenation of, 745
infrared spectrum of, 273
mass spectrum of, 340-341
physical properties of, 679
2-Butenal, physical properties of, 679
preparation of, 755-756
1-Butene, heat of hydrogenation of, 4 15
infrared spectrum of, 353
2-Butene, allylic chlorination of, 543
bond distances in, 37
cis-, heat of hydrogenation of, 415
cis-trans isomers of, 111-1 12
from ethene, by metathesis, 1520-152 1
trans-, heat of hydrogenation of, 4 15
cis-Butenedioic acid, anhydride from, 847
properties and uses of, 849
trans-Butenedioic (fumaric) acid, biological
hydration of, 371-372
in citric acid cycle, 951-954
properties and uses of, 849
Butenedioic anhydride, from benzene oxidation,
1077-1078
copolymerization of, 1452
as dienophile, 496-498, 1077
in fiberglass, 1440
naphthalene addition of, 1077
polyesters from, 1440
3-Buten-Zone, electronic spectrum of, 289
in Robinson annelation, 1477-1478
1-Buten-3-yne (vinylacetylene), bond distances
in, 37
from dimerization of ethyne, 441
nmr spectrum of, 1353
tert-Butoxycarbonyl protecting groups, in peptide
syntheses, 1237- 1247
Butter Yellow, as carcinogen, 1162
from diazo coupling, 1137
Butyl alcohol
tert-Butyl alcohol (see 2-Methyl-2-propanol)
Butyl Carbitol, 656
tert-Butyl hypobromite, bromination of
hydrocarbons with, 106
tert-Butyl hypochlorite, in additions of alkenes, 379
for hydrocarbon chlorinations, 103- 104
with methylbenzene, 1317
Butyl rubber, 506, 508, 1432
N-tert-Butylalkanamides, from Ritter reaction,
1178-1 179
tert-Butylcyclohexane, conformational equilibria of
derivatives of, 458-460
tert-Butylhydroperoxide, alkylzirconocenes
oxidation with, 1514
2-Butyne, bond distances in, 37
hydrogenation of, 4 13-4 14
Butyric acid (see Butanoic acid)
C-alkylation, of enolate anions, 762-763
of ester anions, 833-835
of phenols, solvent effect on, 1297-1298
C-carboxylation, in Kolbe-Schmitt reaction, 1299
of ribulose, 941-942
Cadmium alkyls, ketones from, with acyl
halides, 73 1
Caffeine, 1097
Cahn-Ingold-Prelog convention for configurations,
879-884
Calvin, M., and path of carbon in photosynthesis,
94 1-943
Camphene, 1464
Camphor, as isoprenoid, 1466- 1467
synthesis of, 1467
Cancer chemotherapy, 1163
Cane sugar (see Sucrose)
Cannabinols, 1305
Cannizzaro, S., aldehyde oxidation-reduction
reaction of, 707-709
and atomic weights, 4
Cannizzaro reaction, of ethanedial, 775
Cantharidin, synthesis of, 1497
Caprolactam (see I-Aza-2-cyclopentanone)
Carbamic acids, from tert-butoxycarbonyl group
hydrolysis, 1160
from isocyanates, 1155- 1156
polyurethane foams and, 1455
Carbanions (see also Enolate anions), bonding
and geometry of, 169
C- vs. 0-alkylation of, 762-763, 833-835,
1297-1298
sulfur, nitrogen, and phosphorus stabilized,
reactions of, 691-693, 765-767
Carbazole, from coal tar, 1080
Carbene, carbon-hydrogen insertion of, 1200
from diazomethane, 1200
dichloro- from trichloromethane, formation and
reactions of, 563-564
Carbenes, complexes with transition metals, 1512,
1520-1521
cyclopropanes and cyclopropenes from, 565
electronic structure of, 564
formation of (table), 563-566
reactions and reactivity of, 563-567
rearrangement of, 567
singlet and triplet, 564
in tetrduoroethene preparation, 568
Carbenium ions (see Carbocations)
Carbitols, 656
Carbocations, in alcohol dehydrations, 63 1-633
in alkene hydrations, 368-37 1
from alkyldiazonium salts, 1130-1 131
in arene alkylations, 1047- 1050
aryl, from arenediazonium salts, 1133-1 136
atomic-orbital model of, 223
bonding and geometry of, 169
in halide formation, from alcohols, 626
in halogen additions to alkenes, 361-367
hydrogen-transfer reactions with alkanes,
397-398
Index
hyperconjugation and, 228
methyl groups and stability of, 375
rearrangement of, in alcohol dehydrations,
632-633
relative rates of, 25 1
S,l and E l reactions, 250-251, 632-633, 1010
in Ritter reaction, 1178-1 179
in S,1 reactions, 215-217
stability order of, 226-228
stereochemistry of, 222-223
steric hindrance and, 229
in terpene and steroid biosynthesis, 1484-1489
thermochemistry of formation of, 2 12-2 13
tropylium ion and, 1315
Carbohydrates, classification of (table), 902-908
definition of, 902
determination of configurations of, 909-9 12
enzymatic hydrolysis of, 930
furanose ring in, 920-922
hemiacetal and hemiketal structures of, 903-906
Kiliani-Fischer cyanohydrin synthesis of, 9 11
metabolism of, 944-956
nomenclature of, 903-908
occurrence of (table), 907-908
from photosynthesis, 939-943
physical properties of (table), 907-908
properties of, 909
pyranose ring in, 920-922
ring sizes in, 920
Wohl degradation of, 9 10
Carbon, bonding of, 18-19, 30-34, 162-168,
179-182, 964-968
oxidation states of, 405-409
tetrahedral, 6-7, 34-36, 160-161
valence of, 4-5, 34-36, 160, 405-409
Carbon-carbon bond formation, reactions for
(table), 5 18
Carbon-carbon bonds, lengths of (table), 36-37
Carbon-chlorine bonds, lengths of (table), 37
Carbon dioxide, equilibration with water, carbonic
anhydrase for, 1260
fixation in photosynthesis, 939-943
with organometallic compounds, 570-57 1,
579, 583
with phenols, 1298-1299
Carbon disulfide, physical properties of, 239
Carbon-hydrogen bonds, lengths of (table), 37
Carbon monoxide, with alkylzirconocenes, 1514
with arenes in Gattermann-Koch synthesis, 1053
copolymer with ethene, 1453
with di-n-propenylnickel, 1522
in hydroformylation, 722-723, 1518- 1519
insertion reactions of, 15 12, 1514, 1516, 1518
methanol from, by hydrogenation, 612
from photolysis of 2-propanone, 1379
with transition-metal compounds, 1512- 1516,
1518-1520, 1522-1524
Carbonate esters, amides from, 1177- 1 178
Carbonate ion, and resonance, 176- 177
Carbonic anhydrase, 1260
Carbonium ions (see Carbocations)
Carbonyl bond, alkene bond comparision, 673-674
atomic-orbital model, 675
dipole moment, 674-675
energies (table), 674
hydration of, 673-674
polarity of, 674-678
Carbonyl compounds (see Aldehydes, Ketones,
Carboxylic acids, and so on)
Carbonyl group, addition reactions to, 577-586,
685-7 12
electronic spectra of, 681
genera1 characteristics of, 671-678
infrared properties of (table), 680-68 1
reactivity of, 674-678
Carbonylation, of alkylboranes, 724-726
of methanol, 1520
Carbowax, 662
Carboxylate anions, IUPAC rules of nomenclature
for, 195
Carboxylic acids, from acetoacetic ester acid
synthesis, 854
acid-base equilibria of, 4 1
acyl chlorides from, with phosphorus
chlorides, 809
with thionyl chloride, 809
acyl halides from, 857
acyl phosphate derivatives of, in biochemical
esterifications, 636-637
from acyltetracarbonylferrates, 1516
from acylzirconocenes by oxidation, 1514
from alcohol oxidations, 639, 643, 855
alcohols from, by hydride reduction, 6 10,
809-8 11
aldehydes from, by hydride reduction, 719,
810-81 1
from aldehydes, Baeyer-Villiger, 7 13-7 14
Cannizzaro, 707-709
with oxidizing agents, 855
oxygen, 7 12-7 13
permanganate, 7 12
silver oxide, 712
from 2-alkanones, 855
alkene additions of, 379, 808
from alkene oxidations, 855
amides from, 858, 1177-1 178
from amides, 854
anhydrides from, 771, 857
from Arndt-Eistert synthesis, 855, 1200
biosynthesis of, 1480-1482
borane reduction of, 707-708
bromination of, Hell-Volhard-Zelinsky reaction
and, 814-815
from Cannizzaro reaction, 855
carboxylic esters from, 856
chiral, as resolving agents, 867-869
chlorination of, 815
decarboxylation of, carboxylate radicals and,
812-813
electrolytic, 8 13
with lead tetraethanoate, 8 14
with mercuric oxide, 8 14
silver salts and bromine, 8 13-814
thermal, 8 11-8 12
Index
with diazomethane, 1199
from dicarboxylic acid decarboxylations, 847
dimers of, 791
electronic spectra of (table), 793, 795
esterification of, with alkenes, 808
mechanism and practice of, 6 15-6 18, 807-808
side reactions in, 807-808
steric hindrance and, 807-808
from esters, 854
as fatty acids, 789-791
functional derivatives of (table), 817-820
general characteristics of, 788-791
general reactions of, 796
a-halo, nucleophilic reactivity of, 815-8 17
synthetic uses of, 8 15-8 17
P-halo, from unsaturated acids, 841-842
from haloform reaction, 855
halogenation of, Hell-Volhard-Zelinsky reaction
and, 8 14-8 15
hydrogen bonding of, 791
hydroxy, dehydration of, 843
lactones from, 843
synthesis of, 835-836
thermal reactions of, 843
from unsaturated acids, 841-842
infrared frequencies, 276-277, 680
infrared spectra of, 28 1-282, 793-794
ionization of, constants for (table), 792
electrostatic interpretation of, 799-800
entropy and, 801-802
inductive effects and, 798-800
relative to other acids, 789, 796-797
resonance and 796-798
solvation effects on, 801-802
substituent effects on, 798-802
IUPAC rules of nomenclature for, 195
from ketones, by Baeyer-Villiger oxidation, 855
by Favorskii rearrangement, 748-749
by haloform reaction, 746-747
by Kolbe-Schmitt reaction, 1298-1299
from malonic ester acid synthesis, 854
metabolism of, 837-840
from nitriles, 854
nmr spectra of, 793
nucleophilic attack on, 805-806
from organometallics, 854
from oxidation of alkyl aryl ketones, 1317
from oxidation of alkylarenes, 1317
from 3-oxobutanoic esters, 834, 854
from ozonides and methanol, 432
from phenols, 1298-1299
physical properties of (table), 79 1-792
preparation of (table), 854-855
from propanedioate esters, 834, 854
protecting groups for (table), 1236- 1239
protonation of, 6 17
radical-chain addition to alkenes and
alkynes, 389
reduction of, to aldehydes, 8 10-8 11
with diborane, 8 10-8 11
with metal hydrides, 809-8 10
resolution of chiral forms of, 866-867
with sulfur tetrafluoride, 705
trifluoromethyl derivatives from, 1318
unsaturated, 1,4-additions to, 840-841
in [4 21 cycloadditions (table), 493-494
hydration of, 841-842
hydrogen bromide addition to, 841-842
lactones from, 842-843
rearrangement of, 841
synthesis of, 836
Carboxylic anhydrides, acylation of arenes with,
1051, 1054
alcohols from, with Grignard reagents, 609
by hydride reduction, 824-825
amides from, 858, 1121-1 122, 1177-1 178
with amino acids, 1222
carboxylic esters from, 615-616, 856
from carboxylic acids, with ketene, 771
from dicarboxylic acids, 847
esterification of, 615-618, 856
as functional derivatives of carboxylic acids, 8 18
hydrolysis of, 820
infrared frequencies, 680
as intermediates in enzyme-induced reactions,
1263- 1265
IUPAC rules of nomenclature for, 198
preparation of (table), 557, 857
unsaturated, in [4 21 cycloadditions (table),
493-494
Carboxylic esters, acidities of (table), 736-738
from acids with diazomethane, 1199
acyl halides from, 857
acyloin reaction of, 852-853
from acylzirconocenes, 1514
from alcohols and acyl halides, 616-617, 856
from alcohols and anhydrides, 616-617, 856
from alcohols and carboxylic acids, 6 15-6 18,
806-808, 856
alcohols and ketene, 77 1
alcohols from, with Grignard reagents, 609
by hydride reduction, 824-825
sodium and alcohol reduction, 825
from alcohols, thionyl chloride and carboxylate
salts, 855
aldol additions of, 835
from alkyl halides and carboxylate salts, 856
amides from, 858, 1121-1 122, 1177-1 178
m i n e s from, by Curtius degradation, 1150
biochemical formation of, phosphate esters
and, 635-637
carboxylic acids from, 854
from carboxylic acids, with alcohols, 615-618,
806-808, 856
with alkenes, 808
with diazomethane, 856, 1199
Claisen condensation of, 829-832
enolate anions from, 835-836
by ester interchange, 856
as functional derivatives of carboxylic acids, 818
from Grignard reagents (table), 579, 583
with Grignard reagents, 823-824
hydrazides from, 858
a-hydrogen acidity, 737, 825-826
+
+
l ndex
hydrolysis of, 820-82 1
Harnmett correlation of, 1329-1330,
1334, 1336
hydroxaniic acids from, 858
hydroxy, synthesis of, 835-836
unsaturated esters from, 836
infrared frequencies, 680
interchange reaction of, 82 1
IUPAC rules of nomenclature for, 197-198
from ketones, Baeyer-Villiger, 7 13-7 14
by Favorskii rearrangement, 748-749
mechanism of formation of, 6 15-6 18
from nitriles, 856
preparation of (table), 856
as protecting groups for OH, 652
reactivity correlation of, 1329- 1330
soaps from hydrolysis of, 790
unsaturated, 1,4-additions to, 844-845
in /4 23 cycloadditions (table), 493-494
cycloadditions with diazomethane, 1200
Michael addition of, 844-845
rearrangement of, 841
synthesis of, 836
Carboxypeptidase, mechanism of action of,
1262- 1265
in peptide sequencing, 1231
precursor of, 1269
properties, 1250
proteolytic properties of, 1260
Carcinogens, aflatoxins as, 1163
amines as, 1161-1162
arenes as, 1026
azo compounds as, 1162
chloroethene as, 549
N-nitroso compounds as, 1163- 1164
Cardiac poison, 1473
P-Carotene, electronic absorptions of, 1401
with singlet oxygen, 1393
structure of, 33
as vitamin A precursoi; 1469
Carotenes, biosynthesis of, 1485, 1488
Carvone, structure and odor, 140
CaryophyIlene, 1464
Catalysis (see also Acid catalysis, Base catalysis,
etc.)
of alkene hydrogenation, heterogeneous metals
and, 410-414
homogeneous metal complexes and, 4 17-4 18,
1517-1521
mechanisms for, alkene metathesis, 1520-1 52 1
1,3-butadiene trimerization, 1523
homogeneous hydrogenation with rhodium,
1517-1518
hydroformylation, 1518-15 19
of methanol carbonylation, 1520
methylpropandioyl to butanedioyl coenzyme
A, 1526
of 0x0 reaction, 1518-1519
Catalyst, definition of, 16
Catalytic re-forming, 1079- 1080
Catechol (see 1,2-Benzenediol)
Cationic polymerization, of alkenes, 393-395
+
Cedar, oil of, 1498
Cedrene, synthesis of, 1498
Celery, oil of, 1464
Cellobiose, from cellulose, 933
structure and configuration of, 929
Cellosolves, 656
Celluloid, 933
Cellulose, biological degradation of, 934
derivatives, 933
enzyme induced hydrolysis, 1270
hydrolysis of, 933-934, 1270
properties and occurrence of, 908
structure of, 932-933
uses of, 933
Cellulose acetate, 933
Cellulose acetate butyrate, 933
Cellulose xanthate, 933
Cephalosporins, biosynthesis of, 1492
structure and function of, 1491
synthesis of, 1492
Cercropia moth hormones, 1469
Ceric ion, oxidation of
cyclobutadieneirontricarbonyl with, 1507
Charge relay mechanism, in proteolytic
enzymes, 1266
Charge transfer complexes, from alkenes and
halogens, 367
in arene halogenation, 1044- 1045
of arenes and nitro compounds, 1192-1 193
electronic spectra of, 1192- 1193
quinhydrone as, 1307
resonance and, 1192- 1193
Chemical Abstracts, indexes for, 5 1
Chemical evolution, 1282- 1284
Chemical synthesis, principles in planning of,
5 13-530
Chemically induced dynamic nuclear polarization,
1353-1356
Chemiluminescence, 1395- 1399
Chenopodium, oil of, 1466
Chiral centers (see Chirality)
Chiral recognition, 869
Chirality, achiral and chiral environments, 120
of allenes, 508-5 10
of amines, 1109-1110
asymmetric synthesis and, 893-894
and biological specificity, of sense of taste and
smell, 140- 141
chiral centers, location of, 116- 117
compounds without chiral carbons, 508-5 11
of trans-cycloalkenes, 475-476, 5 11
of cycloalkylidenes, 5 10
D,L convention for, 131-139
definition of, 1 16
diastereotopic groups and, 889
enantiotopic groups and, 888-889
Fischer projection formulas for, 128-139
of hindered biphenyls, 5 10-5 11
meso compounds and, 135-139
optical rotation and, 865-866
prochirality and, 888-889
R,S convention for, 879-884
racemization mechanisms and, 895-897
of spiranes, 510
Chitin, properties and occurrence of, 908
structure of, 936
Chloral (see Trichloroethanal)
Chloral hydrate, 647
Chlordane, 536
Chlordiazepoxide, 1098
Chlorination (see also Halogenation)
of alkanes, with tert-butyl hypochlorite, 103-104
mechanisms for, 88-98, 102-103
photochemical, 83, 91-95
selectivity produced by arenes, 102
with sulfuryl chloride, 102- 103, 108
thermal, 99, 101
of alkenes, by radical mechanism, 543-544
of arenes, 1044- 1046
with tert-butyl hypochlorite, 103-104
energy of, 81-83
of methane, 81-85, 88-96
of methoxybenzene, cyclodextrin effect on,
935-936
radical, of alkylarenes, 546, 1317
side-chain, of methylbenzene, 96-97, 546, 1317
Chlorine, addition to alkenes, 379
addition to benzene, 1076
Chloroacetic acid (see Chloroethanoic acid)
Chlorobenzene (see also Aryl halides)
from benzene, 1291
benzenol from, 1291
hydrolysis of, 557
S, 1 reactivity of, 229
2-Chloro-1,3-butadiene, polymer from, 506
polymer of, 1433
2-Chlorobutane, enantiomers of, 115-1 16
S, reactions of, 220-221
N-Chlorobutanimide and hydrogen fluoride, in
additions to alkenes, 379
N-Chlorobutanimide, in additions to alkenes, 379
3-Chloro-1-butene, preparation of, 542
S,1 solvolysis of, 545
1-Chloro-2-butene, preparation of, 542
S,1 solvolysis of, 545
Chlorobutyric acid (see Chlorobutanoic acid)
Chlorocyclohexane, conformational equilibria and
equilibration of, 456-457
E2 reactions of, 466-468
Chlorocyclopentane, E2 reaction of, 248
1-Chloro-2,4-dinitrobenzene, from
2,4-dinitrobenzenol, 1295
nucleophilic substitution on, 552-553
Chloroethane, bond distances in, 37
Chloroethanoic acid, glycine from, 1225
ionization of, 792, 799
physical properties of, 792
Chloroethene, copolymer with ethenyl
ethanoate, 1435
health hazards with, 549
plastics from, 548-549
polymers and copolymers of, 391, 548-549,
1430-1432, 1435
preparation of, 548
S, 1 reactivity of, 229
Chloroethers, 704
Chlorofluoromethanes, preparation of, 567
Chloroform (see Trichloromethane)
Chloromethane, bond angles of, 171-172
from chlorination of methane, 81-85, 88-96
electronic spectrum of, 289
ion cyclotron studies of reaction of, 1365
ionization of, 212-213
Chloromethoxychloromethane, as carcinogen, 1164
Chloromethoxymethane, as carcinogen, 1164
Chloromethyl cation, in chloromethylation of
aenes, 1319
Chloromethyl ether, 704
bis-Chloromethyl ether, as carcinogen, 1164
Chloromethylation, of arenes, 1054, 1319
mechanism of, 1319
of resins for solid-phase peptide syntheses, 1245
Chloromethylbenzene, from benzene by chloromethylation, 1319
benzenecarbaldehyde from, 1318
and Hammett correlation, 1334
from methylbenzene, 104, 546, 1317
from methylbenzene and tert-butyl hypochlorite, 104
phenylethanenitrile from, 1318
phenylmethanol from, 1318
2-Chloro-2-methylbutane, E l reactions of, 249
E2 reactions of, 245
2-Chloro-2-methylpropane,E l reaction of,
248-249
S,1 reaction of, 248-249
Chloromethyloxacyclopropane (epichlorohydrin),
in epoxy resins, 1444-1445
Chloromethyloxacyclopropane, formation of, 542
1-Chloro-4-nitrobenzene, nucleophilic substitution
reactions of, 554-555
N-Chloro-N-phenylethanamide, rearrangement
of, 1140
Chlorophyll, in photosynthesis, 939
singlet oxygen from, 1392- 1393
structure of, 939
Chloroplasts, 939
Chloroplatinic acid, ether formation with, 655
Chloroprene, 506, 1433
3-Chloropropene, epichlorohydrin from, 541-542
hypochlorous acid addition to, 541-542
preparation of, 541, 543-544
S,2 transition state for, 545-546
N-Chlorosuccinimide (see N-Chlorobutanimide)
Chlorosulfite esters, in alkyl chloride
formation, 627
Chlorosulfonic acid, sulfonyl chlorides from arenes
with, 1056
Chlorotrifluoroethene, ethenylbenzene adduct
of, 1313
polymers from, 391, 1432
Chlorpromazine, 1098
Cholestane, 1475- 1476
Cholestanol, 1477
Cholesterol, biosynthesis of, 1486-1488
occurrence of, 1471
reactions of, 1474- 1476
reduction products of, 1474-1477
structure and stereochemistry, 1471- 1477
structure and determination of, 1475-1477
Cholic acids, 1475- 1476
Chromate esters, in alcohol oxidations, 640-641
Chromatographic separations, affinity, 262
gas-liquid, 259-260
high-pressure, 262
liquid-solid, 26 1-262
Chromatography, reference works for, 346-347
Chromic acid, aldehydes from, with alcohols, 727
azabenzene complex of, oxidation of alcohols
with, 642
kinetic isotope effect in 641
mechanism of, 640-641
oxidation of alcohols with, 640-642
phenols to quinones with, 1300-1301
Chromic oxide (see Chromic acid)
Chromophore, definition of, 1030
Chromophores, benzene derivatives as, 1402-1404
Chromosomes, DNA in, 1271
Chrysene, from coal tar, 1080
Chymotrypsin, histidine function in, 1266
in peptide sequencing, 1233
precursors of, 1269
properties of, 1250
proteolytic properties of, 1260
regulation of, 1269
serine function in, 1265- 1266
Chymotrypsinogen, 1269
CIDNP, 1353-1356
Cinnamic acid (see 3-Phenylpropenoic acid)
Circular dichroism, 89 1
Cis-trans isomers, of 1,3-alkadiene polymers,
504-508
of alkadienes, 114
of 1,2,3-alkatrienes, 5 11
of amides, 1171
of cycloalkanes, 113
definition of, 111- 112
interconversion of, of visual pigments, 1417
IUPAC rules of nomenclature for, 113-1 14
photochemical interconversion of, 1384- 1386
Citral, 1465- 1466
Citric acid (see also 3-Hydroxypentanoic acid)
- in citric acid cycle, 951-954
Citronella, oil of, 1464, 1466
Citronellal, 1465- 1466
Claisen ally1 ether rearrangement, 1298
Claisen condensation, biological equivalent of,
837-839
with carbonate esters, 83 1
Dieckmann variation on, 85 1-852
equilibrium of, 829-83 1
with ethanedioate esters, 831-832
in fatty acid biosynthesis, 1481
with ethyl benzenecarboxylate, 83 1
of ethyl ethanoate, 829-830
of ethyl 2-methylpropanoate, 830-83 1
ethyl 3-oxobutanoate from, 829-830
with ketones, 832
limitations of, 830-83 1
with methanoate esters, 83 1
mixed, 83 1-832
thermodynamics of, 829
triphenylmethylsodium as base for, 83 1
Clarke, F. H., Jr., and cedrene synthesis, 1498
Clemmenson reduction, of aldehydes and
ketones, 711
Cloves, oil of, 1464
Coal, distillation of, 74, 1079
Coal tar, arenes from, 1079-1080
azarenes from, 1079- 1080
oxygen and sulfur compounds from, 1079- 1080
production of, 74, 1079
Cobalt, vitamin B12 and, 1490, 1525-1526
Cobalticinium ion, 1506
Cocaine, 1097
Codeine, 1097
Codons, of messenger RNA
Coenzyme A, ethanoyl derivative (see Ethanoyl
coenzyme A)
and fatty acid biosynthesis, 1480- 1481
structure of, 838
Coenzyme Q, 1309
Coenzymes, B vitamins as, 1267-1268
functions of, 1267- 1269, 1525- 1526
thiamine pyrophosphate as, 1267-1269
types of, 1267-1269
vitamin B12 as, 1525-1526
Cofactors (see Coenzymes)
Coke, formation of, 74
Colchicine, 1316
Cole, W., and equilenin synthesis, 1495
Collagen, function of, 1249
structure and properties of, 1458-1459
Collie, J. N., acetate hypothesis of, 1480-1482
Collman, J. P., and tetracarbonylferrate
reactions, 1516
Color, complementary, 1399- 1400, 1409
and electronic absorptions, 1399- 1404
sensation of, 1399- 1400, 1409
visible wavelengths, 1399- 1400
Color-forming reactions, 1411-1414
Color photography, color transparencies, chemistry
of, 1410-1415
instant color prints from, 1414- 1415
subtractive process of, 1410
Complementary colors, 1399- 1400, 1409-1415
Concerted reactions, [4 21 cycloadditions and,
498-499
formulation of, 88-89, 98
in methane chlorination, 90
Conformational analysis (see Conformations)
Conformations, anti, 124
of 1,3-butadiene, 495
of butane, 123-125
of cis and trans isomers of decalin, 480-481
of cyclobutane, 462
of "cyc1oethane," 463
of cycloheptane, 47 1-472
+
of cyclohexane, 448-46 1
cyclohexane derivatives, equilibria and
equilibration of, 453-46 1
substituent effects, 457
of cyclononane, 473
of cyclooctane, 472
of cyclopentane, 462
of cyclopropane, 463
of cyclotetradecane, 47 1-472
drawings of, 125-126
and E2 reactions, 466-468
eclipsed, definition of, 121
energies of, 121-124
for butane, 125-126
equilibration of, nmr studies of, 1345-1347
of ethane, 121-123
gauche, 124
holding groups for, 458-460
Newman projections of, 125-126
nmr spectra of, 303-304, 1345- 1347
of proteins, 1249-1259
and reactivity, 245-247, 466-468
sawhorse representations for, 125- 126
skew, 124
and spin-spin splittings, 320-32 1
staggered, definition of, 121
syn, 124
torsional angles of, 121- 124
trans, 124
Conformer (see also Conformations)
definition of, 124
Conjugate addition, definition of, 770
of organometallics to alkenones and alkenals,
585-586
Conjugated polyenes (see Polyenes)
Conrotation, definition and occurrence of,
1006-1009, 1013-1014
Constitutional isomers, 45
Contraceptive steroids, 1479
Coolite, 1396
Coordination polymerization, of alkenes, 396-397,
1446, 1511
Cope, A. C., and sigmatropic rearrangement, 1006
Cope rearrangement, 1089
Copolymers, from 1,3-alkadienes, 506-508
definition of, 505
of ethene and propene, 1432, 1435
properties and types of (table), 1432-1433
ratios of incorporation in, 1452- 1453
types of, 1452-1453
Copper catalysis, of arenediazonium salt reactions,
1134-1 136
Copper phthalocyanine, 1414
Coprostane, 1475
Coprostanol, 1477
Coral rubber, 1433
Corey, E. J., and prostaglandin syntheses,
1502- 1503
and synthesis of juvenile hormone, 1470
Corey, R. B., and alpha helix, 1251
Corey-Pauling-Kolton models (see CPK models)
Corn syrup, 935
Cornforth, J. W., and steroid synthesis, 1477-1478
Corrin rings, 1490
Cortisone, structure and occurrence, 1473
synthesis of, 1478-1479, 1495-1497
Cotton, 933
Cotton effect and optical rotatory dispersion,
890-893
Coumarin, 1328
Couper, A., 5
Coupling constants (see Nmr spectra)
Covalent bonds, 18-2 1
CPK models, 37-39
Crafts, J. M., and acylation of arenes, 1051-1053
and arene alkylation, 1047- 1050
Cresols (see also Methylbenzenols), from coal
tar, 1081
Crick, F., and DNA structure, 1249, 1275
Cross-linking (see Polymers)
Crossed Cannizzaro reaction, 754
Crotonaldehyde (see 2-Butenal)
Crotyl alcohol (see 2-Buten-1-01)
Crown ethers, 666
Crystal violet, 1404
Cubane, physical properties and strain energy
of (table), 482-483
Cumene (see I-Methylethylbenzene)
Cumulated double bonds, stereochemistry of,
508-5 11
Curtius degradation, amines from, 1150, 1153, 1156
Cyan dye, 1410-1414
Cyanide ion, in benzoin condensation, 1324- 1325
Cyanides (see Nitriles)
Cyanine dyes, 1412
Cyanoacetic acid, 793, 81 1
Cyanoacetic esters, acidity of, 826
Cyanobenzenamines, base strengths of, 1116
Cyanoborohydride, 1154
Cyanocobalamin (see Vitamin B, ,)
Cyanoethanoate esters, acidity of, 826
Cyanoethanoic acid, 793, 8 11
Cyanogen bromide, addition to alkenes, 379
Cyanohydrin formation, 689-690
Cyanohydrins, in Kiliani-Fischer synthesis, 91 1
Cyclic conjugated polyenes, annulenes, properties
and reactions of, 1087-1088
azulene, properties and reactions of, 1084-1085
cyclobutadiene as, 178, 989-99 1
cyclooctatetraene, properties and reactions of,
1085-1086
fluxional compounds, electrocyclic equilibration
of, 1089- 1090
pentalene, attempts to synthesize, 1086-1087
Cyclic ions, and Hiickel rules, 996-999
Cyclic polyethers (see also Ethers), metal complexes of, 665-666
Cycloadditions, of cyclopropanone, 78 1
of cyclopropenone, 78 1
of diazomethane, 1200
general types of, 492-493
in planning of syntheses, 526-527
+
[2 11 type, with carbenes, 565
[2+2] type, of DNA and RNA, 1393-1394
of ethene, 502
of ethenylbenzene and chlorotrifluoroethene, 1313
with fluoroalkenes, 569, 1014-1017, 1313
and Hiickel rule, 999-1002, 1010-1014
ketene dimerizations as, 503
with ketene, 1002
ketenes and 1,3-cyclopentadiene, 503
mechanism of, 503-504
photochemically induced, 503, 1013- 1014,
1389, 1392-1393
polar mechanism for, 1023- 1024
possible concerted examples of, 1002
1,2-propadiene dimerization, 502
with 1,2-propadiene, 1002
radical mechanism for, 1014-1017
stepwise mechanism for, 1014- 1017
stereospecificity of, 1014- 1017
tetrafluoroethene and 1,3-butadiene, 502
tetrafluoroethene dimerization, 502, 568
thermodynamics of, 502-503
[4+ 11 type, sulfur dioxide and 1,3-butadiene,
500-501
[4 21 type (Diels-Alder), addends for (table),
492-498
of arenes, 1077
1,3-butadiene and 1,4-benzenedione, 1312
concerted nature of, 498-499, 999
exo-endo preferences in, 496-498
and Hiickel rule, 999- 1000, 1004-1005, 1010
kinetic vs. equilibrium control in, 497
mechanism of, 498-499
of naphthalene, 1077
photochemical, 1388
polymerization by, 1420
pressure effects on, 1077
of quinones, 1312
of singlet oxygen, 1391-1392
stereospecificity of, 494-499
substituent effects on, 493-498
synthetic uses of, 526-527
l,2-Cycloalkadienes, from gem-dichlorides, 704-705
Cycloalkanes, cis-trans isomers of, 112- 113
conformations of, 448-463, 480-48 1
for larger rings, 469-474
conformational representations of, 126-127,
449-453, 462, 470-474, 480-48 1
electronic spectra of, 29 1-292
Haworth projections of, 127
heat of combustion and strain energy of
(table), 464
infrared stretching frequencies for, 276, 278-280
larger-ring members of, synthesis of, 469-470
ring-opening reactions of, 466-467
strain energies and bond energies of, 465
Cycloalkanones, from dicarboxylic acids, 846-847
from dicarboxylic esters, 85 1-852
Cycloalkenes, chemical properties of, 474-475
chiral forms of trans isomers of, 475-476
+
heats of hydrogenation of (table), 475
nomenclature for, 60
physical properties of (table), 474-475
strain energies of, 474-475
transition-metal complexes of, 1510
trans-Cycloalkenes, chiral forms of, 5 10
Cycloalkyl halides, physical and chemical properties of, 550-55 1
Cycloalkylidenes, chiral forms of, 5 10
Cycloalkynes, from gem-dichlorides, 704-705
Cyclobutadiene, angle strain in, 99 1
cycloaddition reactions of, 1507
dirnerization of, 990, 1507
electronic configuration of, 992-994
generation of, 1507
iron compounds of, 1507
molecular orbital treatment of, 989-994
quinones of, 1313
and resonance theory, 178, 989
stability of, 178, 990-991
Cyclobutadieneirontricarbonyl, preparation and
reactions of, 1507
Cyclobutadienoquinones (see 3-Cyclobutene1,2-diones)
Cyclobutane, chemical properties of, 466-467
conformations of, 462
heat of combustion and strain energy of
(table), 464
physical properties of (table), 446
ring-opening reactions of, 466-467
substituted, cis-trans isomers of, 113
Cyclobutanols, from ketone photodissociations, 1381
Cyclobutanone, from cyclopentanone photodissociations, 1381
photochemistry of, 1381
physical properties of, 679
preparation of, 717, 766
reactivity of, 677
reduction of, 705-706
Cyclobutene, from 1,3-butadiene, 1389
physical properties and strain of, 475
Cyclobutenedione derivatives, 1313
Cyclobutenediones, angle strain in, 991
Cyclobutenes, electrocyclic reactions of,
1005-1014
1,5-Cyclodecadiene, 1524
Cyclodecane, conformations of, 473-474
heat of combustion and strain energy of
(table), 464
1,4,7-Cyclodecatrienes, 1524
Cyclodecyne, physical properties and strain of, 475
Cyclodextrins, 935-936
1,5,9-Cyclododecatriene, 1523
Cycloheptane, conformations of, 47 1-472
physical properties of (table), 446
1,3,5-Cycloheptatriene,radical from, esr spectrum
of, 1369
synthesis of, 1314
tropolone from, 1314
tropylium ion from, 1315
Cycloheptatrienyl radical, esr spectrum of, 1369
Cycloheptene, physical properties and strain
of, 475
1,3-Cyclohexadienes, electrocyclic reactions of,
1005-1012
1,4-Cyclohexadienes, from Birch reduction,
1074- 1075
1,4-Cyclohexadienone(see 1,4-Benzenedione)
Cyclohexanamine, base strength of, 1114
from benzenamine reduction, 1073
infrared spectrum of, 1104
physical properties of, 1101
Cyclohexane, from benzene reduction, 1072- 1073
boat conformation of, extreme form of, 449-451
"flagpole" hydrogens in, 450
preparation of, 450
stability of, 450
twist-boat form, 450-45 1
carbon-13 nmr spectra of derivatives of, 460
chair conformation of, axial positions in,
452-46 1
equatorial positions in, 452-46 1
equilibria and, 453-461
ring inversion of, 454-461
stability of, 450
chemical properties of, 466-467
cis-trans isomerism of derivatives of, 458-460
conformational representations of, 126-127,
449-445
conformations and conformational analysis of,
448-46 1
cyclohexanone from, 1441
E2 reactions and conformations, 468
heat of combustion and strain energy of (table),
79-80, 464
hexanedioic acid from, 1441
models of, 45 1-453
nomenclature for, 57-58
from petroleum, 1081
physical properties of (table), 239, 446
planar conformation of, strain in, 448-449
Cyclohexanol, from benzenol reduction, 1073
dehydration of, 251
physical properties of, 1291
Cyclohexanols, from alkyl-substituted
phenols, 1300
Cyclohexanone, from cyclohexane, 1441
enamine from, 702
hexanedioic acid from, 1441
oxime of, formation of, 1180
rearrangement of, 1181
physical properties of, 679
Cyclohexene, bromine addition to, 362, 365, 367
bromine substitution of, with tert-butyl
hypobromite, 106
charge-transfer complex with iodine, 367
from ethene and 1,3-butadiene, 492
hydrogen fluoride addition to, 368
oxidation of, with nitric acid, 1043
physical properties and strain of, 475
Raman spectrum of, 285-286
Cyclohexylamylose, 935-936
Cyclonite, 701
Cyclononane, conformations of, 473
heat of combustion and strain energy of
(table), 464
physical properties of (table), 446
cis-Cyclononene, physical properties and strain
of, 475
trans-Cyclononene, physical properties and strain
of, 475
Cyclonoyne, physical properties and strain of, 475
1,5-Cyclooctadiene, from 1,3-butadiene, 1523-1524
nickel complex of, 1510
Cyclooctane, conformations of, 472
heat of combustion and strain energy of
(table), 464
infrared spectrum of, 280
physical properties of (table), 446
Cyclooctatetraene, dianion of, 1085
dication of, 1085
electrocyclic equilibrium of, 1085- 1086
electronic configuration of, 992-994
geometry of, 990
halogen addition to, 1086
iron tricarbonyl complex of, Mossbauer
spectrum of, 1360
molecular-orbital theory of, 989-994
physical properties of, 1085
planar form of, 994, 1085
preparation of, 990, 1085
reactions of, 1086
resonance and, 989
uranium derivative of, 1508
cis-Cyclooctene, physical properties and strain
of, 475
trans-Cyclooctene, chiral forms of, 475-476
physical properties and strain of, 475
Cyclooctyne, physical properties and strain of, 475
Cyclopentadecane, heat of combustion and strain
energy of (table), 464
1,3-Cyclopentadiene,cycloaddition with
ethyne, 1314
[4 21 cycloadducts of, 526-527
dimerization of, 1420
electrocyclic reactions of, 1007- 1008, 1013- 1014
organometallics from, 574
pi (n-) metal derivatives of, 1504-1508,
1512-1514
polymerization of, 1420
sandwich compounds of, 1504-1508, 1512-15 15
transition-metal compounds, 1504- 1508,
1512-1514
Cyclopentadienyl anion, Huckel rule and, 996-998
Cyclopentadienyl cation, and Huckel rule,
997-998
Cyclopentane, chemical properties of, 466-467
conformations of, 462
heat of combustion and strain energy of
(table), 464
physical properties of (table), 446
Cyclopentanone, hydrogenation of, 710
+
photochemistry of, 1381
physical properties of, 679
Cyclopentanophenanthrene, as parent steroid
structure, 1471
Cyclopentene, hydroxylation of, 434-436
physical properties and strain of, 475
Cyclophosphoramide, as carcinogen, 1164
Cyclopropane, alkene-like reactions of, 463-464,
466-467
ball-and-stick model of, 35
bond angles of, 36
chemical properties of, 466-467
conformations of, 463
heat of combustion and strain energy of (table),
79-80, 464
physical properties of (table), 446
from propanamine and nitrous acid, 1131
proton nmr shifts of, 448
rearrangement of, 42
ring-opening reactions of, 466-467
substituted, cis-trans isomers of, 113-1 14
Cyclopropanecarboxaldehyde, preparation of, 7 19
Cyclopropanes, from carbene additions to
alkenes, 565
from carbenes and alkenes, 575
from 1,3-dihalides with metals, 575
Cyclopropanone, hemiketal from, 677-678
preparation and reactions of, 780-78 1
reactivity of, 677-678
Cyclopropanones, addition reactions of, 786-787
in Favorskii rearrangements, 749
ring-openings of, 780-78 1
stability of, 780-78 1
synthesis of, 780
Cyclopropene, physical and chemical properties
of, 474-475
Cyclopropenone, carbonyl double bond in, 78 1
synthesis and reactions of, 781
Cyclopropenyl cation and anion, 997-998
Cyclopropyl halides, S, 1 and S,2 reactivity of, 55 1
Cyclopropylmethyl halides, SN1 and SN2 reactivity
of, 551
Cyclotetradecane, conformation of, 470-47 1
Cysteine, disulfide linkages from, and protein
structures, 1253-1254
in penicillins and cephalosporins, 1492
properties of, 1209
Cystine, properties, 1209
and protein structures, 1253- 1254
in wool, 1457-1458
Cytochrome c, properties, 1250
Cytochromes, in biological oxidations, 1309
Cytosine, as DNA component, 1272-1277
lactam-lactim isomerism of, 1273
in RNA, 1278
2,4-D, 561
Dacron, polyester fiber, 673, 1433, 1438
Dale, J., and conformations of large ring
cycloalkanes, 470-474
Dansyl chloride, in peptide sequence
determinations, 1230
DDT, 536, 561
Decalin, cis-trans isomers of, conformations of,
480-48 1
Decamethylzirconocene and nitrogen
complex, 1508
Decarbonylation, of diphenylpropanetrione, 779
of 2-oxoalkanoate esters, 832
Decarboxylation, 8 11-8 14
of amino acids, 1223-1224
enzymatic of 2-oxobutanoic acid, 1285
ketones from, 732
of 3-oxobutanoic acids, 834
of propanedioic acids, 834
Degenerate orbitals, of cyclic polyenes, 992
and Hund's rule, 153-155
Delocalization energy (see Resonance)
Delphinidin, 1403
Delrin, 696, 1433
Denaturation, of proteins, 1259, 1270
Deoxyadenosylcobalamine, 1525
Deoxyribonucleic acids (see also DNA): electron
microscopy and, 262-263
photochemistry of, 1393- 1394
Deoxyribonucleosides, definition of, 926
Deoxyribose, DNA component, 1272-1274
furanoside structure of, 1274
phosphates of, 1272- 1274
Desoxycholic acid, 1475- 1476
Detergents, action of, 803-804
biodegradation of, 1057
sodium alkylbenzenesulfonates as, 1056- 1057
Deuteration of arenes (see also Electrophilic
aromatic substitution), of arenes, 1057
Dewar benzene, 175, 973-974
Dextrin, 935
Dextrorotatory, definition of, 119, 863
Diacetone alcohol, 752-753, 756-757
2,2-Diaminoazaethene, base strength of, 1118
Diaminobenzenes (see Benzenediarnines)
2,4-Diaminobenzenol, 1311
4,4'-Diaminobiphenyl, as carcinogen, 1162
Diamond, structure of, 17-18
Diastase, 934
Diastereoisomers, carbon- 13 nmr spectral
differences of, 336-337
concept of, 133-139
Diastereotopic groups, definition of, 889
1,3-Diazabenzene, base strength of, 1118
1,5-Diazacyclohexane-1,4-dione, 1222
1,3-Diazacyclopentadiene,base strength of, 1118
Diazacyclopropanes, 1202
1,2-Diazacyclopropene, properties of, 1201- 1202
Diazanes, azides from, 1202
preparation and reactions of, 1194, 1197
Diazirenes (see Diazacyclopropenes)
Diazirines, 1201-1202
Diazo compounds, preparation of, 1199
reactions of, 1199- 1200
Diazo coupling reactions, azo compounds
from, 1137
mechanism, 1137
pH dependence of, 1137
Diazoic acids, in alkanamine-nitrous acid
reactions, 1130
Diazoketones, in Arndt-Eistert synthesis, 1200
formation of, 692-693
1,3-Diazole (see 1,3-Diaza-2,5-cyclopentadiene)
Diazomethane, with acyl halides, 692-693
with alcohols, 1199
Arndt-Eistert reaction of, 1200
with benzenol, 1294
carbene from, 566, 1200
carboxylic esters from, 856, 1199
as carcinogen, 1164
cyclic isomer of, 1201-1202
cycloaddition reactions of, 1200
cyclopropanone from, with ketene, 780
with di-n-propenylnickel, 1522
with enols, 1199
as methylating agent, 1199
methylation of alcohols with, 655
0-methylation with, 1199
photolysis of, 1200
preparation of, 1199
properties of, 1199
pyrazolines from, 1200
ylide reactions of, 692-693
Diazonium ions, from alkanamines, 1129- 1131
from amino acids, 1223
Diazonium salts, from arylamines, reactions of
(table), 1133-1 139
from arylamines, formation of, 1133
Diazotate salts, from diazonium salts, 1130, 1139
Dibenzenechromium, 1506- 1507
Dibenzocarbazole, as carcinogen, 1162
Dibenzocyclopentadiene, acid strength of, 1322
4,5,4',5'-Dibenzothioindigo,1407
Diborane (see also Hydroboration), ether and
sulfide complexes of, 42 1
formation of, 421
hydroboration with, 420-424
reduction of carboxylic acids with, 810
1,2-Dibromobenzene, possible isomers of, 10
Dibromocarbene, formation and addition to
cyclohexene, 575
from tetrabromomethane and alkyllithiums, 566
from tribromomethane and base, 566
3,3-Dibromo-2,2-dimethylbutane,
nmr spectrum
of, 1347
1,1-Dibromoethane, proof of structure by the
substitution method, 8-9
1,2-Dibromoethane, nmr spectrum of, 303-304
proof of structure by substitution method, 8-9
and rotational isomerism, 7-8
Di-tert-butyl peroxide, initiation of polymerization
with, 1447
Dibutyl phthalate, 1435
1,2-Di-tert-butylethylene, heats of hydrogenation
of cis-trans isomers of, 415-416
Dicarboxylic acids, acidities of (table), 846-849
acyloin reaction of, 852-853
anhydrides from, 847
decarboxylation of, 847
Dieckmann condensation of, 85 1-852
hydroxyketones from, 852-853
imides from, 850
ketones from, 732, 847
physical properties of (table), 846-849
thermal behavior of, 846-847
uses of, 848-849
1,2-Dichlorobenzene, 1,2-benzenediolfrom, 1304
Dichlorocarbene, addition reactions of, 564-565
with benzenol, 1299
electronic structure of, 564
from trichloromethane and bases, 563-564
3,4-Dichlorocyclobutene, cyclobutadiene and its
iron carbonyl complex from, 1507
Dichlorodifluoromethane, as atmospheric
contaminant, 537
preparation of, 567
reactivity of, 567
refrigerant and aerosol uses of, 567
1,1-Dichloroethane, bond distances in, 37
1,l-Dichloroethene, copolymers of, 1432
1,2-Dichloroethene, cis-trans isomers of, 113
Dichloromethane, hydrolysis of, 563
uses of, 562
Dichloromethylbenzene, benzenecarbaldehyde
from, 1318
from methylbenzene, 1317
Dichromate (see also Chromic acid), benzenamine
oxidation with, 1145
N,Nf-Dicyclohexylcarbodiimide, peptide syntheses
with, 1240- 1241, 1246
in chemiluminescence reactions, 1399
Dicyclopentadiene, copolymers of, 1435
from 1,3-cyclopentadiene, 1420
Dicyclopentadienyliron, 1504-1506
Dicyclopropylmethane, from di-n-propenylnickel,
1522
Dieckmann condensation, synthesis of
alkoxycarbonylcycloalkanones with, 851-852
Dielectric constant, of solvents (table), 237-239
Diels, O., and [4+2] cycloadditions, 492
Diels-Alder reaction (see also [4 + 21
Cycloadditions), 492-499
pressure effects on, 1077
Dienophiles, definition of, 493
1,1-Diethenoxybutane, polymer of, 1433
Diethyl ether (see Ethoxyethane)
Diethyl malonate (see Propanedioate esters)
Diethyl oxalate (see Ethanedioate esters)
Diethylamine (see N-Ethylethanamine)
N,N-Diethyl-1,4-benzenediamine, as color
developer, 1413-1414
in color photography, 1311
Diethylene glycol, 662
N,N-Diethylethanamine, base strength of, 1118
physical properties of, 1101
Diethylstilbestrol, 1479
N,N-Diethyl-meta-toluamide,
1098
Diffusion control, of reaction rates, 95
gem-Difluorides, from aldehydes and ketones, 705
Difluorocarbene, in tetrafluoroethene
preparation, 568
1,1-Difluoroethene, copolymers of, 1432
elastomer with hexafluoropropene, 568
Difluoromethylbenzene, from
benzenecarbaldehyde, 1318
Difluoromethylbenzenes, from aldehydes, 1318
Digitalis steroids, 1473
Digitogenin, structure and occurrence, 1473
Digitoxigenin, structure and occurrence, 1473
Diglyme, 656
Dihydropyran, 653
1,3-Dihydroxy-9,10-anthracenedione,
1407
Dihydroxybenzenes (see Benzenediols)
2,3-Dihydroxybutandioic acid (see Tartaric acid)
Dihydroxymethane (see Methanal)
1,3-Dihydroxy-2-propanone,
phosphate esters of,
biological aldol addition of, 760-761
in glycolysis, 948
in photosynthesis, 942-943
properties and occurrence of, 907
Diimide, formation of, 4 18-4 19
mechanism of hydrogenation with, 419
self-destruction of, 4 19
stereochemistry of hydrogenations with, 419
thermochemistry of, 4 18
Diisobutylene (see also 2,4,4-Trimethyl-1-butene),
formation of, 394-395
2,4-Diisocyano- 1-methylbenzene, 1454- 1455
Diketene, reactions of, 773
structure of, 773
Diketopiperazines, from amino acids, 1222
Dimethyl sulfate, with benzenolate anion, 1294
preparation of, 629
Dimethyl sulfoxide (see Methylsulfinylmethane)
Dimethylacetylene (see 2-Butyne)
4-N,N-Dimethylaminoazobenzene, as carcinogen,
1162
N,N-Dimethylaniline, coupling with
benzenediazonium salts, 1137
N,N-Dimethylbenzenamine, coupling with
benzenediazonium salts, 1137
1,2-Dimethylbenzene,oxidation of, with oxygen
and vanadium catalysts, 1077-1078
Dimethylberyllium, bond angles of, 159
2,3-Dimethyl-2,3-butanediol,
rearrangement of, 720
3,3-Dimethyl-2-butanone, alkylation of, 763
photochemical CIDNP reaction of, 1353-1356
from rearrangement of pinacol, 720
2,3-Dimethyl-2-butene, heat of hydrogenation
of, 415
Dirnethylchloronium ion, ion-cyclotron resonance
studies of, 1365
1,l-Dimethyldiazane, 1197
Dimethyldiazene, decomposition of, 1198
1,1-Dimethylethanamine, physical properties
of, 1101
N,N-Dimethylformamide (see
N,N-Dimethylmethanamide)
1,1-Dimethylhydrazine
3,4-Dimethylidenecyclobutene, angle strain in, 991
Dimethylmercury, bond angles of, 159
N,N-Dimethylmethanamide, aldehydes from, with
Grignard reagents, 729
physical properties of, 239
solvent properties of, 1168
N,N-Dimethylmethanamine, electronic spectrum
of, 289
2,2-Dimethylpropyl halides, solvolysis of, 250
Dimethylzinc, bond angles of, 159
Dinitramine, 1195
2,4-Dinitroaniline, 1128
2,4-Dinitrobenzenamine, preparation of, 1128
1,4-Dinitrobenzene, synthesis of, 1187- 1189
2,4-Dinitrobenzenol, 1-chloro-2,4-dinitrobenzene
from, 1295
2,4-Dinitrofluorobenzene, in peptide sequencing,
1229- 1230
2,4-Dinitrophenylhydrazones,
698
Dinucleotides, examples of, 926-927
1,2-Diols, from alkene hydroxylations, 434-437
from oxacyclopropane hydrolysis, 435-437
Diosgenin, 1478
1,2-Dioxa-3,4-cyclobutanedione,
chemiluminescence
from, 1396-1398
1,2-Dioxacyclobutanes, chemiluminescence from,
1395-1396
1,2-Dioxa-3-cyclobutanones,
chemiluminescence
from, 1398-1399
1,4-Dioxacyclohexane, formation of, 662
physical properties of, 239, 654
1,4-Dioxane (see 1,4-Dioxacyclohexane)
Dipeptides (see Peptides)
Diphenyl ether, 1295
1,2-Diphenyldiazane,from nitrobenzene, 1194
Diphenyldiazene, decomposition of, 1198
as dye component, 1407
from nitrobenzene, 1194
reduction of, 1194
1,2-Diphenyldiazeneoxide, from
nitrobenzene, 1194
reduction of, 1 194
Diphenylethanedione, rearrangement of, 775
1,2-Diphenylethene, cis-trans, photochemical
isomerization of, 1384- 1386
electronic absorptions of, 1031, 1401
photochemical isomerization to
phenanthrene, 1387
Diphenylmethane, acid strength of, 1322
Diphenylmethanol, from photoreduction of
diphenylrnethanone, 1383
Diphenylmethanone, energy transfer from, to
naphthalene, 1377
intersystem crossing of, 1377
photochemical reduction of, 1382-1383
triplet state of, 1377, with 2-propanol, 1382-1383
Diphenylmethyl cations, 1320, ease of formation
of, 1320
resonance stabilization of, 1320
Diphenylpropanetrione, reactions of, 779
Diphosphoric acid, esters of, formation and
reactions of, 634-637
Dipole moments, of aldehydes and ketones, 675
of alkenals, 769
of amides, 1168
definition of, 675
and ionic character of bonds, 675
of nitriles, 1184
of nitro compounds, 1186
Di-T-propenylnickel, reations of, 1522-1524
stereoisomers of, 1522
Disaccharides, definition of, 925
enzymatic hydrolysis of, 930
examples of, 929-93 1
properties and occurrences of, 907
reducing and nonreducing, 928
structures of, 927-93 1
Dismutation, of alkenes, 1520-152 1
Dispalure, structure and activity of, 141
Dispersion forces, and conformational stabilities,
454-456
Displacement reactions (see Nucleophilic or
Electrophilic displacement reactions)
Disproportionation, of arenoxy radicals, 1301
Disrotation, definition and occurrence of,
1006-1009, 1013-1014
Dissymmetric molecules, 116
Diterpenes, acid of, 1469
alcohols of, 1468
definition of, 1463
DMF (see N,N-Dirnethylmethanamide)
DMSO (see Methylsulfinylmethane)
DNA (see also Deoxyribonucleic acid), bases in,
1271-1275
as genetic material, 1271, 1274- 1275
helical structure of, 1273-1275
molecular weights of, 1271-1272
replication of, 1276- 1277
role of, 1271, 1274-1275
structure of, 1271-1275
Dodecanethiol, as chain transfer agent, 1449
Donor-acceptor complexes (see Charge-transfer
complexes)
Doppler effect in Mijssbauer spectroscopy,
1359-1360
Double bonds, formulation of, 165-167
rotation about, 167, 1384- 1386
Double-bond character, and bond lengths, 987-988
Dreiding, A., molecular models of, 451-453
Dubois, R., and bioluminescence, 1397-1399
Durene (see 1,2,4,5-Tetramethylbenzene)
Dyes, examples of, 1405- 1408
important properties of, 1408
photosensitizing, 1392, 1411-1412
Dylan, 1432
Dynamite, 648
E,Z convention, for cis-trans isomers, 885-887
and oxime isomers, 887
priority order for, 886-887
El reaction (see 1,2-Elimination reactions, El
mechanism)
E2 reaction (see 1,2-Elimination reactions, E2
mechanism)
Ecdysone, role of, 1469
structure and occurrence, 1473
Einstein, A., unit of radiative energy named
for, 269
Elastase, serine function in, 1265-1266
Elastin, function of, 1249
Elastomers (see also Polymers, elastomeric), from
1,3-alkadienes, 505-508
Electrical effects, on acid ionizations, 796-800
on aldehyde and ketone reactivity, 678
definition of, 23, 796-800
Electrocyclic rearrangements, conrotation in,
1006-1009, 1014
cyclobutene-butadiene interconversions,
1005-1014
cyclohexadiene-hexatriene interconversions,
1005- 1009
definition of, 1005
disrotation in, 1006- 1009, 1014
energy charge of, 1005
equilibration by, in fluxional molecules,
1089- 1090
,
of ergosterol, 1394
Huckel rule, 1005-1012
photochemical, 1013-1014, 1387-1388
stereospecificity of, 1006-1009
Electrocyclic rearrangements, equilibration by, in
cyclooctatetraene, 1085-1086
Electrode potentials of quinones, 1306-1307
Electrolysis, of carboxylic acid salts, 8 13
Electromagnetic radiation, energy of, 269
wavelengths of, 265-268
Electromagnetic spectrum, frequency units for,
266, 268
spectroscopic uses of, 265-267
Electron contours, 180- 182, 440, 983
Electron delocalization (see also Resonance), and
bonding in hydrogen, 963-964
Electron diffraction, 265
Electron microscopy, for determination of
structures, 262
Electron-pair bonds, theoretical treatment of,
961-964
Electron paramagnetic resonance spectroscopy
(see Esr spectroscopy)
Electron spectroscopy for chemical analysis
(ESCA), 1358
Electron-spin resonance spectroscopy (see Esr
spectroscopy)
Electronegativity, and acid ionizations, 798-799
and alkene additions, 377, 380-381
and bond angles, 171-172
and carbon-13 shifts, 337
and proton nmr chemical shifts, 307-3 14
Electronegativity scale, definition of, 377
table, 378
Electronic configurations, of atoms, 152-153, in
valence states, 158-160, 163, 168
of hydrogen, 962
Electronic excitation energy transfer, 1376-1377
Electronic repulsions, between bonding electrons,
and bond angles, 157-164, 169-172
theoretical calculations and, 982
Electronic spectra, of alcohols, 605
of alkenals and alkenones, 767-768
of alkenes, 353
of alkynes, 356
of anthracene, 1033
applications of, 293
of arenes, 1030- 1034
auxochromes and, 1030- 1031
Beer-Lambert law in, 291, 293
benzene chromophore and, 1030- 1034
of benzene derivatives, 1032- 1033
benzenoid band in, 1032- 1034
of carboxylic acids (table), 793, 795
/3-carotene, 1401
of charge-transfer complexes, 1192- 1193
chromophores and, 1030-103 1
of chrysene, 1034
of conjugated polyenes, 1401
conjugation effects on, 290-293
1,2-diphenylethene, 1401
energy levels in, 287-293
energy range of, 1372
of ethers, 605
excited states of, 1372-1375
general characteristics of, 287-293
of lycopene, 1401
n to n transitions in, 288-290
of naphthacene, 1033-1034
of naphthalene, 1033
of nitro compounds, 1187
of pentacene, 1033- 1034
of phenanthrene, 1034
of phenols, 1288
n to n'x transitions in, 288-293
of polyenes, 29 1-292
of polynuclear aromatic hydrocarbons,
1033-1034
prediction of band positions, 293
of pyrene, 1034
reference works for, 348
and resonance stabilization, 1401- 1404
rotational energy levels and, 287
transition energies of (table), 287-293
vibrational energy changes and, 287
Electronic spectrum, of amines, 1105
of amino acids, 1216
of benzene, 1032
2-butanone, 292
3-buten-2-one, 292
and color, 1399-1408
molecular-orbital treatment of, 980-98 1
of 2-propanone, 288
Electrophilic aromatic substitution, acylation, of
arenes, 1051-1053
of azulene, 1084
aldehyde syntheses by, 1053- 1055
alkene additions and, 1037- 1040
alkylation, limitations of, 1049- 1050
mechanism of, 1047- 1050
procedures for, 1047-1048
rearrangements in, 1049- 1050
of anthracene, 1069, 1072
of arenamines, 1128- 1129
in arene alkylations, 1047- 1050
of azulene, 1084
of benzene (table), 1037-1040
catalysts for, 1041
chlorination by, cyclodextrin effect on, 935-936
chloromethylation, 1054, mechanism of, 1319
chlorosulfonylation, of benzene, 1056
Friedel-Crafts alkylation, 1047- 1050
Gattermann reaction and, 1054- 1055
Gattermann-Koch reaction and, 1053
halogenation, orientation in, 1070- 1072
procedures for, 1044- 1045
hydrogen exchange by, 1057
intermediates in, 1037- 1040
@so substitution in, 1066-1068
kinetic vs. equilibrium control in, 1066
metalation, by mercuric salts, 1058
of naphthalene, 1069- 1071
nitration, mechanism of, 1041
orientation in, 1058-1072
procedures for, 1041- 1043
nitro compounds from, 1187-1 190
nitrosation, with arylamines and nitrous
acid, 1136
orientation in, electronic substituent effects
in, 1059-1068
meta-directing groups (tables), 1060-1062
ortho-para directing groups (tables),
1060- 1064
patterns of (table), 1059-1060
steric effects of substituents in, 1064
structure proofs for, 1058-1059
transition state and, 1060- 1064, 1066- 1072
of phenanthrene, 1069, 1071
of phenols, 1296-1300
of polynuclear arenes, 1069-1072
scope and mechanism, 1037-1040
sulfonation, procedures for, 1055- 1057
reversal of, 1055
Electrophilic catalysis, of S, mechanisms, 232-234
Electrophilic reagents, definition of, 207-21 1
Electrophoresis, 1248
Electrostatic effects, and carboxylic acid
ionizations, 799-780
Elimination, definition of, 42
Elimination-addition mechanism (see Nucleophilic
aromatic substitution)
Elimination reactions, general characteristics of,
240-25 1
1,l-Elimination reactions, carbenes from, 563-566
1,2-Elimination reactions, characteristics of,
240-252
conformational preferences in, 466-468
El mechanism, acid catalyzed, 25 1
with alcohols, 63 1-632
amines with nitrous acid, 1130- 1131, 1133
carbocations in, 249-25 1, 63 1-633
in competition with SN1, 248-249
leaving groups for, 249-25 1
orientations in, 249-250
reactivity order in, 249
rearrangements in, 250-25 1, 632-633
scope of, 248-251
E2 mechanism, acid catalyzed, 251
with alcohols, 630
alkene mixtures from, 245
alkoxides for, 615
of alkyl compounds, 241-248
antarafacial character of, 245-248
antarafacial route, 245-247
basic reagents and, 241-244
competition with S,2, 241
as concerted reaction, 241
concerted vs. stepwise, 247
of ethenyl halides, 243
kinetics of, 241
leaving groups for, 242
orbital model of, 247
orientation effects in, 245
with phosphate esters, 634
reactivity orders for, 242-244
reagents for, 241-245
solvent effects on, 242
stereochemistry of, 245-248
stereospecificity of, 247-248
steric effects and, 242-243
structural effects on, 242-244
suprafacial route, 246-248
temperature effects on, 244
of tetraalkylammonium salts, 242, 1126
in Williamson ether synthesis, 6 15
references for, 252
1,3-Elimination reactions, in amines with nitrous
acid, 1131
cyclopropanes from, 564
Embalming compound, 775
Emulsion, 930
Enamines, alkylation of, 764-765
from amines, 1122
in biological aldol, 760-76 1
formation of, 702
Michael additions of, 845
rearrangement of, 703
Enantiomers, asymmetric synthesis of, 893-894
of 2-butanol, 119
definition of, 115
and diastereomers, 135-139
mechanisms for interconversion of, 895-897
and meso compounds, properties of, 137-138
physical properties of, 119- 120
racemization of (see Racemization)
resolution of, 866-872
rotation of polarized light by, 119-120
sawhorse drawings of, 127
separation of (see Resolution)
Enantiotopic groups, definition of, 888
Enantiomeric purity, definition of, 870-87 1
determination of, by gas chromatography, 871
by nmr spectroscopy, 871-873
Endo-exo isomerism, 496-497
Endothermicity, definition of, 76
Ene reaction, of singlet oxygen, 1392
Energy transfer, in chemiluminescence, 1395-1396
definition of, 1374
diphenylmethanone to naphthalene, 1376-1377
ketones to alkenes, 1385-1386
in visual process, 1417
Enolate anions, addition reactions of, 749-75 1,
757-758, 770
ambident nature of, in aldol additions, 751
in nucleophilic substitutions, 762
enols from, 738-739
formation of, 736-738
in halogenations, 742-747
nucleophilic displacements with, 761-763,
833-834
resonance stabilization of, 650
Enols, acidities of (table), 736-738
acidity of, 649-65 1
from enolate ions, 738-739
from hydration of alkynes, 383-384
resonance stabilization of, 650
stabilities of, 648-65 1, 740-741
Enthalpy, definition of changes in, 76
of organic compounds, reference works for,
105-106
Entropy, and carboxylic acid ionizations, 801-802
concept of, 85-87
definition of, 85
effect in methane-steam gas reaction, 410
of gases, 86
and heat of reaction, 84-85
and molecular disorder, 85-86
of organic compounds, reference works for,
105-106
of ring formation, 87
of solids, 86
Enzymes, cell-wall hydrolysis with, 1254
cellulose hydrolysis with, 1270
cleansing uses of, 1270
for decarboxylation, 1285
denaturation of, 1270
disaccharide configurations with, 930
in hydration of trans-butenedioic acid, 371-372
immobilization of, 1270
induced fit in, 1261-1262
inhibition of activity of, 1269-1270
lock-and-key fit, 1261
mechanisms of operation of, of
carboxypeptidase, 1263- 1265
intermediates in, 1262- 1266
serine in, 1265-1266
substrate complexes, 1260- 1262
nomenclature of, 1260
peptide hydrolysis with, 1231- 1234
properties of, 1260- 1266
proteolytic, 1260, 1263-1266
regulation of activity of, 1269
ynthetases and, 1270-127 1
technology of, 1270- 1271
x-ray structure determinations of, 1261- 1262
Eosin, 1392
Epichlorohydrin, in epoxy resins, 1444- 1445
preparation of, 541-542
Epinephrine, 1099
Epoxidation of alkenes, 435-437, 662
Epoxides (see Oxacyclopropanes)
Epoxy resins, chemistry of, 1444-1445
epichlorohydrin for, 542
Equatorial positions (see Cyclohexane)
Equilenin, structure and occurrence of, 1472
Equilibrium constants, and reactivity, 81-88
Equilibrium control, of additions to alkenes,
374-376
in carbocation rearrangements, 633
Ergosterol, structure and occurrence of, 1472
vitamin D from, by irradiation, 1394
Erythro, definition of, 883
Erythromycin A, 1482
D-Erythrose, properties and occurrence of, 904, 907
D-Erythrulose, structure and configuration of, 906
ESCA (electron spectroscopy for chemical
analysis), 1358
Esr spectroscopy, of biological reactions, 1368
elements of, 267, 1366- 1367
exchange effects on, 1367-1368
of radicals and radical ions, 1366-1367
Essential oils, 1462
Ester interchange, 82 1
Esterification, acid catalysis of, 615-6 18
equilibrium of, 618
mechanism of, 6 16-6 18
thermodynamics of, 616
Esters (see Carboxylate esters, Sulfonate esters,
etc., as appropriate)
Estradiol, structure and occurrence, 1472
Estrogenic hormones, 1462, 1479
Estrone, contraceptives from, 1479
methyl ether of, 1479
structure and occurrence of, 1472
Ethanal, aldol additions of, 749-752, 755, 759
ammonia addition to, 700
electronic absorption, 795
from ethanol oxidation, 639
from hydration of ethyne, 383
infrared spectrum of, 794
pentaerythritol from, 754
physical properties of, 679
polymerization of, 696
2-Ethanamidofluorene, 1162, as carcinogen, 1162
Ethanamine, physical properties of, 1101
Ethane, acidity of, 439-440
atomic-orbital model of, 162
bond distances in, 37
bromine cleavage of, 359
conformations of, 121-123
electronic spectrum of, 289
energies of conformations of, 121-122
from ethene reduction, 41 1-412
Ethane, fluorination of, 97
from photolysis of 2-propanone, 1379
reaction with bromine, 14
rotational barrier of, 121-123
saturated character of, 14-15
single bond in, 3 1
space-filling model of, 38
Ethanedial, from benzene and ozone, 1078
reactions of, 744-775
1,2-Ethanediamine,physical properties of, 1101
Ethanedioate esters, in Claisen condensations, 832
Ethanedioic acid, decarboxylation of, 847
esters of, chemiluminescence in perhydrolysis
of, 1396
properties and uses of, 847
1,2-Ethanediol, as automotive antifreeze, 437
ethers of, 654-656
polyesters from, 1433
polymerization of, 1423
Ethanedioyl dichloride, acyl halides from, 857
Ethanenitrile, bonding in, 3 1-32
physical properties of, 239
in Ritter reactions, 1178- 1179
synthesis of, 1185
Ethanoic acid, acidity of (table), 736-738
in alkaloid biosynthesis, 1489
ammonia addition to, 700
in aromatic ring biosynthesis, 1481-1482
bonding in, 3 1-32
in cholesterol biosynthesis, 1486-1488
from ethanol oxidation, 639
in fatty acid biosynthesis, 1480-148 1
infrared spectrum of, 794
ketene from, 772
physical properties of, 239, 792
in terpene biosynthesis, 1483-1485
in vinegar, 49
Ethanoic anhydride, with 1,4-benzenedione,
1311-13 12
with glycine, 1222
Ethanol, acidic properties of, 6 12-6 13
alkoxide from, 612-613
azeotrope with water, 607
dehydration of, ethene from, 630-63 1
ethoxyethane from, 630-63 1
drying of, 607
formation of, 12
from hydration of ethene, 361
with hydrogen bromide, 13
infrared spectra, hydrogen bonding and,
602-604
nrnr spectrum of, characteristics of, 295-296
exchange effects on, 3 11-3 13
oxidation of, ethanal from, 639
ethanoic acide from, 639
physical properties of, 60 1
space-filling model of, 38
from starch, 935
Ethanoyl coenzyme A, acyl transfer with, 837-840
in carbohydrate metabolism, 944, 949-953
and fatty acid biosynthesis, 1480- 1481
Ethanoyl nitrate, 1043
N-Ethanoylaminoethanoic acid, 1222
Ethanoylbenzenamines, base strengths of, 1116
2-Ethanoyloxybenzenecarboxylic acid
(aspirin), 1328
Ethene, ab initio calculations of, 180-182
acidity of, 439-440
addition to 1,3-butadiene, 493
atomic-orbital model of, 165- 167
ball-and-stick models of, 35
bond angles of, 35-36
bond distances in, 37
bromine addition to, 14-16, 359
carbon monoxide copolymer of, 1453
copolymer with propene, 396
as "cycloethane," 463, 467
1,3-cyclopentadieneadduct of, 526-527
dimerization of, 502
double bond in, 3 1
electronic spectrum of, 289-290
from ethanol dehydration, 630-63 1
ethanol from, by hydration, 607
heat of hydrogenation of, 415
hydration of, 361
hydroboration of, 420
hydrogenation of, 4 11-4 12
molecular-orbital treatment of, 964-965
oxacyclopropane from, with oxygen, 437
oxidation of, 43
photoelectron spectrum of, 1357
polymerization of, Ziegler mechanism for, 1446
polymers from (see also Polyethene),
physical properties of, 1425-1427, 1430,
1434-1435
radical-chain polymerization of, 395-396
reaction with bromine, 14-16
resonance structures for, 176
rotation about double bond of, 167
space-filling model of, 38
thermodynamic stability of, 359
valence-bond treatment of, 965-966
Ethenol, rearrangement to ethanal, 648
Ethenone (see Ketene)
Ethenyl cations, formation of, 549
Ethenyl ethanoate, copolymer with
chloroethene, 1435
polyvinyl alcohol from, 1433
preparation of, 649
Ethenyl trifluoromethanesulfonate, S, 1 solvolysis
of, 549
Ethenylbenzene (styrene), anionic polymerization
of, 1451-1452
block polymer from, 1452
chlorotrifluoroethene adduct of, 1313
copolymer with 1,3-butadiene, 506
copolymers from, 1452-1453
electronic absorptions of, 1030-1033
in fiberglass, 1440
with oxygen, 1453
polymers of, 391, 1430, 1433
radical polymerization of, 1447-1448
Ether (see Ethoxyethane)
Ethers, acid cleavage of, 656-657
from alcohols, 655
and diazomethane, 1199
by Williamson synthesis, 6 14-615, 655
from alkenes, 655
aryl, cleavage of, 1295
preparation of, 1294, 1297-1298
autoxidation of, 658-659
block polymers of, 1454
boron trifluoride complexes of, 656
chloro, formation and reactivity of, 704
classification of, 654-656
complexes with Grignard reagents, 577
cyclic, Hantzch-Widman nomenclature for,
659-660
IUPAC rules fo nomenclature of, 659-661
metal complexes of, 665-666
electronic spectra of, 605
infrared stretching frequencies for, 276
IUPAC rules of nomenclature for, 192, 654-656
mass spectra of, 607
oxonium salts from, 656-657
peroxides from, 658-659
phenylmethyl, as protecting group for OH,
65 1-652
physical properties of, 654-656
preparation of (table), 655
reactivity of, 600, acids and, 656-657
bases and, 656
oxygen and, 658-659
radicals and, 658-659
as solvents for organometallic reactions,
571-572, 577
spectroscopic properties of, 656
trimethylsilyl, as protecting group for OH,
65 1-652
unsaturated, protecting group formation with,
529-530
Williamson synthesis for, 6 14-6 15, 655
Ethoxyethane, boron fluoride complex of, 656
3om ethanol dehydration, 630-63 1, 650-65 1
physical properties of, 239, 654
triethyloxonium salts from, 657
Ethyl acetate (see Ethyl ethanoate)
Ethyl acetoacetate (see 3-Oxopropanoate esters)
Ethyl alcohol (see Ethanol)
Ethyl aminoethanoate, diketopiperazine from, 1222
ethyl diazoethanoate from, 1223
with nitrous acid, 1223
Ethyl benzenecarboxylates, hydrolysis rates and
Hammett equation, 1329-1330
Ethyl bromide (see Bromoethane)
Ethyl chloride (see Chloroethane)
Ethyl cyanoacetate, acidity of, 826
Ethyl diazoethanoate, preparation of, 1223
Ethyl ether (see Ethoxyethane)
Ethyl hydrogen sulfate, in dehydration of ethanol,
630-63 1
Ethyl iodide (see Iodoethane)
Ethyl malonate (see Propanedioate esters)
Ethyl nitroacetate (see Ethyl nitroethanoate)
Ethyl nitroethanoate, acidity of, 826
synthesis of, 1191
Ethyl orthoformate (see 1,1,1-Triethoxyethane)
Ethyl oxalate (see Ethanedioate esters)
Ethyl 3-phenylpropenoate (ethyl cinnamate),
Michael additions of, 844
-
Ethylene (see Ethene)
Ethylene chlorohydrin (see 2-Chloroethanol)
Ethylene glycol (see also 1,2-Ethanediol),
industrial perparation of, 647
properties of, 647
uses of, 647-648
Ethylene oxide (see Oxacyclopropane)
Ethylenediamine (see 1,2-Ethanediamine)
N-Ethylethanamine, nmr spectrum of, 1105
2-Ethyl-1-hexanol, industrial perparation of, 759
Ethyne, acidity of, 437-440
atomic-orbital model for, 167-168
ball-and-stick models of, 35
bond angles of, 35
bond distances in, 37
bromine addition to, 359
cycloaddition with 1,3-cyclopentadiene, 1314
cyclooctatetraene from, 990
1,3-cyclopentadiene adduct of, 526-527
dimerization to butenyne, 44 1
electrophilic addition to, bromine in, 382
characteristics of, 382-384
water in, 383-384
ethanoic acid addition to, 649
ethenyl esters and ethers from, 649
explosive decomposition of, 359
methanol addition to, 649
photoelectron spectrum of, 1357
physical properties (table), 446
polymerization of, 393
spectroscopic properties of, 446-448
thermodynamic stability of, 359
in welding, 359
Ethynyl cations, formation of, 549
Ethynylbenzene, infrared spectrum of, 356
nmr spectrum of, 357
17-Ethynylestradiol, 1479
Eucalyptus, 1,8-cineole from, 1466
Eugenol, rearrangement of, 1327
structure of, 1304
vanillin from, 1327
Eutectic mixtures, definition of, 258
Exclusion principle, 153-1 55
Exo-endo isomerism, 496-497
Exothermicity, definition of, 76
Explosives, nitro compounds as, 1191- 1192
Eye chemistry, 1416-1417
FAD (see Flavin adenine dinucleotide)
Faraday, M., 10
Farnesene, 1464, 1468
Farnesol, as insect hormone, 1468
pyrophosphate of, 1485, 1488
squalene from, 1485, 1488
as terpene alcohol, 1468
Farnesyl pyrophosphate, 1485, 1488
Fats, soaps from, 790
Fatty acids, biosynthesis of, 1480- 1481
characteristics of, 789-79 1
metabolism of, 837-840
Favorskii rearrangement, 748-749
Fehling's solution, 9 13
Fenchone, 1467-1468
Fermentation, in glycolysis, 949
of starch, 935
Ferric bromide, catalysis of arene bromination
with, 1044- 1046
Ferric chloride, with phenols (color test),
1294-1295
Ferricinium ion, 1506
Ferrocene, discovery of, 1504- 1505
electronic configuration of, 1505- 1506
physical properties of, 1504- 1506
reactions of, 1504-1506
structure and conformations of, 1505- 1506
Fiberglass, 1440
Field effect, and carboxylic acid ionizations,
799-780
Fireflies, 1397-1399
'
Fischer projection formulas, 128-159
Fischer, E., and determination of sugar configurations, 909-9 12
Fischer, E. 0 . H., 418
Fischer, H., and heme synthesis, 1257-1258
Fischer, O., and mauveine structure, 1406
Fischer-Tropsch process, 723
Flavin adenine dinucleotide, as biological oxidizing
agent, 646
in carbohydrate metabolism, 946
Flavin mononucleotide, in biological oxidations,
1308- 1309
Flavone, structure as prototype, 1461- 1462
Flavonoids, 1461- 1462
Flax, 933
Flower pigments, 1403
Fluoranthrene, from coal tar, 1080
Fluorene, acid strength of, 1322
from coal tar, 1080
Fluorescamine, with aminoacids, 1217
Fluorescein, 1392
Fluorescence, of benzene, 1375
definition of, 1374
Fluorination, of alkanes, 99
difluoromethylbenzenes from, 1318
trifluoromethylbenzenes from, 1318
Fluoroacetic acid, 792
Fluoroarenes, from arenediazonium salts,
1134-1135
Fluorocarbons, as blood replacements, 569
definition of, 568
development of, 568
physical and chemical properties of, 569
physiological properties of, 569
Fluorochloromethanes, 567
1-Fluoro-2,4-dinitrobenzene,
in peptide
sequencing, 1229-1230
Fluoroethanoic acid, 792
2-Fluoroethanol, toxicity of, 569
Fluoroethene, polymer of, 39 1, 1430- 1432
Fluoromethane, 18
ion-cyclotron resonance studies of, 1365
Fluxional molecules, 1089- 1090
Folic acid, structure and biochemical formation,
1123-1 124
sulfanilamide effect on, 1123- 1124
Formal bonds, in resonance treatment, 973
Formaldehyde (see Methanal)
Formic acid (see Methanoic acid)
Formose, and prebiotic evolution, 1283
Formulas, molecular, determination of, 3-4
N-Formylaminomalonic ester synthesis of amino
acids, 1226
Four-center reactions, hydroboration as, 424
Franck-Condon principle, definition of, 1372
in singlet excitation, 1372- 1374
Free energy, definition of, 84
of organic compounds, reference works for,
105-106
standard, 84-85
values for, 85, 87
Free radicals (see Radicals)
Free rotation, concept of, 7-8, 121-123
Friedel, C., and acylation of arenes, 1051-1053
and arene alkylation, 1047- 1050
Friedel-Crafts alkylation of arenes, 1047-1050
Friedel-Crafts ketone synthesis, 1051- 1053
Friedman, L. J., and cantharidin synthesis,
1497-1498
Front-side approach, 219-223
D-Fructose, 1,6-diphosphate, from biological
aldol reaction, 760-76 1
in glycolysis, 947-948
in photosynthesis, 943
hemiacetal form of, 62 1
osazone from, 924
6-phosphate, conversion to mannose
6-phosphate, 9 19
in glycolysis, 947-948
properties and occurrence of, 907
structure and configuration of, 906
Fructoside, definition of, 925
Functional derivatives, of carboxylic acids (table),
817-820
Functional groups, classification of, 39-42
reactions of, 41-42, 524-525
table of, 40
Furan (see Oxa-2,4-cyclopentadiene)
Furanose rings, 920-922
Furfural, 938
g factors, in esr spectroscopy, 1367
Gabriel synthesis, amines from, 1127, 1148
imides in, 1176
D-Galactose, properties and occurrence of, 907
structure and configuration, 905
Galactoside, definition of, 925
L-Galacturonic acid, 937
Gallic acid, 1304
Gammexane, 1076
Gasoline, composition of, 74
Gates, M., and morphine synthesis, 1499
Gattermann aldehyde synthesis, 1053-1055
Gattermann-Koch aldehyde synthesis, 1053
Gauche conformation, definition of, 124
Gel filtration, 1248
Gel polymers (see Polymers, gel)
gem, definition of, 647
Generalized theory of acids and bases, 208-211
Genetic code, 1271, 1276- 1277
Genetic control, DNA in, 1271, 1274-1275
Gentiobiose, amygdalin and, 1327
Geon, 1432
Geranial, 1465- 1466
Geraniol, 114- 115
Geranyl pyrophosphate, 1484-1485
Gibbs free energy (see Free energy)
Ginger, oil of, 1464
D-Glucaric acid, 9 13
Gluconeogenesis, 955-956
D-Glucose, absolute configuration of, 876-877
aldehyde derivatives of, 913-914
aldehyde form of, equilibrium with, 917
aldehyde reactions of, 9 13-9 14
a and ,B forms of, 914-918
amine derivatives of, 936-937
with amines, 923
amygdalin and, 1327
anomers of, 914-9 18
carbon- 13 nmr spectrum of, 9 17-9 18
configuration of, 908-909
conformation of, 9 15-9 16
D-glucaric acid from, 913
glucosylamines from, 923
in glucovanillin, 925-926
hemiacetal form of, 621
metabolism of, 944-950, 955-956
methanol reaction of, 914
methylation of, 92 1-922
mutarotation of anomers of, 917-9 18
occurrence of, 908
osazone from, 924
periodate oxidation of, 921-923
with phenylhydrazine, 924
(;-phosphate, in gluconeogenesis, 955-956
in glycolysis, 947-948
properties and occurrence of, 907
pyranose ring in, 920-922
reanangement to fructose and mannose,
918-919
as reducing sugar, 913
ring-size determination of, 92 1-923
sodium periodate oxidation of, 92 1-922
sorbitol from, 913
structure and configuration, 905
tetramethyl derivative of, 92 1-922
Glucosidase, 930, 935
Glucoside, definition of, 925
Glucosylamines, 923
Glucovanillin, 925-926
Glutamic acid, in carboxypeptidase, 1263-1264
properties, 1209
synthesis of, 1226
Glutamine, hydrolysis of, 1229
properties, 1209
Glutaric acid (see Pentanedioic acid)
Glutathione, 1242- 1243
Glyceraldehyde, chiral forms of, 132-133
D-Glyceraldehyde, absolute configuration of,
875-876
in gluconeogenesis, 955
in glycolysis, 947-948
3-phosphate, biological aldol reaction of,
760-76 1
in photosynthesis, 942-943
properties and occurrence of, 907
structure and configuration, 904
D-Glyceric acid, phosphates of, in photosynthesis, 942
phosphates of, in glycolysis, 949
Glycerides, hydrolysis of, 790
Glycerol (see 1,2,3-Propanetriol)
Glycin, 1311
Glycine, in carboxypeptidase, 1263- 1264
from chloroethanoic acid, 1225
in collagen, 1458
diketopiperazine from, 1222
with ethanoic anhydride, 1222
ethyl ester of, diketopiperazine from, 1222
ethyl diazoethanoate from, 1223
with nitrous acid, 1223
forms of, 1212-1213
ionizations of, 1212-1213
isoelectric point of, 1212
properties of, 1208
Glycols (see appropriate diols)
Glycolysis, mechanism of, 946-950
Glycosides, structures of, 925-937
Glymes, 656
Glyoxal, 774-775, 1078
Glyptal resins, 1439- 1440
Goddard, W. A., 111, and GVB orbital theory,
180-182
and ozone structure, 433
Gomberg, M., and triphenylmethyl radical, 1323
Gout, 1316
Graft polymers, 1454- 1455
Grape flavor, 1328
Graphite, properties and structure of, 17-18
Greek letters, and substitution positions, 225
Grignard, V., and organomagnesium
compounds, 576
Grignard reagents (see
Organomagnesium compounds)
Griseofulvin, 536
Guanidine, base strength of, 1118
Guanine, as DNA component, 1272-1277
in RNA, 1278
Guanosine diphosphate, in citric acid cycle,
95 1-954
structure of, 953
D-Gulose, structure and configuration, 905
L-Guluronic acid, 937
Gutta-percha, 507, biosynthesis of, 1485, 1488
GVB method, for benzene, 983-984
of ethane C-H bond, 439-440
of ethene bonding, 180-182.
of ethyne C-H bond, 439-440
of ozone, 433
Gyromagnetic ratio, 297
Hair curling, 1458
Haller-Bauer cleavage of ketones, 747
Hallucinogens, 1098
Haloalkanes, physical properties of (table),
537-538
Haloalkynes (see Alkynyl halides)
Haloarenes (see also Aryl halides), from arenediazonium salts (table), 1133-1 135, 1138
Halocycloalkanes (see Cycloalkyl halides)
Haloform reactions, with alkenones, 747
ethanoylarenes to arenecarboxylic acids
with, 1317
mechanism of, 746-747
synthetic uses of, 746-747
Halogen-metal exchange, preparation of organometallic compounds by, 573-574
Halogenation, selectivity in, of alkanes, 98-102
Halogenation of arenes (see also Electrophilic
aromatic substitution), 1044- 1045,
1070- 1072
Halogens, additions to alkenes, 360-367
with Grignard reagents, 586-587
a-Haloketones (see Ketones, a-halo)
Halomethanes, radical-chain addition to alkenes
and alkynes, 389
Hammett, L. P., and reactivity correlations,
1329-1337
Hammett equation, formulation of, 1330-133 1
limitations of, 1336-1337
scope of, 1335
Hammett rho ( p ) constant (table), 1330-1337
Hammett sigma (o) constants (table), 1330-1337
Hashish, 1305
Hassel, O., and conformational analysis, 124, 450
Haworth, W. N., and oligosaccharide structures,
928-929
Haworth projections, 9 15
Heart poison, 1473
Heat of reaction, calculation of, 76-80
definition of, 76
reference works for, 105-106
Heat of solution, of ions, 212-2 13
Heats of formation, of alkanes, 86-87
Heats of hydrogenation, of alkenes (table)
415-416
Heavy-metal salts, electrophilic catalysis of halide
S, reactions, 234
Index
Heisenberg, W., uncertainty principle of,
1343-1346
Heme, structure of, 1257
Hemiacetals (see also Memiketals), from alcohols
and carbonyl compounds, 621-624
D-glucose as, 9 13-9 18
mechanism of formation of, 622-624
Hemicelluloses, 937-938
Hemiketals (see also Hemiacetals), from alcohols
and carbonyl compounds, 62 1-624
from cyclopropanones, 780-78 1
mechanism of formation of, 622-624
Hemoglobin, function, 1249-1250, 1254-1259
as oxygen carrier, 1258-1259
properties, 1250
Hemp, 933
Henderson-Hasselbalch pH equation, 209
Heparin, 936-937
Heptanedioic acid, properties and uses of, 849
Heptoses, properties and occurrences of, 907
Herbicides, nitro compounds as, 1195
Herschel, W., discovery of infrared radiation, 271
Heterocyclic compounds, Hantzsch-Widman
nomenclature for, 659-66 1
IUPAC rules of nomenclature for, 659-661
Heterogeneous catalysis, of alkene hydrogenation,
410-414
of reduction of nitrogen to ammonia, 410-41 1
Heterolytic reactions, definition of, 207
kinds of, 207
Hexachlor, 1076
Hexachlorocyclopentadiene, in [4+21 cycloadditions, 493
Hexachloroethane, bond distances in, 37
Hexachlorophene, 56 1
1,4-Hexadiene, copolymers of, 1432, 1435
1,5-Hexadiene, from di-T-propenylnickel, 1522
Hexafluoroacetone hydrate, 647
Hexafluoropropene, copolymers of, 568, 1432
elastomer with 1,1-difluoroethene, 568
Hexamethylenetetramine, formation of, 700
nitration of, 701
structure of, 700
1,6-Hexanediamine, polymer from, 1433, 1441
synthesis of, 1441
Hexanedioic acid, from cyclohexane and
cyclohexanone, 1441
polymer from, 1433, 1441
"Hexaphenylethane," formation and structure
of, 1323
1,3,5-Hexatriene,benzene and, 967-968
with bromine, 968, 971
electrocyclic reactions of, 1005- 1012
with hydrogen, 968
molecular-orbital treatment of, bromine
with, 971
with nitric acid, 968
with ozone, 968
reactions of, 967-968
with tetracyanoethene, 968
Hexoses, structures and configurations of, 904-907
Hi-fax, 1432
4 565
Hindered rotation (see Restricted rotation)
Hinokitiol, 1314
Hinsberg test for amines, 1123
Histidine, in myoglobin, 1058
properties of, 1210
in proteolytic enzymes, 1266
Hodgkin, D., and vitamin B,,, 1490
and x-ray diffraction structure determinations, 1249
Hoffmann, R., and orbital symmetry rules, 1005
Hofmann degradation, amines from, 1150,
1153, 1155
Hofmann elimination, 1126
Holding groups, and E2 reactions, 468
stabilization of conformations with, 458-460
Homo, definition of, 1211
HOMO orbitals, 98 1
Homocysteine, 1211
Homogeneous catalysis, of alkene hydrogenation,
417-418, 1517-1518
Homogeneous catalysts, stereochemistry of
hydrogenation of alkenes with, 417
Homology, definition and uses of, 71-73
and physical properties, 7 1-73
Homolytic reactions, definition of, 206-207
Homopolymer, definition of, 505
Homoserine, 1211
Huckel, E., aromaticity rule, and cyclic ions,
996-998
and cyclic polyenes, 989-995
Huckel, W., and cis and trans isomers of
decalin, 480-48 1
Huckel orbital systems, energy levels of, 993
Hiickel rule, and cycloaddition reactions,
999-1005, 1010-1014
and electrocyclic reactions, 1005- 1014
and sigmatropic rearrangements, 1006, 1010- 1012
and tropylium cation, 1315
Hughes, E. D., and nucleophilic substitution
mechanisms, 22 1
Hund's rule, of electrons in degenerate orbitals,
153-155, 992-993
Hunsdiecker reaction, 813
Hybrid orbitals (see Atomic orbitals)
Hybridization, of atomic orbitals, 159- 161
and bond lengths (table), 987-988
Hydration of alkenes, 608
Hydrazides, in Curtius degradation, 1150,
1153, 1156
as functional derivatives of carboxylic acids, 819
preparation of (table), 858
Hydrazine, oxidation to diimide, 419
Hydrazines, aldehyde additions of, 698
from arenediazonium salts, 1138
azides from, 1197, 1202
ketone additions of, 697-699, 702
preparation of, 1194, 1197
reactions of, 1194- 1197
uses of, 1197
Hydrazobenzene, rearrangement of, 1140
Hydrazoic acid, in Schmidt degradation, 1150, 1153
Hydrazones, from aldehydes and ketones, 698
Index
Hydride reductions, alcohols from, 610
Hydride shifts, in transition-metal complexes,
1510-1514, 1517-1519, 1526
Hydroboration, of alkenes, alcohols from, 608
with alkyl and dialkylboranes, 422-424
with 9-BBN, 423
of 1,5-cyclooctadiene, 423
mechanism of, 425
orientation in additions to alkenes, 42 1-424
stereochemistry of, with alkenes, 422-424
Hydrocarbon acids, strengths of (table), 1322
Hydrocarbon alkylation, mechanism of, 397-398
Hydrocarbons (see Alkanes, Alkenes, etc., as
appropriate)
Hydro forming, 1079- 1083
Hydroformylation, aldehydes from, with
alkenes, 729
of alkenes, 722-723, 1518-15 19
industrial alcohol syntheses by, 759
mechanism of, 1518-1519
Hydrogen, calculations of bond energy of,
982-983
Hydrogen bonding, in alcohols, concentration
effects on, 3 11-3 12
infrared spectra and, 602-604
of alcohols, 600-605
and alpha helix, 1152-1 153
of amides, 1168
of amines, 1103- 1105
of carboxylic acids, 791
in DNA structure, 1275-1277
of enols, 740, 776
in enzyme reactions, 1262- 1263, 1266
ethanol, infrared spectra and, 602-604
and hydrogen fluoride, 20
infrared stretching frequencies for, 277
intramolecular hydrogen bonding, of
2,4-pentanedione, 740-742
of phenols, 1288-1291
in phenols, 1288
and pleated sheet, 1252-1253
in proteins, 1251-1253, 1259
and proton nmr spectra, 311-313, 741-742,
1291-1292
in tRNA structure, 1279-1282
Hydrogen bromide, addition to alkenes, 379
radical-chain addition to alkenes, 386-389
Hydrogen chloride, addition to alkenes, 379
Hydrogen cyanide, addition to alkenals and
alkenones, 768
addition to aldehydes and ketones, 689-690
physical properties of, 239
in prebiotic evolution, 1282-1284
Hydrogen fluoride, addition to ethyne, 382
additions to alkenes, 368, 379
physical properties of, 19-20, 239
Hydrogen halides, additions to alkenes,
367-368, 370-371, 373-376
Hydrogen molecule, bonding in, 960-964
Hydrogen molecule-ion, bonding in, 156
- Hydrogen peroxide, addition to alkenes, 434-437
in nitrile hydrolysis, 1178
oxidation of amines with, 1143- 1144
Hydrogen sulfate esters, from additions to alkenes,
369-371
Hydrogen sulfide, bond angles of, 172
Hydrogen sulfite, additions to aldehydes and
ketones, 695
Hydrogenation, of aldehydes and ketones, 710
of alkenes, heats of (table), 415-4 16
of alkynes, 413-414
of arenes, 414, 1072-1074
of benzenols, 1300
of carbon monoxide, 612
of carbonyl compounds, 611
catalysts for, 411-414, 417-418, 1517-1518
homogeneous, mechanism for rhodium catalyst,
1517-1518
homogeneous catalysts for, 417-418
Hydrogen-deuterium exchange, of arenes, 1057
Hydroperoxides, from alkenes, with hydrogen
peroxide, 72 1
from Grignard reagents and oxygen, 587
ketones from, by rearrangement, 721-722, 732
rearrangements of, to carbonyl compounds,
721-722, 732
Hydroquinone (see 1,4-Benzenediol)
Hydroxamic acids, from esters, 858
as functional derivatives of carboxylic acids, 819
2-Hydroxyalkanoic acids, lactides from, 843
3-Hydroxyalkanoic acids, from ketones and esters,
835-836
from Reformatsky reaction, 836
from unsaturated acids, 841-842
unsaturated acids from, 843
4-Hydroxyalkanoic acids, lactones from, 843
2-Hydroxybenzenecarbaldehyde, from
benzenol, 1299
hydrogen bonding in, 1288
physical properties of, 1290
4-Hydroxybenzenecarbaldehyde, physical
properties of, 1288, 1290
2-Hydroxybenzenecarboxylic acid, from benzenol,
1298- 1299
ethanoate ester of (aspirin), 1328
hydrogen bonding in, 1288
methyl ester of, 1327-1328
4-Hydroxybenzenecarboxylic acid, from benzenol,
1298-1299
3-Hydroxybutanal (aldol), dehydration of, 755-756
preparation of, 749-75 1
2-Hydroxybutanedioic (malic) acid, from biological
hydration of trans-butenedioic acid, 371-372
as intermediate in citric acid cycle,
95 1-954
2-Hydroxybutanoic acid, oxidation of, NAD+
and, 645
Hydroxycyclobutenediones, 1313
2-Hydroxy-1,2-diphenylethanone, formation and
reactions of, 1324-1325
Hydroxyketones, by acyloin reaction, 852-853
by aldol addition, 752-753, 756-758, 760-761
,
Hydroxylaminesulfonic acid (azanyl hydrogen
sulfate), organoborane reactions, 427,
430-43 1
Hydroxylysine, properties, 1209
2-Hydroxy-6-methylbenzenecarboxylic acid,
biosynthesis of, 1481- 1482
2-Hydroxymethyl-2-methyl- 1,3-propanediol,
polyesters from, 1440
3-Hydroxypentanoic acid, from 2-oxobutanoic
acid, 840
N-(4-Hydroxyphenyl)aminoethanoic acid, 1311
4-Hydroxphenylmethanol, from benzenol, 1300
11-Hydroxyprogesterone, from progesterone by
microbial oxidation, 1478
Hydroxyproline, and alpha helix, 1252
in collagen, 1458
with ninhydrin, 1217
properties of, 1210
2 - ~ ~ d r o x ~ ~ r o ~acid,
a n oini cgluconeogenesis,
955-956
in glycolysis, 949-950
oxidation of, NAD+ and, 645
2-Hydroxypyrimidine, lactam-lactim isomerism
of, 1273
Hyperconjugation, definition of, 228
and stability of carbocations, 228
Hyperfine interactions in esr spectra, 1369-1360
Hypochlorous acid, additions to alkenes, 360,
378-379
Hypoiodous acid, addition to alkenes, 379
I-effect (see Inductive effecl)
D-Idose, structure and configuration, 905
Imidazole (see 1,3-Diazacyclopentadiene)
Imides, acidity of, 1176
as functional derivatives of carboxylic acids, 818
ladder polymers of, 1456
Imines, amines from, 1146, 1148, 1154
formation of, 696-699
rearrangement of, 1122
in visual process, 1416-1417
1,2,3-Indanetrione (see Ninhydrin)
Indanthrene Brilliant Orange, 1407
Indene, acid strength of, 1322
Indigo, 1403
Indole, alkaloids related to, 1461- 1462
structure as prototype, 1461-1462
Inductive effects, amine basicities and, 1114-1 116
in aromatic substitution, 1060- 1064
and carboxylic acid ionization, 798-800
Infrared spectra, of alcohols, hydrogen bonding
effects on, 604
of alkanediols, hydrogen bonding effects on, 604
of alkenes, 351-352
of alkynes, 356
of amides, 1170-1171
of amines, 1104
of amino acids, 1215
of arenes, 1027-1030
bending vibrations in, 272-282
of carbonyl compounds (table), 680-681
of carboxylic acids, 281-282, 793-794
conjugation effects on, 292
of diatomic molecules, 272
elements of, 267
of ethanol, 602-604
of ethers, 656
fingerprint region of, 278
hydrogen bonding effects on, 277, 281, 602-604,
793, 1104, 1171
of nitriles, 1184
of nitro compounds, 1187
overtones in, 352-353
practice of, 273-274
reference works for, 347-348
stretching vibrations in, and atomic masses,
274-275
and bond types, 275
energy changes in, 277
force constants for, 274-275
general considerations, 272-284
and rotational transitions, 275-277
table of, 276-277
structure determination with, 28 1-282, 3 13-3 14
Infrared spectrum, of 3-bromopropene, 324
of 2-butanone, 273
of I-butene, 351-353
of cyclohexanamine, 1104
of cyclooctane, 280
of cyclopropanecarboxylic acid, 28 1-282
of dimethylbenzenes, 1029
of N,N-dimethylmetl~anamide, 1171
ethanal in tetrachlorometlzane, 794
ethanoic acid in tetrachloromethane, 794
ethanol in tetrachloromethane, 794
of ethynylbenzene, 356
N-methylbenzenamine, 1104
of methylbenzenes, 1028
of methylcyclohexane, 280
of octane, 279
of N-phenylethanarnide, 1171
of propanamide, 1171
of 2-propanone, 273
of 2,2,4-trimethylpentane, 279
of tropylium ion, 1315
Ingold, C. K., and nucleophilic substitution
mechanisms, 22 1
Inhibitors, of chain reactions, 95
of radical polymerization, 1449
Insect pheromones, isomerism and activity of, 141
Insecticides, aryl halides for, 56 1
examples of, 1328
Insulin, function of, 1249
properties, 1250
Interelectronic repulsions, theoretical calculations
and, 982
International Union of Pure and Applied
Chemistry nomenclature (see IUPAC rules)
Intersystem crossing, definition of, 1374-1375
of diphenylmethanone, 1379
of methanal, 1374-1375
Inversion, of amines, 1109- 1110
in S, reactions (see Nucleophilic displacement
reactions)
Invertase, 930
Iodination, of arenes, 1044- 1046
Iodine chloride, addition to alkenes, 379
Iodine, addition to alkenes, 379
addition to cyclohexene, 367
charge-transfer complex with cyclohexene, 367
Iodobenzene, electronic absorptions of, 1032-1033
preparation of, 1046- 1047
N-Iodobutanimide and hydrogen fluoride, in
additions to alkenes, 380
1-Iodo-2,2-dimethylpropane,
rearrangements in
solvolysis of, 250
Iodoethane, nrnr spectrum of, 3 16-3 18
Iodoform, 746
Iodomethane, amines from, 1125
electronic spectrum of, 289
1-Iodopropane, microwave spectrum of, 27 1
Iodopsin, 1416-1417
Ion-cyclotron resonance, elements of, 267,
1364- 1365
gas-phase acidities from, of alcohols, 1364
of alkynes and water, 437
of carboxylic acids, 802
halide displacement reactions in, 1365
nitrogen and xenon fixation in, 1365
uses of, 1364-1365
Ion-exchange chromatography, for amino acids,
1219- 1220
for protein separations, 1248
synthesis of resins for, 1221
Ionization equilibria, of amino acids, 1212- 1215
Ionizing power, of solvents, 237-239
Ions, solvation of, 237-238
Ipso substitution of arenes, 1066-1068
Iron compounds, ferrocene as, 1369, 1504- 1506
Mijssbauer spectroscopy of, 1359
Iron tricarbonyl, 1,3-butadiene complex of, 152'
cyclobutadiene complex of, 1359, 1507
cyclooctatetraene complex of, 1359
norbornadiene complex of, 1510
Isobutane (see 2-Methylp'ropane)
Isobutyl alcohol (see 2-Methyl- 1-propanol)
Isobutylene (see 2-Methylpropene)
Isocitric acid, in citric acid cycle, 951-954
Isocyanates, carbamic acids from, 1155-1 156
in Curtius degradation, 1156
in Hofmann degradation, 1155-1 156
Isoeugenol, 1327
Isoleucine, properties of, 1208
Isomerism, cis-trans, 111- 114, 475-476, 511,
885-887
and sense of taste and smell, 140-141
configurational, 114
conformationd, examples of, 121-125, 448-463,
469-474, 480-48 1, 1345- 1347
diastereomers, 133- 139
geometric, 111
optical, of 2-butanol, 119-120
configurations of, 119, 874-877
conventions for, 119, 879-884
D,L convention for, 131- 139
Fischer projections for, 128-159
isomer numbers, 134- 139
representations for, 119, 127, 128-139
resolution and determination of purity of,
866-873
and rotation of polarized light, 118-1 19,
862-866
and taste and odor, 140-141
of threonine, 133-135
types of, 44-45
Isomers, constitutional, 45
position, 44-46
structural, 45
Isoniazid, as carcinogen, 1164
Isonicotinic acid hydrazide, as carcinogen, 1164
Isooctane (see 2,2,4-Trimethylpentane)
Isopentenyl pyrophosphate, as biological isoprene
unit, 1463, 1483-1485
Isophthalic acid, polyesters from, 1440
Isoprene (see 2-Methyl- 1,3-butadiene)
Isoprene rule, basis of, 1462- 1463, 1483- 1488
definition of, 68
3-methyl-3-butenyl pyrophosphate and, 1463,
1483-1485
Isoprenoid compounds, of animal origin, 1469
biosynthesis of, 1483- 1488
structures and types of, 1462-1469
Isopropyl (see 1-Methylethyl)
Isopropyl alcohol (see 2-Propanol)
Isopropylbenzene [see (1-methylethy1)benzene)l
4-Isopropyltropolone, 1314
Isotactic polymers, 1430-1435
Isotope effect (see Kinetic isotope effect)
IUPAC rules of nomenclature, for acyl halides, 198
for acids, 195
for alcohols, 191
for aldehydes, 192- 193
for alkanecarbonyl groups, 196
for alkanes, 5 1-57
for alkanoyl groups, 193
for alkenes, 59-61
for alkoxy groups, 192
for alkoxycarbonyl groups, 197- 198
for alkyl halides, 56
for alkyl radicals, 52-56
for alkynes, 61-62
for amides, 199, 1169
of amine salts, 1102
for amines, 200-201, 1100-1102
for amino groups, 201
for anhydrides, 198
of arenes, 62-64, 1024-1025
for benzene and its derivatives, 61-63,
1024- 1025
for benzenols, 191
for carboxamides, 199
for carboxylate groups, 195
Index
for carboxylic acids, 195
for carboxylic anhydrides, 198
for carboxylic esters, 196-198
for cycloalkanes, 57-58
for cycloalkenes, 60
for ethers, 192
functional groups, precedence order of, 186- 187,
188-189
table of, 188-189
for ketones, 194
names to structures, 187-189
for nitriles, 192
for nitroalkanes, 56
numbering of chains in, 52-56, 186-189
for 0x0 derivatives, 194
parentheses in, 54-56
for phenols, 191
of polycycloalkanes, 476-479
for polyenes, 60-61
primary groups, 54
reference books for, 62, 141-142, 204
secondary groups, 54
single- or multiple-word names in, 203-204
of spiranes, 478
for stereoisomers, reference works for, 141-142
structures to names, 186-187
substituents, precedence of, 56
for substituted alkanes, 56
tertiary groups, 54
Jensen, F. R., and cyclohexane conformational
equilibria, 456-457
Johnson, W. S., and biomimetic steroid syntheses,
1488-1489
and estrone synthesis, 1496- 1497
Jute, 933
Juvenile hormone, isolation and action of, 1469
as isoprenoid compound, 1469
synthesis of, 1470
KekulC, A., and cyclobutadiene, 989
and molecular formulas, 5
and structure of benzene, 10
structures for benzene, 173-176, 972-975
Kel-F, 568, 1432
Kendrew, J., and x-ray diffraction structure
determinations, 1249
Keratin, 1259
Kerosine, 74
Ketals, from alcohols and carbonyl compounds,
62 1-624
as ethers, 667
hydrolysis of, 624
mechanism of formation of, 622-624
as protecting groups for carbonyl functions,
715-716
Ketene, acylating reactions of, 772
anhydrides from, 857
from cyclobutanone photodissociation, 1381
cyclopropanone from, with diazomethane, 780
dimerization of, 772
from photolysis of %-propanone, 1379
properties of, 772
Ketenes, carbenes from, 566
cycloadditions with, 773
dimerization of, 503
preparation of, 77 1
Keto-en01 equilibria, 736-741, 776-778, 827-828
Ketoketenes, 77 1
Ketones, acidities of (table), 736-738
from acyl halides, and alkyltetracarbonylferrates,
1516
and alkylzirconocenes, 1514- 1515
with cadmium alkyls, 731
additions to, of alcohols, 694
carbon nucleophiles, 689-793
general characteristics of (table), 685-689
of hydrogen cyanide, 689-690
of hydrogen sulfite, 695
of nitrogen nucleophiles (table), 697-703
of organometallics, 577-582
table of examples, 688-689
of thiols, 694
ylides, 69 1-692
from alcohol oxidations, with
azabenzene-chromic oxide, 642
biochemical with NAD+, 644-646
with chromic acid, 640-641, 730
Oppenauer method, 730
with permanganate, 643
alcohols from, with Grignard reagents, 609
by Meerwein-Ponndorf-Verley reduction, 6 11
by reduction, 6 10-61 1
aldol additions of, 752-754, 756-758, 760-761
from 1,2-alkanediols, by oxidation, 7 17, 730
by rearrangement, 720, 73 1
from alkenes, by hydroboration and
carbonylation, 732
and ozone, 730
alkyl aryl reactivities, Hammet correlation
of, 1334
alkylation of, carbon vs. oxygen, 762-763
enamines as alternatives, 764-765
thermodynamics .of, 762
from alkylboranes, by carbonylation, 725-726
from alkylcadmiums with acyl halides, 584
from alkylcoppers, 584
aluminum complexes of, 1052
amides from, by Haller-Bauer cleavage, 747
amines from, 1148, 1154
from arene acylations, 1051- 1053
azines from, 698
borane reduction of, 707-708
borohydride reduction of, 705-708
from cadmium alkyls and acyl halides, 584
carboxylic acids from, 855
chiral, optical rotatory dispersion of, 890-893
racemization mechanisms of, 895-896
CIDNP in photochemical reactions of,
1353-1356
Claisen condensations with, 832
from copper alkyls and acyl halides, 584
from decarboxylation of dicarboxylic acids, 847
diazo derivatives of, 693
diazomethane reactions with, 692-693
from dicarboxylic acids, by decarboxylation, 732
gem-dichlorides from, 704
electronic excitation of, 1375-1376
electronic spectra of, 681
enamines from, 702
en01 and enolate reactions of, 735-763
en01 content of (table), 740
enolization of, acid induced, 739
base induced, 736-738
equilibrium for, 736-738, 740-741
by Grignard reagents, 582
in haloform reaction, 746-747
in halogenation, 742-745
in nucleophilic reactions, 749-754, 76 1-763
excited states of, 1375-1376
fluorescence and phosphorescence of, 1375-1376
general characteristics of, 671-678
from Grignard reagents (table), 579, 583-584
Haller-Bauer cleavage of, carboxamide from, 747
a-halo, reactivity of, 225, 748-749
haloform reactions of, 746-747
arenecarboxylic acids from, 1317
a-halogenated, Favorskii rearrangement
of, 748-749
reduction of, 748
SN1 and S,2 reactivity of, 748
halogenation of, base and acid catalyzed,
742-745
mechanism of, 742-745
hemiketal formation from, 62 2 -624
hydration of, 647, 673-674
hydrazones from, 698
from hydroperoxides by rearrangement,
721-722, 732
3-hydroxyalkanoic acids from, 835-836
imines from, 697-699
infrared frequencies, 276, 680-68 1
IUPAC rules of nomenclature for, 194
ketal formation from, 62 1-624
from lithium reagents and carboxylates, 583
mass spectra of, 684
Meerwein-Ponndorf-Verley reduction of,
709-7 10
nitriles from, 1185
from nitriles, with Grignard reagents, 73 1
nmr spectra of, 684
from Oppenauer oxidation, 730
from organoboranes, 428-429
oxidation of, Baeyer-Villiger, 7 13-7 14
oximes from, 698
from 3-oxoalkanoic esters, by hydrolysis, 73 1
from 3-oxobutanoic acids, 834
from ozonization of alkenes, 43 1-433
with phosphorus pentachloride, 704
photocl~emicalcycloadditions of, with alkenes,
1389-1390
photochemistry of, CIDNP effects on, 1353-1356
photoreduction of, 1382- 1383
as photosensitizers, 1385- 1386
physical properties of (table), 678-679
preparative methods for (table), 7 17-729
protecting groups for, 7 15-7 16
reactivity of, and angle strain, 677-678
and bond polarity, 674-678
and electronegative substituents, 678
reduction of, with aluminum alkoxides, 709-710
Clemmenson, 7 11
by Grignard reagents, 582
with hydrides (table), 705-708
by hydrogenation, 7 10
photochemical, 1382- 1383
by Wolff-Kishner, 71 1-712
semicarbazones from, 698
with sulfur tetrafluoride, 705
unsaturated (see also Alkenones)
1,baddition of organometallics to, 585-586
addition reactions of, 768-770
electronic spectra of, 767
photochemical cycloadditions of, 503
spectral properties of, 767-768
Ketoses, structures and occurrence of, 903-908
Kharasch, M. S., radical mechanism for hydrogen
bromide additions to alkenes, 386
Kinetic control, of additions to alkenes, 374-376
in carbocation rearrangements, 633
Kinetic isotope effect, in chromic acid oxidation, 641
Kolbe electrolysis, 8 13
Kolbe-Schmitt reaction, 1298-1299
Krebs, H. A., and citric acid cycle, 944, 951-954
Krebs cycle, 944, 951-954
aldol addition in, 839-840
Kuhn, R., and cis-trans isomers of cumulated
trienes, 5 11
P-Lactamases, 1492
Lactams, as functional derivatives of carboxylic
acids, 8 19
P-Lactams, in penicillins and cephalosporins, 1492
Lactic acid (see 2-Hydroxypropanoic acid)
Lactic acid dehydrogenase, 645
Lactide formation, 843
Lactones, as functional derivatives of carboxylic
acids, 8 19
from hydroxy acids, 843
from unsaturated acids, 842-843
Lactose, properties and occurrence of, 907
structure and configuration of, 929
Ladder polymers, 1456- 1457
Ladenburg, A., structure for benzene, 12
Ladenburg benzene, prismane and, 482
LAH (see Lithium aluminum hydride reduction)
Lanosterol, structure and biosynthesis of,
1486-1487
Lanthanide shift reagents, 872-873
Le Bel, J. A., 6
and asymmetric carbon, 116
and tetrahedral carbon, 118
Least structural change, principle of, 13
Leather, 1459
Leaving groups (see also Nucleophilic displacement reactions), for amide formation,
1177-1 178
Lemon, oil of, 1464, 1466
Leucine, isomers of, and taste, 140
properties of, 1208
Levorotatory, definition of, 119, 863
Lewis, G. N., and acid-base theory, 208-209
and theory of valence, 19
Lewis acids definition of, 208-209
Lewis bases, definition of, 208-209
Lewis structures, and electron-pair bonds, 19
Librium, 1098
Lichen pigment, 1304
Light (see Photochemistry, Electronic spectra, etc.)
Light absorption (see Electronic spectra or
Photochemistry)
Lily-of-the-valley, 1468
Limonene, 1464
Linalool, 1465-1466
Lindane, 536-537, 1076
Lindlar catalyst, for selective reduction of
alkynes, 414
Line spectra, 268-269
Line widths in nmr spectra, 1343-1344
Linoleic acid, 789-790
Lipids, 790, 805
Lithium aluminum hydride reduction, alcohols
from, with carbonyl compounds, 610,
809-810, 824
with oxacyclopropanes, 6 10
aldehydes from, acids and acyl derivatives,
728, 8 10-81 1, 824-825
amide and nitrile reductions, 719, 728,
824-825
amines from, 824-825, 1146- 1148, 1154
of carboxylic acids to alcohols and aldehydes,
810-811
of nitriles to aldehydes, 719, 824
procedures for, 705-706
Lithium bis(trimethylsilyl)amide, enolate anion
formation with, 836
Lithium hydride, bonding and physical properties
of, 19-21
reactions of, 20-21
"Living" polymerizations, 1451- 1452
London, F., dispersion forces and, 455
London forces, 455
Lowry, T. M., and acid-base theory, 208
LSD, 1097
Lubricating oils, 74
Lucas, H. J., and alcohol-type test, 626
Luciferin and lucerifase, 1397- 1399
Lucite, 1433
LUMO orbitals, 98 1
Lustron, 1433
Lycopene, biosynthesis of, 1485, 1488
electronic absorptions of, 1401
as isoprenoid hydrocarbon, 1464
structure of, 1401
Lynen, F., and fatty acid biosynthesis, 1480
Lysergic acid, 1097
Lysine, codon for, 1282
genetic code for, 1277
ionization equilibria of, 1214- 1215
properties, 1209
Lysozyme, carbon-13 spectrum of, 1286
disulfide bridges in, 1254- 1255
function of, 1254
properties, 1250
structure of, 1254-1255
D-Lyxose, structure and configuration, 904
Magenta dye, 1410-1414
Maleic acid (see cis-Butenedioic acid)
Maleic anhydride (see cis-Butenedioic anhydride)
Malonic ester acid synthesis, 833-834
Malonic esters (see Propanedioate esters)
Maltose, properties and occurrence of, 907
from starch, 934
structure and configuration of, 929
D-Mannose, osazone from, 924
6-phosphate, conversion to fructose
6-phosphate, 919
properties and occurrence of, 907
structure and configuration, 905
D-Mannuronic acid, 937
Markownikoff's rule, definition of, 376
uses of, 377-381
violation of, electron-attracting groups and,
380-381
by radical addition reactions, 386-388
Mass spectra, of alcohols, 607
of aldehydes, 340-341, 684
of alkynes, 357
of amines, 1106- 1108
of amino acids, 1216
apparatus for, 340, 1361-1363
characteristics of, 340-345
chemical ionization procedure for,
1361-1363
elemental compositions from, 341-343
of ethers, 607, 656
field ionization procedure for, 1361
fragmentations in, 344-345, 1360- 1365
hydrocarbons, chemical ionization of, 1362
isotopes and, 342-343
of ketones, 340-341, 684, 1362
methane, chemical ionization of, 1361- 1362
molecular formulas from, 341-343
molecular weights from, 341
parent peak in, 341-345, 1361-1363
rearrangements in, 345
reference works for, 342, 349, 1370
sample volatilization in, 1363
Mass spectrum, of 2-butanone, 340-341
of I-(3,4-dimethoxyphenyl)ethanone,1362
of 2,2-dimethylbutane, 344
of ethyl butanoate, 344
of methylbenzene, 345
of octadecane, 1363
of 2-pentanone, 346
of propanal, 34e341
of 2-propanone, 340-341
Mauveine, 1406
Mayer, V., 27-28
Mayo, F. R., radical mechanism for hydrogen
bromide additions to alkenes, 386
Meerwein reaction, 1135-1 136
Meerwein-Ponndorf-Verley reduction, 6 11,
709-7 10
Meisenheimer, J., and aryl addition complexes, 555
Melmac (melamine) resins, 1444
Melvalonic acid, in cholesterol biosynthesis,
1486- 1488
in terpene biosynthesis, 1483-1485, 1488
Membrane lipids, 790, 805
Menadione, 1310
Menthol, 1466- 1467
Menthone, 1466- 1467
Mercaptobenzothiazole, 1429
Mercaptoethanoic acid, with wool, 1458
Mercuration of arenes, 1058
Mercuric salts, addition to alkynes, 383-384
additions to alkenes, 380
Merrifield, R. B., and solid-phase peptide
syntheses, 1242- 1247
Mescaline, 1097
Mesityl oxide, 756
Mesitylene (see 1,3,5-Trimethylbenzene)
Meso compounds (see also Chirality and Isomerism), 135-139
Mess,enger RNA, 1279-1282
Mestranol, 1479
meta, definition of, 63
Meta-directing groups (tables) 1060-1062
Metabolism (see Biosynthesis, Glycolysis, etc.)
Metal carbonyls (see Transition-metal complexes)
Metal chelates, of 2,4-pentanedione, 777
Metal-halogen exchange, preparation of organometallic compounds by, 573-574
Metaldehyde, 696
Metalloporphyrins, 1256-1259
Metaphosphoric acid, esters of, formation and
reactions of, 634-637
Metathesis of alkenes, 1520- 1521
Methanal, alcohols from, with Grignard reagents,
577, 579, 608
in aldol additions, 753-754
ammonia addition to, 700
Bakelite resins from, 1442- 1443
ball-and-stick model of, 35
with benzenol, 1442- 1443
bond angles of, 35
bonding in, 31-32, 674-675
Cannizzaro reaction of, 707-709
in chloromethylation of arenes, 1054, 1319
electronic excitation of, 1375-1376
excited states of, 1375-1376
fluorescence and phosphorescence of,
1375-1376
geometries of excited states of, 1376
hexamethylenetetramine from, 700
molecular energy levels of, 1375-1376
physical properties of, 679
polymerization of, 696
in prebiotic evolution, 1282-1284
resins from, 1442-1444
with urea to give resin, 1443-1444
Methanamide, physical properties of, 239
Methanamine, physical properties of, 1101
Methane, bonds and geometry of, 169
in chemical ionization mass spectrum of,
1361-1362
chlorination of, 8 1-85, 88-96
combustion of, 76
electronic spectrum of, 289
heat of combustion of, 76
ionization of, 1361
mass spectral use of, 1361-1362
from photolysis of 2-propanone, 1379
physical properties of, 19-2 1
polychlorination of, 100
in prebiotic evolution, 1282
space-filling model of, 38
steam-gas reaction of, 410
Methanediol, 646-647
Methanenitrile, bonding in, 3 1-32
Methanoic acid, physical properties of, 239, 792
Methanol, acidic properties of, 613
atomic-orbital model of, 164-165
with carbon monoxide, ethanoic acid from, 1520
electronic spectrum of, 289
ethanoic acid from, 1520
hydrogen bromide salt of, 613-614
industrial preparation of, 6 12
physical properties of, 239, 601
Methide anion, geometry of, 169
Methionine, properties, 1209
Methodology of organic synthesis, 5 13-5 15
Methoxybenzene, benzenol from, 1295
from benzenol, 1294
chlorination of, cyclodextrin effect on,
935-936
cleavage with hydrogen bromide, 1295
Methoxychloromethane, as carcinogen, 1164
Methoxyethene, physical properties of, 654
preparation of, 649
Methoxymethane, electronic spectrum of, 289
with hydrogen bromide, 13
trimethyloxonium salts from, 657
Methyl anthranilate, 1328
Methyl bromide (see Bromomethane)
Methyl Carbitol, 662
Methyl carbocation, geometry of, 169
Methyl Cellosolve, 656
Methyl chloride (see Chloromethane)
Methyl chloromethyl ether, as carcinogen, 1164
Methyl ethyl ketone (see 2-Butanone)
Methyl fluoride (see Fluoromethane)
Methyl D-glucosides, 9 15
Methyl 2-hydroxybenzenecarboxylate, 1327- 1328
Methyl iodide (see also Iodomethane)
amines from, 1125
nucleophilic reaction with rhodium, 1520
Methyl methacrylate (see Methyl 2-methylpropenoate)
Methyl 2-methylpropenoate, block polymer
from, 1452
copolymerization of, 1452
polymers of, 391, 1433, 1451
Methyl parathion, 1328
Methyl phenyl ether (see Methoxybenzene)
Methyl phenyl ketone (see Phenylethanone)
Methyl radical, geometry of, 169- 170
Methyl salicylate, 1327- 1328
Methyl vinyl ketone (see 3-Buten-2-one)
Methylacetylene (see Propyne)
Methylamine (see Methanamine)
4-N-Methylaminobenzenol, 1311
N-Methylaniline (see N-Methylbenzenamine)
4-Methylbenzenamine, base strength of, 1115
N-Methylbenzenamine, infrared spectrum of, 1104
Methylbenzene, benzenecarboxylic acid from, 1317
benzenol from, 1292-1293
bromination of, with bromotrichloromethane,
103-104
chlorination of, with tert-butyl hypochlorite,
103-104
halogenation of, ring, 1046
industrial syntheses based on, 1083
iodination of, 1046
mass spectrum of, 345
nitration of, 1042-1043, 1189
. from petroleum, 1079- 1083
physical properties of, 1027
side-chain halogenation of, 97, 104, 546-547,
1046, 1317-1318
stabilization energy of, 985
Methylbenzenes, infrared spectra of, 1027-1029
4-Methylbenzenol, physical properties of, 1289
Methylbenzenols, from coal tar, 1291
2-Methyl-1,3-butadiene, anionic polymerization
of, 1451
copolymer with 2-methylpropene, 506, 508
copolymerization of, 1453
polymers and copolymers of, 1432-1433
cis-trans isomers of, 507-508
elastic properties of, 507-508
purification through sulfur dioxide adduct,
500-501
stabilization energy of, 986
sulfur dioxide adduct, 500-501
2-Methylbutane, bromination of, 101- 102
chlorination of, 100- 102
2-Methyl-2-butanol, nmr spectrum of, 305
2-Methyl-2-butene, heat of hydrogenation of, 415
3-Methyl-3-butenyl pyrophosphate, as biological
isoprene unit, 1463, 1483-1485
Methylcyclohexane, carbon-13 nmr spectrum
of, 460
conformational equilibria of, 453-454, 457, 460
infrared spectrum of, 280
from petroleum, 1081
Methylene (see Carbene)
Methylene blue, 1392
Methylene glycol, 646-647
(I-Methylethenyl)benzene, nmr spectrum of,
325-327
(I-Methylethy1)benzene (isopropyl benzene),
acid strength of, 1322
autoxidation of, 721
benzenol from, 72 1-722, 1293
physical properties of, 1027
2-propanone from, 721-722, 1293
3-Methyl-3-hydroxypentanedioic acid
(mevalonic acid), 1483- 1488
Methyllithium, 18
Methylmalonyl coenzyme A, conversion to
succinyl coenzyme A, 1526
N-Methylmethanamide, nitrogen-15 nmr spectrum
of, 1175
2-Methyl-l,4-naphthalenedione,
vitamin K activity
of, 1310
N-Methyl-N-nitrobenzenamine, as carcinogen, 1164
1-Methyl-3-nitrobenzene,synthesis of, 1190
N-Methyl-N-nitrosourea, as carcinogen, 1164
N-Methyl-N-nitro-2,4,6-trinitrobenzenamine, 1192
Methylphenols (see Methylbenzenols)
2-Methylpropane, in alkylation of 2-methylpropene, 397-398
heat of combustion of, 79
yield calculations for bromination of, 5 15-5 16
Methylpropanedioyl coenzyme A, conversion to
butanedioyl coenzyme A, 1526
Methylpropanoic acid, conversion to butanedioic
acid, vitamin B,, and, 1526
2-Methyl-2-propanol, acidic properties of, 613
dehydration of, 63 1-632
industrial preparation of, 607
2 - ~ e t h ~ l ~ r o ~alkylation
e i e , by 2-methylpropane:
397-398
cationic polymerization of, 393-395
copolymer with 1,3-butadiene, 506, 508
from dehydration of 2-methyl-2-propanol,
63 1-632
diisobutylene from, 394-395
hydration of, 369
hydrogen bromide addition to, kinetic vs.
equilibrium control in, 374-376
polymers and copolymers of, 391, 1432
radical-chain polymerization of, 396
in Ritter reaction, 1178-1 179
2-Methylpropenenitrile, 689
N-Methylpyrrolidine, solvent properties of, 1168
Methylstyrene [see (I-Methyletheny1)benzenel
Methylsulfinylmethane, in Gabriel m i n e
synthesis, 1127
oxidation of alcohols and halides with, 718
physical properties of, 239
as solvent, 238
1-Methyl-2,4,6-trinitrobenzene (TNT), from
methylbenzene, 1189
oxidation of, 1189
1,3,5-trinitrobenzenefrom, 1189
Metol, 1311
Micelles, formation of, 803-804
reactions in, 804-805
Michael addition, of alkenones, 770
amino acids from, 1226
in annelation reactions, 1478
in color photography, 1413-1415
of enamines, 845
in methanal-benzenol reaction, 1442
of nitro compounds, 1196
in steroid syntheses, 1478
of unsaturated esters, 844-845
Microwave spectroscopy, elements of, 267
of 1-iodopropane, 27 1
reference works for, 347
uses of, 270-27 1
Migration aptitudes of groups, 714
Miller, S., and prebiotic evolution, 1283
Mint, 1462
Mirror image isomers (see Chirality)
Mobius, A. F., strip of, 1001
Mobius orbital systems, and cycloadditions,
1000-1004, 1010-1014
and electrocyclic reactions, 1005-1014
energy levels of, 1000-1003
and sigmatropic rearrangements, 1006,
1010-1012
Models, ball-and-stick, 3
Mohr, E., strainless cyclohexane theory of,
464, 480
Molecular disorder, and entropy, 85-87
Molecular energy levels, electronic component of,
270, 287-293
rotational component of, 270-271, 275
vibrational component of, 270-286
Molecular formulas, conventions for, 3 1-34
determination of, 2, 3
three-dimensional representations of, 125- 130
Molecular geometry (see Bond angles, Bond
lengths, and specific compounds)
Molecular-orbital treatment, ab initio method and,
98 1-984
a parameter of, 964-965, 970-971
of benzene, 969-971
of benzene with bromine, 971
p parameter of, 964-965, 970-971
of 1,3-butadiene, 975-977
calculation of energy levels, 992-994, 1002
of cyclic ions, 996-998
of cyclic polyenes, 989-995
of 1,3,5-cyclohexatriene, 969-9
of electrocyclic rearrangements, 1005-1014
of electron-pair bonds, 96 1-963
and electronic spectra, 980-98 1
of ethene, 964-965
GVB method and, 983-984
of 1,3,5-hexatriene with bromine, 97 1
of hydrogen, 96 1-964
of pericyclic reactions, 999-10 17
of propenal, 977
of 2-propenyl cation, 979-980
of sigmatropic rearrangements, 1006,
1010-1012
stabilization energies (table), 985-986
Molozonides, as intermediates in ozonization
reactions, 433
Molybdenum hexafluoride, aryl side-chain
fluorides from, 1318
Monosaccharides, definition of, 902-903
Morphine, 1097
synthesis of, 1499- 1500
Mossbauer spectroscopy, elements of, 267
organoiron compounds and, 1359-1360
principles and uses of, 1359-1360
Moth hormones, 1469, 1473
Mutarotation, of L-glucose anomers, 9 17-9 18
Mylar, polyester film, 1433
Myleran, as carcinogen, 1164
Myoglobin, function, 1249- 1250, 1254- 1259
as oxygen carrier, 1254-1259
properties, 1250
structure of, 1254-1259
Myrcene, 1462-1464
NADH (see Nicotinamide adenine dinucleotide,
reduced form)
NADPH (see Nicotinamide adenine nucleotide
phosphate)
Name reactions, 1053
1-Naphthalenamine, from 1-naphthalenol,
1295-1296
2-Naphthalenamine, as carcinogen, 1162
from 2-naphthalenol, 1295-1296
Naphthalene, acylation of, 1070
from azulene, 1084
1,s-bis(bromomethy1)-, crystal structure of,
264-265
bromination of, 1070
from coal tar, 1080
cycloadditions to, 1077
1,s-dibromo-, space-filling model of, 37-38
electronic spectra of, 1033
energy transfer to, from
diphenylmethanone, 1377
hydrogenation of, 1073
inhibition of diphenylmethanone
photoreduction, 1383
negative radical ion of, esr spectra of, 1367
nitration of, 1043, 1070
phosphorescence of, 1377
physical properties of, 1027
quinones of, 1305-13 10
sodium in ethanol reduction of, 1073
stabilization energy of, 985
substitution reactions of (table), 1069- 1071
sulfonation, 1070
triplet state of, 1377
1,2-Naphthalenedione, as quinone, 1305
1,4-Naphthalenedione, blood coagulants from, 1310
as quinone, 1305
vitamin K activity of, 1310
2,6-Naphthalenedione, as quinone, 1306
I-Naphthalenol, with aryldiazonium salts, 1300
I-naphthalenamine from, 1295-1296
physical properties of, 1290
2-Naphthalenol, 2-naphthalenamine from,
1295-1296
physical properties of, 1290
Naphthalenols, from coal tar, 1081
Naphthols (see Naphthalenols)
Naphthylamines (see Naphthalenamines)
Natta, G., and polymer stereochemistry, 1430- 1435
Natural products, approaches to study of,
1461-1462
biosynthetic pathways for, 1461-1462
definition and classification of, 1460- 1461
structure determination of, 1461
and synthetic chemistry, 1461
Natural rubber, 507-508
biosynthesis of, 1485, 1488
vulcanization of, 1429- 1430
NBS (see N-Bromobutanimide)
Neopentane (see 2,2-Dimethylpropane)
Neopentyl derivatives, rearrangement of, in
solvolysis reactions, 250
solvolysis of, 250
steric hindrance in SN reactions of, 224-225
Neopentyl iodide, synthesis, 587
Neoprene, 506, 1433
Neral, 1465-1466
Nerol, 1465-1466
Neryl pyrophosphate, 1484- 1485
Neutron diffraction, 265
Newman projections, 125-126
Niacin, 1099
Nickel, 1,3-butadiene trimerization with, 1523
1,5-cyclooctadiene complex of, 1510
T-propenyl complexes of, preparation of, 1522
reactions of, 1522- 1524
structures of, 1522-1523
Nicotinamide adenine dinucleotide (oxidized form,
NADC), alcohol oxidation with, 644-647
Nicotinamide adenine dinucleotide (reduced form,
NADH), in carbohydrate metabolism,
945-952
Nicotinamide adenine dinucleotide phosphate
(oxidized form, NADPf), in photosynthesis,
940-941
Nicotinamide adenine dinucleotide phosphate
(reduced form, NADPH), in fatty acid
biosynthesis, 1481
in terpene biosynthesis, 1485
Nicotinic acid, 1099
Ninhydrin, 779
with amino acids, 1216-1218, 1221
Nitrate ion, and resonance, 176- 177
Nitration, of alkanes, 105
of arenes (see also Electrophilic aromatic
substitution), acyl nitrates in, 1043
alkyl substituted, 1042- 1043
ips0 mechanism for, 1066- 1068
mechanism of, 1041
nitric and sulfuric acids in, 1041-1042
nitronium salts in, 1041, 1044
orientation in, 1041- 1042, 1058- 1072
Nitrenes, in Curtius degradation, 1156
in Hofmann degradation, 1155- 1156
Nitric acid (see also Nitration)
cyclohexene oxidation with, 1043
in iodination of arenes, 1045-1046
in nitration of arenes, 1041-1043
oxidations of alkylarenes and alkyl aryl ketones
with, 1317
Nitriles, acidities of (table), 736-738
from aldehydes and ketones, 1185
aldehydes from, by hydride reduction, 7 19,
728, 824
alkylation of, 1185
amides from, 858, 1177-1178
from amides, 1185
amines from, by hydride reduction, 824-825
from arenediazonium salts, 1134, 1185
as carboxylic acid derivatives, 202, 819
carboxylic acids from, 854, 1185
dipole moments of, 1185
from halides, 1184- 1185
infrared spectra of, 1184
infrared stretching frequencies for, 276
IUPAC rules of nomenclature for, 202
ketones from, with Grignard reagents, 73 1
from oximes, 1185
preparation of, 1184- 1185
reactions of, 1185
reduction to aldehydes, 719, 728, 824
reduction to amines, 1146- 1147
Ritter reaction and, 1149, 1178-1 179
solvent properties of, 1184
unsaturated, in [4 21 cycloadditions (table),
493-494
Nitrilium ions, in Ritter reaction, 1178--1179
Nitro compounds, aci forms of, 1195-1 196
acidity of, 1195- 1196
aldol additions of, 1196
from aldol and Michael additions, 758, 1196
from alkanes, 1187
from alkyl halides, 1190- 1191
from arene nitration, 1039- 1044, 1058- 1072,
1187-1188
from arenes, 1187- 1190
charge-transfer complexes of, 1 192-1 193
diazene oxides from, 1194
dipole moments of, 1186
electronic spectra of, 1187
+
as explosives, 1191- 1192
as herbicides, 1195
infrared spectra of, 1187
Michael additions of, 1196
as polymerization inhibitors, 1449
reduction of, amines from, 1146- 1147,
1151, 1193
azanols from, 1194
nitroso compounds from, 1193- 1194
resonance and, 1186
by Sandmeyer reaction, 1191
thermochemistry of, 1191
unsaturated, in [4 21 cycloadditions (table),
493-494
volatility of, 1186-1 187
water solubility of, 1187
Nitroalkanes, acidities of (table), 736-738
aldol additions of, 758
preparation of, 105, 1187
Nitroanilines (see Nitrobenzenamines)
Nitroarenes, from arenediazonium salts, 1134
by nitration, 1041- 1044, 1059- 1060, 1065- 1071
2-Nitrobenzenamine, from
N-nitrobenzenamine, 1140
4-Nitrobenzenamine, base strength of, 1115
N-Nitrobenzenamine, rearrangement of, 1140
Nitrobenzenamines, base strengths of, 1115-1 116
Nitrobenzene, from benzene, 1041
electronic absorptions of, 1402- 1403
nmr spectrum of, 1036-1037
reduction of, azanols from, 1193-1 194
azo compounds from, 1194
azoxy compounds from, 1194
benzenamine from, 1193- 1194
diazanes from, 1194
hydrazines from, 1194
reagents for, 1193- 1194
as solvent, in arene acylations, 1052, 1070
Nitrobenzenecarboxylic acids, and Hammett
equation, 1329- 1330
4-Nitro- l,2-benzenedicarboxylic acid, 1317
4-Nitrobenzenol, acidity of, 1294
and anion, electronic absorptions of, 1402
electronic absorptions of, 1402- 1403
physical properties of, 1289
Nitrobenzenols, hydrogen bonding in, 1291-1292
nmr spectra of, 1291-1292
4-Nitrobiphenyl, as carcinogen, 1162
Nitroethane, 1187
from alkane nitrations, 105
Nitroethanoate esters, acidity of, 826
Nitrogen (see also Amines, Amides, Nitriles, etc.),
fixation of, by decamethylzirconocene, 1508
by titanocene, 1508
oxidation states of, 1141-1 142
Nitrogen bases, drugs from, 1098-1099
naturally occurring examples, 1097-1099
Nitrogen mustard, as carcinogen, 1164
Nitrogen ylides, 692-693
Nitromethane, aci form of, 1195
acidity of, 1195
aldol addition of, 1196
+
from alkane nitrations, 105, 1187
from nitroethanoic acid, 1191
physical properties of, 239
thermochemistry of, 1191
Nitronium ion, in arene nitration, 1041-1044
formation of, 1041
Nitronium salts, 1044
2-Nitropropane, aldol and Michael addition
reactions of, 1196
Nitropropanes, 1187
N-Nitrosamines, from alkanamines, 1129- 1131
Nitrosamines, rearrangement of, 1139
Nitrosation, of alkan- and benzenamines,
1129-1130, 1136
N-Nitrosazacyclohexane, as carcinogen, 1164
Nitroso compounds, azo compounds from, 1194
N-Nitrosoamides, diazomethane from, 1199
Nitrosobenzene, from
N-phenylhydroxylamine, 1194
N-Nitroso-N-methylbenzenamine, rearrangement
of, 1139
Nitrosyl chloride, additions to alkenes, 380
Nitrous acid, with alkanamines, 1129-1 131
amine reactions of, alcohols from, 1096
with amino acid esters, 1223
with amino acids, 1223
azides from, 1202
with diazanes, 1202
tertiary m i n e complexes with, 1130
Nitrous oxide, and resonance, 176- 177
Nitryl chloride, additions to alkenes, 380
Nmr spectra, of alcohols, 605
of aldehydes, 684
of alkenals and alkenones, 768
of alkenes, 353
of alkynes, 356-357
of amides, broad lines in, 1172- 1173
cis-trans isomerism and, 1172- 1173
nitrogen-15 in, 1175
proton exchange and, 1172
of amines, chemical shifts in, 1105
hydrogen exchange in, 1105-1 106
inversion effects on, 1110- 1111
of arenes, ring current effects on, 1034-1035
spin-spin splittings in, 1036- 1037
of carbon-13, characteristics of, 335-339
chemical shifts of, 335-336
and cyclohexane derivatives, 460
decoupling of protons and, 336-337
of D-glucose, 9 17-9 18
of lysozyme, 1286
sensitivity of detection of, 335
structural analysis with, 336-337
of warfarin, 336-337
of carbon-13 satellites in, 338
of [18]annulene, ring-current effect on, 1035
of carboxylic acids, 793-795
and chemical exchange, chemical-shift effects
from, 311-313
spin-spin splitting effects from, 321-322
chemical shift in, averaging by chemical
exchange, 3 11-3 13
averaging by conformational equilibration,
303-304, 456, 460-46 1, 1345-1347
and carbon bond types, 3 10-3 11
and chemical exchange of protons, 3 11-3 13
and chirality, 302-304
conventions for, 304-306
of cyclopropane protons, 448
diamagnetic effects in, 300-301
electronegativity effects on, 307-310
equivalence of atoms in, 300-304
exchange averaging of, 1345- 1346
general characteristics of, 300-3 15
and hydrogen bonding, 3 11
and infrared for structure determination,
3 13-3 14
magnetic field strength and, 304-306
pprn scale for, 306
proton values for (table), 306-3 11
reference standard for, 304
shielding parameters of, 300-301
Shoolery7srule for, 3 10
standard for, 304
stereochemistry and, 301-304
structure correlations for, 306-3 15
tetramethylsilane as reference, 304
units for, 304-306
chemically induced dynamic polarization and,
1353-1356
chiral-shift reagents and, 872-873
chiral solvents and, 871-872
CIDNP and, 1353-1356
conformational equilibration and, 303-304, 456,
460-461, 1345-1347
of cycloalkanes, 447-448
and decoupling, 322
diastereotopic atoms in, 303
of I, 1-difl9orocyclohexane, fluorine-19, 460
elements of, 267
enantiomeric purity and, 87 1-872
enantiotopic atoms in, 303
energies of transitions in, 299
of ethers, 656
exchange effects on, 1345-1346
field sweep in, 298-299
field-frequency relations for, 297-298
fluorine-19 of cyclohexane derivatives, 46 1
fluorine- 19 splittings in, 539
forbidden transitions in, 1352
frequency sweep in, 298-299
of Grignard reagent, 1524
and hydrogen bonding, 605, 793-795, 1291-1293
hydrogen bonding effects on, with carboxylic
acids, 793-795
instrumentation for, 295-296
integrals of peaks, 300, 322
of ketones, 684
lanthanide shift reagents and, 872-873
lifetime of states and, 1343-1346
line widths in, 1343-1344
magnetic energy levels in, 295, 297-299,
1349-1352
magnetic field effects on, 304-306
of methylcyclohexane, carbon- 13, 460
of nitrobenzenols, 1291-1292
nitrogen- 15, of N-methylmethanamide, 1175
nuclear spin and, 297
nuclei for, 295-296
paramagnetic ion effects on, 1344
peak areas in, 300
principles of, 295-299
proton chemical shifts of, 310
reference works for, 348, 1369
relaxation effects on, 1344
resonance frequencies, 297
ring-current effect on, 1034- 1035
in annulenes, 1035, 1088
ringing in, 298-299
and rotation about single bonds, 303-304,
1345- 1347
shift averaging in, 1345- 1346
shift reagents and, 872-873
spin quantum numbers for, 297-298
spin-spin splitting in, alkenes, 320, 325-326
of benzene protons, 1036- 1037
binomial coefficients and, 3 19
calculation of, 1348-1353
characteristics of, 3 16-322
chemical-shift effects on, 305, 317, 332-333
and conformations, 32 1-32 1
coupling constants for, 317, 319-321, 325-326
and decoupling, 322, 336
equivalent nuclei and, 3 16, 3 19, 332
ethyl groups, 3 16-3 18
first-order, 3 16
intensities of lines with, 3 18-3 19, 325-326
iodoethane, 3 16-3 18
line multiplicities in, 316-318, 325-326
long-range, 320
n + 1 rule for, 3 17-3 19
patterns of, 3 16-3 19, 325-327
proton structural variations of, 3 19-32 1,
325-327
saturated systems, 319-32 1
second-order, 3 16-3 17, 333
and structural analysis, 322-327
theory of, 1348- 1353
three-bond, 3 19-32 1
two-bond, 3 19-320
in structural analysis, 322-327
7 scale for, 306
and uncertainty principle, 1343- 1346
Nmr spectrum, of Zbromobutane, 328
of 3-bromopropene, 324
of I -buten-3-yne-4-D, 1353
carbon- 13, of D-glucose, 9 18
of lysozyme, 1286
of methylcyclohexane, 460
of polypropene, 1434
of warfarin and its sodium salts, 336-337
of cyclooctane, 447
temperature
of 3,3-dibromo-2,2-dimethylbutane,
effects on, 1347
of 1,I-dimethoxyethane, 3 19
of (2,2-dimethoxyethyl)benzene, 328
of ethanol, 295-296, 3 11-3 12
of ethyl 3-oxobutanoate, 827
of N-ethylethanamine, 1105
of ethynylbenzene, 357
of D-glucose, carbon-13, 9 17-9 18
iodoethane, 3 16
of methyl methoxyethanoate, 3 13-3 14
of 2-methyl-2-butanol, 305
of methylcyclohexane, carbon- 13, 447
of I-methylethyl ethanoate, 328
of 1-methylethenyl ethanoate, 328
of 1-(methylethenyl)benzene, 325-327
methylketene dimer, 774
of nitrobenzene, 1036
of nitrobenzenols, 1291- 1292
nitrogen- 15, of N-methylmethanamide, 1175
of octane, 334
of 2,4-pentanedione, 742
of 1-phenylethanamine, 873
of phenylethanoic acid, 795
of phenylnlethanol, 795
of propanal, 323
of propanamide, 1173
of 2-propenylmagnesium bromide, 1524
temperature effects
of 2,2,3,3-tetrachlorobutane,
on, 1345-1346
of 1,1,2-trimethylazacyclopropane, 1111
of 2,2,4-trimethylpentane, 334
of warfarin and its sodium salt (carbon-13),
336-337
Nomenclature (see also IUPAC rules)
philosphy of, 49-5 1
single- or multiple-word names in, 203-204
Nonane, heat of formation of, 86
Nonbonded interactions (see also Steric hindrance)
in methane chlorination, 89-90
between neon atoms, 89
potential energy of, 89
Nonpolar substances, definition of, 20
Norbornadiene, 1,3,5-cycloheptatriene from, 1314
iron tricarbonyl complex of, 1510
quadricyclene from, 503
synthesis of, 1314
thermal rearrangement of, 1314
Norbornene, 999
Nordel, 1432
Norrish, R. G. W., and type I and I1
photodissociations of ketones, 1379- 1380
Novocaine, 1098
Nuclear magnetic resonance spectra (see Nmr
spectra)
Nucleic acids (see also Deoxyribonucleic acids
and Ribonucleic acids), definition of, 927
Nucleophiles (see Nucleophilic reagents)
Nucleophilic displacement reactions, acid
catalysis of, 232-234
of alkenyl halides, 549-550
of alkyl halides, 539-541
of alkynyl halides, 549-550
of allylic halides, 544-546
of aril halides, activating substituents for,
552-555
by addition-elimination mechanisms, 552-555
benzenamines from, 552-553, 557-558, 1120
benzenols from, 554-555, 557-559
benzyne intermediates in, 558-559, 1120
elimination-addition path for, 557-559, 1120
mechanism of, 553-555, 1120
Meisenheimer complexes and, 555
rearrangements in, 558-559
by S,I and S,2 mechanisms, 552
crown ethers and, 666
of cycloalkyl halides, 550-55 1
of cyclopropyl halides, 55 1
of cyclopropylmethyl halides, 55 1
electrophilic catalysis of, 233-234
general characteristics of, 2 13-2 14
kinetics of, 215-2 17
leaving group reactivity and acid strengths,
232-233
leaving group selection for, 230-233
leaving groups, and reactivity in, 230-233
mechanisms of, 2 14-2 17
nucleophilicity, and base strength, 236
and solvation, 236
and structure, 235-237
of phenylmethyl halides, 546
on polyhaloalkanes, 563-564
radical mechanisms for, 572-573
reagents for, 207-2 11
references for, 252
reversibility of, 236-237
S, reactions, characteristics of, 215-218
S,I mechanism, amines with nitrous acid,
1130-1131, 1133
of haloalkanoic acids, 8 17
ion pairs in, 223
kinetics of, 2 15-2 17
leaving group structures and rates of,
230-233
in micelles, 804-805
of oxacyclopropane ring openings, 663-665
phenyl reactivity enhancement of, 228-229
racemization with, 897
reactivity of organic halides in, 226-230
rearrangements in, 250-25 1
silver-ion enhancement of, 234
solvent effects on, 237-238
stereochemistry of, 222-223
steric acceleration of, 229
steric hindrance effects on, 229
transition states for, 226-227
S,2 mechanism, and alkyl group structure,
224-225
amines and alkyl halides, 1125-1126
in competition with E2 elimination, 241
crown ether catalysis of, 666
electrophilic catalysis of, 232-234
with enamines, 764-765
of enolate anions, 761-763, 833-834
in Gabriel synthesis, 1127
of haloalkanoic acids, 815-8 16
kinetics of, 215-217
nitriles from, 1184- 1185
of oxacyclopropane ring openings, 663-665
and racemization, 896
reactivity of nucleophiles (table), 235-237
reactivity of organic halides in, 224-225
with solvent, 218
solvent effects on, 238
stereochemistry of, 219-221
and steric hindrance, 224-225
in sulfonamide syntheses of mines, 1127
with sulfur-stabilized carbanions, 765-766
transition metals and, 1516, 1520, 1526
solvent effects on, 236-239
solvent participation, kinetics of, 218
solvolysis, mechanisms for, 2 18
structural effects on, 224-234
thermochemistry of, 2 12-2 13
Nucleophilic reagents, definition of, 207-2 11
Nucleophilicity, and base strength, 210-2 11
and structure, 235-237
Nucleosides, structure of, 1274
Nucleotides, base-pairing of, 1274- 1275
definition of, 926-927
in DNA chains, 1274-1275
sequences of, in genetic code, 1276-1277
structure of, 1274
Nylon 6, 673, 1181, 1433, 1441
Nylon 66, 1181, 1433, 1441
hydrogen bonding in, 1426- 1427
properties of, 1433
0-alkylation, of enolate anions, 762-763
of phenols, solvent effect on, 1297-1298
Ocimene, 1464
Ocimum basilicum, oil of, 1464 .
T-Octadienylnickel, from 1,3-butadiene, 1523
cycloaddition reactions of, 1523- 1524
Octafluorocyclobutane, from dimerization of
tetrafiuoroethene, 502, 568
physical properties of, 569
Octane, heat of combustion of, 79
infrared spectrum of, 279
nrnr spectrum of, 334
cis-2-Octene, synthesis of, 5 18-522
Odors and stereoisomerism, 140- 141
Oil of wintergreen, 1327-1328
Olefins (see Alkenes)
Oleic acid, 789-790
Oligosaccharides, definition of, 927
properties and occurrences of, 907
Oppanol, 1432
Oppenauer oxidation, aldehydes from, with
alcohols, 727
ketones from, with alcohols, 730
Opsin, 1416-1417
optical activity (see also Chirality), discovery
of, 118
origin of, 862-864
and polarized light, 118- 120
rotation of polarized light in, 118-120
wavelength variation of rotations, 890-893
Optical antipodes (see Enantiomers)
Optical isomerism (see Chirality, Isomerism, and
Optical activity)
Optical rotation (see also Optical activity),
conventions for, 865-866
molecular, 866
specific, 865-866
wavelength variation of, 890-893
Optical rotatory dispersion, absolute configurations
from, 892-893
Cotton effect and, 890-893
definition of, 890-89 1
Oral contraceptives, 1479
Orange, oil of, 1464
Orbital hybridization, 159- 161
Orbital phase, 156
Orbitals (see Atomic orbitals or Molecular orbitals)
Organic chemistry, definition of 2 1-22
scope of, 21-22
uses of, 22
Organic photochemistry (see Photochemistry)
Organic syntheses, principles in planning of,
5 13-530
Organoboranes (see also Hydroboration), acid
cleavage of, 427, 429
alcohols from, 427-428
from alkenes and diborane, 420-424
alkyl- and dialkyl-, addition to alkenes and
alkynes, 422-424
preparation of, 420-423
stability of, 423
from alkynes and diborane, 422-423
h i n e s from, 427
azanyl hydrogen sulfate and, 427
hydrocarbons from, 427
isomerization of, 424-426, 523-524
oxidation of, alcohols from, 427-430
aldehydes from, 428-429
ketones from, 428-429
mechanism of, 429-430
stereospecificity of, 427-428
properties of, 420-421
rearrangements in reactions of, 430
in syntheses, 426-429, 521, 523-525
Organohalogen compounds, definition of, 535
general characteristics of, 535
insecticides of, 536-537
naturally occurring, 535-536
physical properties of (table), 538
spectroscopic properties of, 539
Organolithium compounds, 1,4-addition to
alkenones and alkenals, 585-586
alcohols from, 58 1-582
alkylcoppers from, 584
ketones from, with carboxylates, 583
with ketones, 581-582
thermochemistry of additions of, 578
Organomagnesium compounds, 1,4-addition to
alkenones and alkenals, 585-586
alcohols from (table), 577-581
with acyl halides and
anhydrides, 609
with aldehydes, 609
with esters, 609
with ketones, 609
with methanal, 577, 579, 608
with oxacyclopropanes, 609
aldehydes from, with N,Ndimethylmethanamide, 729
with triethoxymethane, 729
with aldehydes, 577-580
table, 577-579
alkylcadmiums from, 584
with alkynes, 578
with arnides (table), 579
with carbon dioxide (table), 579, 583
carboxylic acids from (table), 579, 583
dialkylmagnesium compounds, 576
enolizations with, 582
ether complexes of, 577
ferric chloride coupling with, 1505
with halogens, 586-587
hydrolysis of products of, 580
ketones from, with nitriles, 731
with oxacyclopropanes, 578
with oxygen, 586-587
preparation of, with aryl halides, 576
coupling in, 572
from 1,6dihalides, 575
with ethenyl halides, 572
Grignard procedure, 576
with 3-halopropenes, 572
solvents for, 571-572
reduction of carbonyls with, 582
side reactions in additions of, 582
structure and equilibria of, 577
with sulfur, 586-587
Organometallic compounds, 1,4-addition to
alkenones and alkenals, 585-586
carbenes from (table), 566, 575-576
general characteristics of, 570
ionic character of C-M bonds of, 571-572
preparation of, from acidic hydrocarbons, 574
by halogen-metal exchange, 573-574
by metal exchange, 574
metals with halides, 57 1-573
from polyhalogen compounds, 575
procedures for (table), 590
radical mechanisms in, 572-573
solvents for, 571-572
reactivity of, 570-57 1
thermochemistry of additions of, 578
of transition metals, alkene complexes,
1509-1510, 1521-1524
with alkyl-metal bonds, 1510- 1516, 1520,
1525-1526
carbene complexes, 1512, 1521
sandwich type, 1505-1508
vitamin B,, as, 1525-1527
Organonilrogen compounds, types of
(summary), 1184
Organopotassium compounds, reactivity of,
570-57 1
Organosodium compounds, reactivity of,
570-57 1
Orientation in aromatic substitution, 1059-1072,
1187-1 190
Orlon, 1427, 1433
Orsellinic acid, 1480
ortho, definition of, 63
Ortho-para directing groups (tables), 1060- 1064
Osmium tetroxide, alkene additions of, 434
Osmium tetroxide-sodium periodate, ketones
from, with alkenes, 730
Overlap, of atomic orbitals, 155- 161
Oxacycloalkanes, nomenclature systems for,
659-66 1
Oxacyclobutane (trimethylene oxide, oxetane),
reactions of, 661
Oxacyclobutanes, from photochemical
cycloadditions, 1389- 1390
Oxa-2-cyclobutanone, as carcinogen, 1164
Oxa-2-cyclohexene, protecting group for OH
with, 653
Oxacyclopentane (tetrahydrofuran, THF, oxolane),
physical properties of, 654
as solvent, 661
for organometallic preparations, 572
Oxacyclopropane (ethylene oxide, oxirane), from
ethene oxidation, 42, 437
hydrolysis to 1,2-ethanediol, 437
industrial uses of, 66 1-662
physical properties of, 654
polymerization of, 1423
reactions of, 66 1-662
Oxacyclopropanes, alcohols from, with Grignard
reagents, 609
by hydride reduction, 6 10
from alkene oxidations, 435-437
with Grignard reagents, 578
hydrolysis of, 435-437
preparation of, 662-663
ring-opening reactions of, 663-665
from ylide reactions of ketones, 692-693
Oxalic acid (see Ethanedioic acid)
Oxaloacetic acid (see 2-Oxobutanoic acid)
Oxalyl chloride (see Ethanedioyl dichloride)
Oxalyl derivatives (see Ethanedioyl derivatives)
3-Oxa- 1,5-pentanediol, 662
Oxazacyclopropanes, inversion rates of, 1110
Oxazine dyes, 1406
Oxidation (see also individual oxidizing agents, as
Ozone, etc.), of arenes, with oxygen,
1077- 1078
of arenes, with ozone, 1078-1079
balancing equations of, 406-409
definition of, 42-43, 405-409
Oxidation states, of carbon (table), 405-409
of nitrogen, 1141-1 142
Oxidative phosphorylation, in alcohol
oxidations, 646
Oximes, from aldehydes and ketones, 698
amides from, 1180- 1181
Beckmann rearrangement of, 1149, 1153,
1180-1181
E,Z convention for, 887, 1181
nitriles from, 1185
reduction to amines, 1146, 1148
stereoisomerism of, 1131
sulfonate esters of, 1180
syn and anti isomers of, 1181
Oxiranes (see also Oxacyclopropanes), 660
0x0 reactions (see also Hydroformylation),
722-723
2-Oxoalkanoate esters, decarbonylation of, 832
3-Oxoalkanoate esters, acidities of (table), 736-738
from 2,4-dioxoalkanoate esters, 832
ketones from, by hydrolytic cleavage, 730
3-Oxoalkanoic acids, in alkanoic acid metabolism,
837-840
2-Oxobutanedioic acid (oxaloacetic acid), in citric
acid cycle, 951-954
from 2-hydroxybutanedioic acid, NAD+
and, 645
in terpene biosynthesis, 1482- 1488
3-Oxobutanedioyl coenzyme A, in terpene
biosynthesis, 1482, 1488
3-Oxobutanoate esters, acidity of, 826
acylation of, 835
alkylation of, 833-834
carboxylic acids from, 834
from diketene, 773
from 2,4-dioxoalkanoate esters, 832
enol-keto interconversion of, 827-828
enolization of, 826-828
ketones from, 834
Michael addition of, 844
nmr spectrum of, 827
separation of forms of, 828
2-Oxobutanoic acid, citric acid from, 840
enzymatic decarboxylation of, 1285
3-Oxobutanoic acid, decarboxylation of, 812, 834
Oxonium salts, of alcohols and ethers, 613-614,
656-657
2-Oxopentanedioic acid, in citric acid cycle,
95 1-954
2-Oxopropanoic acid, decarboxylation of, thiamine
pyrophosphate and, 1267-1269
en01 phosphate of, as phosphorylating agent, 649
in gluconeogenesis, 955-956
in glycolysis, 946, 949-950
from 2-hydroxypropanoic acid, with NAD+, 645
Oxygen, with alcohols, 639
copolymer with ethenylbenzene, 1453
coupling into metabolic processes, 1308-1309
as diradical, 1391
electronic configuration of, 1391
with Grignard reagents, 586-587
as radical-chain inhibitor, 95
role in carbohydrate metabolism, 944-945
singlet state of, with biological systems, 1393
chemical generation of, 1392- 1393
chemistry of, 1391-1393
electronic configuration of, 1391
photochemical generation of, 1391-1392
with triphenylmethyl radicals, 1323
Oxygen carriers, hemoglobin as, 1258-1259
myoglobin as, 1255-1259
synthetic, 1258
Oxytocin, structure and synthesis, 1242-1244
Ozone, alkene reactions of, 43 1-433
destruction in atmosphere by
chlorofluorocarbons, 537
electronic structure of, 433
with triethyl phosphite, 1393
Ozonides, formation of, 43 1-433
methanol reaction of, 432
reduction of, 43 1-432
Ozonization, aldehydes from, 727
of arenes, 1078- 1079
ketones from, with alkenes, 730
mechanism of, 432-433
procedures for, 43 1-432
Palmitic acid, 789-790
Pantothenic acid, structure, 1211
Paper chromatography, for amino acids, 1218- 1219
para, definition of, 63
Para Red, 1407
Paradigm of transition-metal compound
stabilities, 1504
Paradigms, of organic chemistry, 3
Paraffin hydrocarbons (see Alkanes)
Paraformaldehyde, 696
Paraldehyde, 696
Partial rate factors (see Electrophilic aromatic
substitution)
Pasteur, L., and resolution of tartaric acid, 118
Paterno, E., 3, 8
Pauli, W., and exclusion principle, 153- 155
Pauli principle, bonding in hydrogen and, 961
Pauling, L., and alpha helix, 1251
electronegativity chart, 377
and x-ray diffraction structure
determinations, 1249
Pectins, 937
Pederson, C. J., and metal complexes of cyclic
polyethers, 666
Penicillins, biochemical action of, 1490
biosynthesis of, 1492
enzymatic degradation of, 1490
structure and function of, 1491
synthesis of, 1492
1,3-Pentadiene, heat of hydrogenation of, 4 15
stabilization energy of, 986
1,4-Pentadiene, heat of hydrogenation of, 415
Pentaerythritol, 754
polyesters from, 1440
Pentalene, 1086- 1087
bis-nickel derivative of, 1508
Pentanedioic acid, properties and uses of, 847
2,4-Pentanedione, acidities of (table), 736-738
alkylation of, 763
beryllium salt of, 777
copper salt of, 777
with diazomethane, 1199
enolization of, 740-742, 776-777
physical properties of, 679
salts with metals, 777
2-Pentanone, photochemistry of, cyclobutanols
from, 1381
dissociation in, 1380
cis-2-Pentene, heat of hydrogenation of, 415
trans-2-Pentene, heat of hydrogenation of, 415
Pentoses, structures and configurations of,
904-907
Pentyl alcohol (see 1-Pentanol)
Peppermint, oil of, 1466
Pepsin, precursor of, 1269
Peptides, abbreviations for, 1228-1229
alpha helix of, 1251-1252
a i d e groups in, 1227-1228
amino-acid backbone, 1227-1229
amino-acid compositions of, 1229
amino-acid sequences, determination of,
1229-1234
C-terminus of, 1228
carboxypeptidase hydrolysis of, 1231
chymotrypsin hydrolysis of, 1233
conventions for, 1228
with dansyl chloride, 1230
denaturation and, 1228
Edman degradation of, 1230- 1231
formation of, in prebiotic evolution, 1284
helical structures of, 1251-1252
hydration of, 1228
hydrolysis of, 1229
N-terminus of, 1228
peptide bond of, 1227
primary and secondary structure of, 1228
separation from proteins, 1248
structure of, 1227-1229
synthesis of, coupling reagents for, 1240-1247
Merrifield procedure for, 1242-1247
procedures for (table), 1236-1247
protecting groups in (table), 1236-1247
racemization problems in, 1238- 1240
solid-phase supports for, 1242-1247
yield problems in, 1236, 1238-1240
tertiary structure of, 1228
thiohydantoins from, 1230-123 1
trypsin hydrolysis of, 1232-1233
Perfluorocarbons, preparation of, 99
Performic acid (see Peroxymethanoic acid)
Perfume ingredients, 1328
Pericyclic reactions, Claisen ally1 ether
rearrangement and, 1298
cycloadditions and, 999-1005, 1010- 1017
definition of, 419, 498
electrocyclic type, 1005- 1014
and Hiickel rule, 999-1017
rules for prediction of, 1010- 1012
sigmatropic type, 1006, 1010
of singlet oxygen, 1391-1392
Periodate, oxidation of 1,2-alkanediolswith, 717
Perkin, W. H., and founding of dye industry,
1405-1406
Perlon, 1433
Permanganate, aldehyde oxidation, 7 12
1,2-alkanediols from, with alkenes, 643
1,3,5-cycloheptatriene to tropolone, 1314
hydroxylation of alkenes, 434
mechanism of oxidation with, 643
methylbenzene to benzenecarboxylic acid, 1317
for nitro compounds from amines, 1144
oxidation of alcohols with, 643
Peroxidation of alkenes, diols from, 434-436
mechanism of, 436
Peroxide effect, in hydrogen bromide addition to
alkenes, 386-389
Peroxides, from arenoxy radical dimerizations, 1302
ascaridole as, 1466
and chemiluminescence, 1395- 1399
chlorination induced by, 102- 103
decomposition of, 102- 103
from ethers, 658-659
polymeric from ethenylbenzene, 1453
in prostaglandin biosynthesis, 1494
from semiquinone dimerization, 1307
Peroxybenzenecarboxylic acid, 713
with alkenes, 435-436
Peroxycarboxylic acids, in additions to alkenes, 380
alkene additions of, 435-436
oxidation of amines with, 1143-1144
Peroxymethanoic acid, with alkenes, 435-436
Peroxytrifluoroethanoic acid, with alkenes, 436
Perutz, M., and x-ray diffraction structure
determinations, 1249
Pesticides, aryl halides for, 561
PETN, 754
Petroleum, arenes from, 1079-1083
chemicals from, 1079-1083
composition of, 74
gases from, 74
refining of, 74
source and uses of, 74-75
pH, definition and equations for, 209
Phenacetin, 1328
Phenanthrene, bromination of, 1071- 1072
from coal tar, 1080
nitration of, 1071
oxidation of, with ozone, 1079
from photolysis of 1,2-diphenylethene, 1387
physical properties of, 1027
reduction of, 1074
stabilization energy of, 985
sulfonation of, 1071
Phenobarbital, 1098
Phenol (see Benzenol and Phenols)
Phenolphthalein, 1405
Phenols, acidities of (table), 736-738, 1289-1290,
1293-1294, 1334
aldehydes from, 1299
aldol-type reactions of, 1300
arenamines from, 1295- 1296
from arenamines, 1293
from aryl halides, 557-559
with aryldiazonium salts, 1300
bromination of, 1296- 1297
Bucherer reaction and, 1295-1296
C-alkylation of, 1297-1298
from coal tar, 1291
with dichlorocarbene, 1299
electronic spectra of (table), 1288-1290
as enols, 65 1, 1288
esters from, 1294
ethers of, cleavage of, 1295
preparation, 1294, 1297-1298
ferric chloride complexes of, 1294- 1295
haloarenes from, 1295
Hammett reactivity and acidity correlations
with, 1334
hydrogenation of, 1300
infrared stretching frequencies for, 277
IUPAC rules of nomenclature for, 191
Kolbe-Schmitt reaction of, 1298-1299
0-alkylation of, 1297-1298
oxidative coupling of, 1301-1302
physical properties of (table), 1288- 1291
radicals in oxidation of, 1301-1302
resonance in, 1288
salts of, with alkyl halides, 1294
C-alkylation of, 1297- 1300
0-alkylation of, 1297-1300
with 2-propenyl halides, 1297-1298
with trichloromethane, 1299
Phenyl cations, from benzenediazonium salts, 1133,
1135-1 136
Phenyl esters, amides from, 1177-1178
Phenyl isothiocyanate, in Edman degradation of
peptides, 1230- 1231
Phenylacetic acid (see Phenylethanoic acid)
Phenylalanine, anticodon of, 1282
properties of, 1210
synthesis of, 1226
Phenylamine (see Benzenanline)
N-Phenylazanol, azo compounds from, 1194
from nitrobenzene, 1 194
rear-rangelnent of, 1140
1-Phenylbutanone, photochemistry of, 1381
Phenylcyclobute~ledione,synthesis and
derivatives of, 1313
Phenyldiazane, synthesis and reactions of, 924,
1138, 1140
Phenylethanenitrile, from chloromethylbenzene, 1318
Phenylethanoic acid, nmr spectrum of, 795
Phenylethanoic acids, Hammett acidity correlations
with, 1334
Phenylethanone, from acyclation of benzene, 1052
physical properties of, 679
9-Phenylfluorene, acid strength of, 1322
Phenylglycine, synthesis of, 1225
Phenylhydrazine, with u-glucose, 924
synthesis and rearrangement of, 1138, 1140
N-Phenylhydroxylamine, from nitrobenzene, 1194
reactions of, 1140, 1194
Phenylmagnesium bromide, ferric chloride
coupling of, 1505
Phenylmercuric ethanoate, from mercuration of
benzene, 1058
Phenylmethanol, from chloromethylbenzene, 1318
nmr spectrum of, 795
Phenylmethoxycarbonyl protecting groups, in
peptide syntheses, 1237-1247
Phenylmethyl cations, ease of formation of, 1320
Phenylmethyl chloride (see Chloromethylbenzene)
Phenylmethyl halides, preparation of (table),
546-547, 587-588, 1046, 1054
reactions of, 546
reactivity in SN2reactions, 225
reactivity of (table), 589
S,I reactivity of, 228-229
Pheromones, insect, isomerism and activity of, 141
reference works for, 142
Phillips catalyst for alkene polymerization, 396
Phloroglucinol (see 1,3,5-Benzenetriol)
Phosphate esters, adenosine and, 635-637
biochemical derivatives of, 635-637, 1483-1485
DNA and, 1273
formation of, 634-635, 940-956
hydrolysis of, 635-637
nucleotides as, 926-927
Phosphine, bond angles of, 172
Phosphines, radical-chain addition to alkenes
and alkynes, 389
Phosphoenolpyruvate, in glycolysis, 949
Phosphoglycerides, 790, 805
Phospholipids, 790, 805
Phosphorescence, of benzene, 1375
definition of, 1375
of naphthalene, 1377
Phosphoric acid, esters of, formation and reactions
of, 634-637, 940-956, 1483-1485
Phosphorus halides, alkyl halides from alcohols
and, 626-627
Phosphorus pentachloride, in acyl chloride
formation, 809
with ketones, 704
Phosphorus trichloride, in acyl chloride
formation, 809
Photochemical initiation of polymerization, 1447
Photochemistry, alkene isomerizations by,
1384-1386
of biological systems, 1371, 1393-1394
chemiexcitation, 1395-1399
chlorination of alkanes, 91-95
of chlorofluorocarbons in atmosphere, 537
CIDNP effects in, 1353-1356
of color photographic processes, 1410-1415
cyclizations in, of dienes, 1387
of 1,2-diphenylethene, 1387
cycloadditions in, alkenes with ketones,
1389-1390
of DNA and RNA, 1394
electrocyclic reactions of, 1013- 1014
1,3-dienes to cyclobutenes, 1387
1,2-diphenylethene to phenanthrene, 1387
stereochemistry of, 1387- 1388
energy transfer in, characteristics of, 1374,
1376-1377
diphenylmethanone to naphthalene, 1376-1377
of ethene-carbon monoxide polymers, 1453
excitation of carbonyl group, 1375-1376
Franck-Condon principle and, 1372
of ketones, CIDNP effects in, 1353-1356
Norrish type I, 1379-1381
Norrish type 11, 1380-1381
of methanal, excited states of, 1375-1376
and nmr CIDNP effects, 1353-1356
photodissociation in, mechanism of, 1373-1374
of 2-propanone, 1379-1380
quantum yields in, 95
photodissociation processes, 1379
reduction by, benzopinacol from, 1382- 1383
of diphenylmethanone, 1382- 1383
mechanism of, 1382-1383
singlet states in, of benzene, 1375
energy transfer from, 1374
Franck-Condon principle in formation of,
1372-1374
intersystem crossing and, 1374-1375
lifetimes of, 1374-1375
of methanal, 1375-1376
potential-energy curves for, 1373
as primary product of electronic excitation,
1372-1373
triplet states from, 1374-1375
vibrational relaxation of, 1374
triplet states in, of benzene, 1375
electronic configuration of, 1373-1374
Hund's rule and stability of, 1373
lifetimes of, 1375
of methanal, 1375-1376
phosphorescence from, 1375
potential-energy curves for, 1373
from singlet states by intersystem crossing,
1373-1375
uses of, 1371
vision and, 1416-1417
Photodissociation, of ketones, 1379-138 1
mechanism of, 1374
Norrish types I and 11, 1379-1381
Photoelectron spectroscopy, elements of, 267
of hydrocarbons, 1357- 1358
principles and uses of, 1356-1357
Photoelectron spectrum, of benzene, 1357
of ethene, 1357
of ethyne, 1357
Photographic developers, chemistry of, black and
white, 1310-131 1
chemistry of, color, 1411-1414
Photosensitization, "and energy transfer, 1377
ketones for, 1385-1386
in photographic films, 1411-1412
singlet oxygen from, 1392
Photostationary states, 1386
Photosynthesis, Calvin cycle, 94 1-943
carbohydrates from, 939-943
character of, 939-943
chlorophyll in, 939-94 1
esr spectra during, 1368
path of carbon in, 941-943
phosphorylation in, 94 1-943
Phthalic acid (see 1,2-Benzenedicarboxylic acid)
Phthalic acids (see respective benzenedicarboxylic
acids)
Phthalic anhydride (see 1,2-Benzenedicarboxylic
anhydride)
Phthalimide (see 1,2-Benzenedicarboximide)
Phthdimidomalonic ester synthesis of amino
acids, 1226
Phthalocyanines, 1408
Phytol, as diterpene, 1468- 1469
occurrence of, 1468- I469
Pi (7~)bonds, of ethene, molecular-orbital
treatment of, 964-965
valence-bond treatment of, 965-966
formulation of, 165- 167
Pi (7~)complexes (see also Charge-transfer
complexes), from alkenes and halogens, 367
in arene halogenation, 1044- 1045
of nitro compounds, 1192- 1193
of transition metals with alkenes, 1509-1510,
1517-1519, 1523
Pi (n) electron rules (see Hiickel rules)
Picolines, from coal tar, 1080
Picrates, 1192
Picric acid, 1192
physical properties of, 1289
Pigments, copper phthalocyanine as, 1408
uses of, 1408
Pinacol (see 2,3-Dimethyl-2,3-butanediol)
Pinacol-pinacolone rearrangement, 720
Pinacolone (see 3,3-Dimethyl-2-butanone)
Pinene, 1464
Piperidine (see Azacyclohexane)
Piperonal, 1328
Planck's constant, definition of, 269
and uncertainty principle, 1343
Plant gums, 937
Plasticizers, for polychloroethene, 1435
Plastoquinone, 1309
Platinum, alkene complexes of, 1509- 1510
cyclohexyne complex of, 1510
Pleated sheets, protein conformations as,
1252-1253
Plexiglas, 1433
Poison ivy, 1304
Polarized light, circularly, 864
origin of optical activity and, 862-864
plane, 862-864
Polaroid color-print process, 1414- 1415
Polycarbonate resins, 1439
Polychloroethene, physical properties and uses of,
391, 1430, 1432, 1435
Polycycloalkanes, IUPAC rules of nomenclature
of, 476479
physical and chemical properties of (table), 482-484
propellane types of, 483-484
Polyenes, nomenclature for, 60-6 1
as visual pigments, 1416-1417
Polyesters, synthesis of, 1438-1440
Polyethene, characteristics of, 1425-1426, 1430,
1432, 1434-1435
formation and uses of, 395-397
Polyethenylbenzene, physical properties of,
1430, 1433
Polyethers (see also Ethers), cyclic, metal
complexes of, 665-666
Polyfluoroethene, physical properties of, 568,
1430, 1432
Polyfunctionality, characteristics of, 488, 788
Polyhaloalkanes, reactions with metals, 575
uses of, 562-563
Polyhydric alcohols (see Alkanediols,
Alkanepolyols)
Polyisobutylene, formation and uses of, 393-395
Polyketides, 1481- 1482
Polymerization (see also Copolymers and
Polymers), addition, of
1,3-cyclopentadiene, 1420
of 1,3-alkadienes, by 1,2 addition vs. 1,4
addition, 504
atactic vs. isotactic polymers from, 505
commercial products from, 504-508
monomers for (table), 504-508
alkene monomers for (table), 391
of alkenes, 390-397
anionic mechanism for, 392-393
cationic mechanism for, 393-395
chain transfer in, 1449
condensation, Bakelites from, 1442- 1443
epoxy resins from, 1444-1445'
of 1,2-ethanediol, 1423
melamine resins from, 1443-1444
polyamides from, 1441
polyesters by, 1438-1440
reactions for, 1438
urea-methanal resins from, 1443-1444
copolymers of ethene and propene, 396, 1435
degree of, 1420
fiberglass by, 1440
growing chain in, 1420
inhibitors, 1449
initiators, 1447
"living" mechanism, 1451- 1452
of methanal, 696
radical mechanism of, catalysts for, 395, 1447
chain transfer in, 1449
direction of addition in, 1447- 1448
inhibitors for, 1449
initiation of, 395, 1447- 1448
termination of, 396, 1447- 1449
Polymers (see also Copolymers, and individual
polymers), addition, of alkenes, 1446- 1453
atactic, 504-505, 1430-1435
by anionic mechanism, 392-393, 1452-1453
by cationic mechanism, 393-395, 1451
copolymers from, 1452- 1453
by radical mechanism, 375-376, 1446-1449
by Ziegler mechanism, 396-397, 1446
from 1,3-alkadienes, uses of, 505-508
vulcanization of, 505
amorphous, properties of, 1427- 1435
backbone of, 1420
bifunctional, 1452
block, ester-ether type, 1454
polyurethanes as, 1454-1455
by Szwarc procedure, 1452
from chloroethene, 548-549
cold drawing of, 1428, 1435
cross-links in, effects of, 1422-1423, 1428-1430,
1435, 1439-1440, 1443-1445, 1457
crystallites in, 1425-1435
decomposition temperatures of, 1427, 1456- 1457
definition of, 1419
of 1,l-difluoroethene and hexafluoropropene
(Viton), 568
elastomeric, characteristics of, 1422, 1428-1429
cross-links in, 1428-1430, 1435
of ethene and propene, 1435
plastic flow in, 1428-1429
vulcanization of, 505, 1429- 1430, 1435
emulsion, 1447
end groups on, 1420, 1448-1449, 1452
fiber formation, 1427-1428, 1435
fiberglass, 1440
flexibility of chains in, 1427- 1429, 1435, 1456
gel, 1422
glass temperatures of (table), 1427-1435
graft, preparation of, 1455
high-temperature, 1456-1457
hydrogen bonding in, 1426- 1427
importance of, 1419
isotactic; 504-505, 1430- 1435
ladder, arenecarboxarnides as, 1457
polyimides as, 1456
quinoxalines as, 1456
melting points of (table), 1427-1435
of methanal, 696
molecular weights, number average, 1420- 1421
weight average, 1421
oriented and unoriented, 1428, 1435
photodegradable, 1453
photoinitiation of, 1447
hhysical properties of (table), 1422- 1423,
1425- 1435
plastic flow in, 1422
polyaldehyde type, 696
polyethene, crystallites in, 1425-1426
properties of, 396, 1425-1426, 1430, 1432,
1434-1432, 1434-1435
polypropene, 396, 1430-1435
preparation of (see Polymerization)
PVC plastics, 549, 1430, 1432, 1435
solvent swelling by, 1422
stereoisomerism of, 504-505, 1430- 1435
structural elements of, 1419-1420
syndiotactic, 1430-1435
of tetrafluoroethene (Teflon), 568, 1430-1432
thermoplastic, characteristics of, 1422,
1425-1429
thermosetting, characteristics of, 1422- 1423
types of, 1421-1423
uses of (table), 1432-1433
van der Waals forces and, 1422, 1426-1429
Polymethanal, properties of, 696, 1430, 1433
Polynuclear arenes, oxidation of, 1078- 1079
Polynuclear aromatic hydrocarbons (see also
Polynuclear arenes)
angular and linear, 1025
IUPAC rules of nomenclature for, 1025--1026
reduction of, 1073-1074
ring index for (reference), 1026
Polynucleotides, definition of, 927
Polyols, urethane foams from, 1455
Polyoxymethylene, 696
Polypropene, atactic, 1430- 1435
carbon-13 nmr spectrum of, 1434
isotactic, 1430- 1435
physical properties, 396, 1430-1435
stereoisonlers of, 1430-1435
syndiotactic, 1431, 1434
Polypropenenitrile, properties of, 1427, 1433
spinning of, 1427
Polypropylene (see Polypropene)
Polysaccharides (see also Cellulose, Starch, etc.)
definition of, 927
properties and occurrence of, 908
Polystyrene, 1430, 1434
Polytetrafluoroethene, physical properties of,
568, 1430-1432
Polyurethane foams, 1454- 1455
Polyvinyl alcohol, polymers of, 1433
Polyvinyl chloride (see Polychloroethene)
Polyvinyl derivatives (see Polyethenyl derivatives)
Polyvinyl fluoride, physical properties of,
1430, 1432
Polyvinylbutyral, safety-glass laminates of, 1433
Porphin, 1257
Porphyrins, vitamin B,, and, 1490
Porter, G., and photochemistry, 1380
Position isomers, 44-46
Potassium tert-butoxide, elimination reactions
with, 615
Potassium permanganate (see Permanganate)
Potassium phthalimide (see Gabriel synthesis)
Potential-energy curve, for hydrogen molecule,
960-96 1
Prebiotic evolution, 1282- 1284
Primaquine, 1098
Primary structures, of peptides, 1228
Principle of least structural change, 13
Prismane, physical and chemical properties of, 482
Procarboxypeptidase, 1269
Prochiral center, 889
Prochirality, in biochemical transformations,
888-889
definition of, 888
Progesterone, structure and occurrence of, 1472
microbial oxidation of, 1478
Projection formulas (see Chirality)
Proline, and alpha helix, 1252
in collagen, 1458
with ninhydrin, 1217
properties of, 1210
Proof of structure (see Structure determination)
1,2-Propadiene (allene), atomic-orbital mode1
of, 408-509
1, [2 + 21 cycloadditions, 1002, 1017
dimerization of, 502
heat of hydrogenation of, 415
hydration of, 512
isomerization of, 5 12-5 13
Propanal, mass spectrum of, 340-341
nmr spectrum of, 323
physical properties of, 679
Propane, from di-v-propenylnickel, 1522
nitration of, 105, 1187
Propanedioate esters, acidity of, 826
acylation of, 835
alkylation of, 833-834
amino acids from, 1225-1226
1,2-benzenedicarboximido derivative of,
amino-acid syntheses and, 1224
carboxylic acids from, 834
N-formamido derivative of, amino-acid
syntheses and, 1224
methanamido derivative of, amino-acid
syntheses and, 1224
Michael additions of, 844
from 2-oxobutanedioate esters, 832
phthalimido derivative, amino-acid syntheses
and, 1224
Propanedioic acid, decarboxylation of, 847
properties and uses of, 847
1,2-Propanediol, in fiberglass, 1440
polyesters from, 1440
Propanedioyl ACP, 1481
Propanenitrile, synthesis of, 1185
1,2,3-Propanetriol (glycerol), from fats, 790
manufacture of, 542
physical properties of, 239
polyesters from, 1439- 1440
properties of, 648
uses of, 648
1,2,3-Propanetriyl trinitrate, as explosive, 648
Propanoic acid, physical properties of, 792
1-Propanol, physical properties of, 601
2-Propanol, acidic properties of, 613
chromic acid oxidation of, 640-641
from hydration of propene, 361
industrial preparation of, 607
in photoreduction of diphenylmethanone,
1382-1383
2-Propanone, acidities of (table), 736-738
aldol additions of, 752-753
to benzenecarbaldehyde, 756
to methanal, 753
aldol product of, dehydration of, 756-757
preparation of, 752-753
from chromic acid oxidation of 2-propanol,
640-64 1
from 1,2-dioxacyclobutane,triplet state of,
1395-1397
electronic absorption, 287-289, 795
from ethanoic acid, 49-50
halogenation of, base and acid catalyzed, 742-745
from hydration of propyne, 383-384
from hydroperoxide rearrangement, 72 1-722
infrared spectrum of, 273
from isopropylbenzene, 1293
ketene from, 77 1-772
keto-en01 equilibrium of, 736-740
mass spectrum of, 340-341
oxime of, rearrangement of, 1180
photochemistry of, 1379-1380
from photoreduction of
diphenylmethanone, 1383
physical properties of, 679
from 1,2-propadiene, 512
as solvent, 238
Propellanes, physical and chemical properties of
(table), 482-484
Propenal, molecular-orbital treatment of, 978
physical properties of, 679
valence-bond treatment of, 974-975
Propene, alkene metathesis of, 1520- 1521
allylic bromination of, with N-bromobutanimide,
542-543
allylic chlorination of, 543
bond-dissociation energies of, and resonance,
177-178
bromine substitution of, with
N-bromobutanimide, 104, 542-543
chlorine substitution on, 178, 543
copolymer with ethene, 396, 1435
electronic absorptions of, 289
ethene and butene from, 1520-1521
heat of hydrogenation of, 415
hydration of, 361, 383-384
polymerization of, 390-391, 396, 1446
polymers and copolymers of (see also
Polypropene), properties of, 39 1, 396,
1432, 1435
radical-chain addition of HBr to, 385-389
radical-chain polymerization of, 396
Propenenitrile, anionic polymerization of, 1451
copolymer with 1,3-butadiene, 506
coupling with arenediazonium salts, 1136
in glutamic acid synthesis, 1226
Michael addition to, 1226
polymers from, 391
2-Propenyl cation, molecular-orbital treatment of,
979-980
valence-bond treatment of, 978-979
2-Propenyl halides, with benzenolate anions,
1297-1298
preparation of (table), 541-544, 587-588
reactions of, 544-546
reactivity in SN2 reactions, 225
reactivity of (table), 589
SN1reactivity of, 228-229
2 - ~ r o ~ e n ~ l m a ~ n e sbromide,
ium
nmr spectrum
of, 1524
Propenylnickel complexes, chemistry of, 1525- 1524
as (T) complexes, 1521-1524
2-Propenyloxybenzene, preparation and
rearrangement of, 1298
Propiolactone, as carcinogen, 1164
Propionaldehyde (see Propanal)
Propionic acid (see Propanoic acid)
Propylbenzene, from acylation and reduction of
benzene, 1053
physical properties of, 1027
Propylene (see Propene)
Propylene oxide (see Methyloxacyclopropane)
Propyne, heat of hydrogenation of, 415
radical-chain addition of HBr to, 390
Prostaglandins, biosynthesis of, 1493- 1494
structure and function of, 1492-1493
synthesis of, 1493-1494, 1502-1503
Prostanoic acid, 1492
Prosthetic groups, of myglobin, 1256-1257
Protecting groups, for m i n e functions, 1157- 1161
for carbonyl functions, 7 15-716
general characteristics of, 529
for hydroxyl function, 529-530, 65 1-653
illustration of use of, 529-530
in peptide syntheses, 1236- 1239, 1244- 1246
Proteins, biosynthesis of, DNA and, 1271, 1277
coiling of, 1249- 1252
collagen as, 1458-1459
cystine linkages in, 1253- 1254
denaturation of, 1259, 1270
fibrous, 1259
formation of, in prebiotic evolution, 1284
functions of (table), 1249-1250
industrial uses of, 1270- 1271
properties of (table), 1250
quaternary structures of, 1259
RNA in, 1277-1280
separations of, affinity chromatography, 1248
electrophoresis, 1248
gel filtration, 1248
ion-exchange chromatography, 1248
ultracentrifugation, 1248
stereoisomers of, 894
structures of, three-dimensional, 1249-1259
synthesis of, RNA and mechanism of, 1277-1282
wool a ~ 1457-1458
,
Protic solvents, 238
Protoporphyrin IX, 1257
Pseudomauveine, 1406
Pseudopelletierene, 990
D-Psicose, structure and configuration of, 906
Puffer fish toxin, 599
Purine, derivatives of, in DNA, 1273
Purity of organic compounds, tests for, 258-262
Pyranose rings, 920-922
Pyranthrone, 1407
Pyrazolines, cyclopropanes from, 1200
from diazomethane, 1200
Pyrene, from coal tar, 1080
quinone of, 1306
1,8-Pyrenedione, as quinone, 1306
Pyridine (see Azabenzene)
Pyridoxal phosphate, with amino acids,
1224- 1225
Pyridoxamine, 1099
Pyrimidine, derivatives of, in DNA, 1273
lactam-lactim isomerism of, 1273
Pyrogallol (see 1,2,3-Benzenetriol)
Pyromellitic anhydride, polyesters from, 1440
Pyrophosphoric acid, esters of, formation and
reactions of, 634-637
Pyruvic acid (see 2-Oxobutanoic acid)
Quadricyclene, from norbornadiene, 503
ring opening of, 1013
Quantum theory, advanced, of simple molecules,
179-182, 981-984
and organic chemistry, 23
Quantum yields, definition and use of, 95,
1379, 1383
Quaternary structures, and hemoglobin, 1259
keratin and, 1259
of proteins, 1259
Quercetin, 1305
Quinhydrone, 1307
Quinine, 867, 1097
Quinoline, 1080, 1118
Quinoneimines, in photographic development, 1311
Wurster's Blue as, 1307
Quinones (see also Benzenediones,
Naphthalenediones, etc.), addition reactions,
1311-1313
of benzene, 1301, 1303, 1305-1307, 1309-1312
biologically important examples, 1308- 1310
of biphenyl, 1306
of 1,3-cyclobutadiene, 1313
electrochemistry of, 1306- 1307
of naphthalene, 1305-1306, 1310
as photographic developers, 1310-13 11
as polymerization inhibitor, 1449
preparation of, 1145, 1301-1303
of pyrene, 1306
reduction of, 1306-1307
reduction potentials of, 1306- 1307
semiquinones from, 1307
types of, 1305-1306
Quinoxalines, 1326
as ladder polymers, 1456
R,S convention for configurations, priority order
of groups in, 879-884
uses of, 133, 879-884
Racemic acid (see Tartaric acid)
Racemization, definition of, 117-1 18
mechanisms for, 895-897
in peptide syntheses, 1238- 1240
in SN1reactions, 222-223
Radical anions, from aryl halides and metals, 573
in Birch reduction, 1075
from naphthalene, esr spectra of, 1367-1369
Radical-chain addition, of hydrogen bromide, to
alkenes, 386-388
Radical-chain polymerization, of alkenes, 395-397,
1446-1449
Radical-chain reactions, inhibition of, 95, 1449
initiation of, 91-94, 102-103, 391, 1447
polymerization as, 1446-1449, 1452-1453
steps of, 93-95, 395-397, 543-544, 1446-1449
termination of, 94-95, 392, 1448-1449
Radicals, in addition copolymerizations, 1452- 1453
in addition polymerization, 395-396, 1444-1449
alkyl, relative stabilities of, 388
from azo compounds, 1198
bonding and geometry of, 169-170
in cycloadditions, 1014- 1017
in phenol oxidations, 1301-1302
in photochemical reactions, 1353-1356, 1379- 1381
Raffinose, properties and occurrence of, 907
Raman spectra, of alkenes, 284-286
of alkynes, 356
reference works for, 348
of tropylium ion, 1315
Raman spectroscopy, elements of, 267
and infrared spectra, 284-286
principles of, 284-286
Raman spectrum, of cyclohexene, 286
of tetrachloroethene, 285
Raney nickel, preparation and use of, 413
Rate-determining step, 90
Rayon, 933
Reaction constants, of Hammett equation,
1330-1337
Reaction kinetics, 2 15-2 17
Reaction mechanisms, concerted vs. stepwise, 98,
498-499, 1014-1017
concerted, 89-90, 98
elementary ideas of, 15-16
formulation of, 98
radical chain, 93-96
rate-determining step in, 90
stepwise, 89-90, 98, 1014-1017
Reaction order, 2 15-2 17
Reaction rates, problems of predicting, 96-97
Reaction types, classifications of, 42-43
Reactions, heat of, 76-80
Reactivity, elementary ideas of, 14
Rearrangements, 1,2-alkanediols to carbonyl
compounds, 720
1,2-alkyl shifts in carbocations, 250
of alkylbenzenes, 1050
in alkylborane carbonylations, 725-726
of alkylzirconocenes, 1513-15 14
in arene alkylations, 1049- 1050
Beckmann, of oximes, 1180- 1181
benzilic acid, 1326
carbocation, in alcohol dehydrations, 632-633
in mines with nitrous acid, 1131
in SN1 and El reactions, 250-25 1
in Curtius degradation, 1156
eugenol to isoeugenol, 1327
Favorskii, with halo ketones, 748-749
in Hofmann degradation, 1155-1 156
1,2-hydrogen shifts in carbocations, 250
ketones from, of 1,2-alkanediols, 73 1
migration aptitudes in, 714
of N-substituted benzenamines, 1139-1 140
of unsaturated alkanoic acids, 841
Redox reactions, balancing equations of, 406-409
of carbon, 405-409
Reducing and nonreducing disaccharides, 928
Reducing sugar, D-glucose as, 913
Reduction (see also Aldehydes, reduction of, etc.),
balancing equations of, 406-409
definition of, 42-43, 405-409
of halides, with tin hydrides, 109
with hydrides, of carbonyl compounds (table),
705-708
Reductive alkylation of aldehydes and ketones,
amines from, 1149, 1154
Reductive amination, 1154
Reflection symmetry, 116
Reformatsky reaction, 836
Reimer-Tiemann reaction, 1299
Relaxation effects, on nmr spectra, 1343-1344
Reppe, W., cyclooctatetraene synthesis of, 990
Reserpine, medical use of, 1500
synthesis of, 1500-1502
Resolution of enantiomers, of alcohols, 867-868
of amines, 868, 1109-1 110
biochemical specificity and, 869
of carboxylic acids, 866-867
chromatographic procedures for, 869
definition of, 117- 118
diastereomer formation and, 866-869
kinetic procedure, 869
Pasteur method, 870
spontaneous crystallization, 870
of tartaric acid, 118
Resolving agents, for alcohols, 868-869
for amines, 868
. for carboxylic acids, 865-867
Resonance, ab initio calculations of, for ethene,
180-182
acidity of 4-nitrobenzenol and, 1294
amide acidities and, 1176
amide basicities and, 1176
in amides, 1168
and m i n e base strengths, 1113- 1115
and annulenes with large rings, 1090
and azulene, 1084
and benzene, 11, 972-975
and benzenol acidity, 1293
and bonding in hydrogen, 963-964
and 1,3-butadiene, 977
and carboxylic acid ionizations, 796-798
and charge-transfer complexes, 1192- 1193
and Cold War politics, 11
and color, 1401-1404
concepts of, 172- 179, 96 1-964, 972-975,
981-984
cyclobutadiene and, 178, 989
cyclooctatetraene and, 989
and delocalization energy, 173-176, 963-964, 967
Dewar benzene and, 973-974
and diphenylmethyl cation, 1320
of electron-pair bonds, 96 1-963
and electronic spectra, 290-293
and en01 acidities, 649-65 1
in ethene, 965-966
formal bonds in, 973
and guanidine base strength, 1118
GVB method and, 983-984
and Hammett correlation, 1331-1332, 1337
and hyperconjugation, 228
and infrared spectra, 292
and nitro compound conjugate bases, 1195
and orientation in aromatic substitution,
1060- 1072
in phenols, 1288
of 2-propenyl cation,. 978-979
and reactivity, 177-178
representations for, 175- 178
rules for, 175-177
stabilization energies (table), 985-986
stabilization of carbocations by, 228-229
and tropolone, 1314- 1315
in tropylium ion, 1315
Resorcinol (see 1,3-Benzenediol)
Retina, structure and pigments, 1416-1417
Retinal, 1416-1417 .
Reversed micelles, 804
Rhizopus nigricans, progesterone oxidation
with, 1478
Rho ( p ) constants (table), 1330-1337
Rhodium, catalysts of, hydroformylation,
1518-1519
hydrogenation, 4 17-418, 1517- 1518
in methanol carbonylation, 1520
mechanism for homogeneous hydrogenation
with, 1517
Rhodopsin, 1416-1417
Riboflavin, 1099
Ribonuclease, properties, 1250
Ribonucleic acids (see RNA)
Ribonucleosides, definition of, 926
D-Ribose, in nucleosides, 926
phosphate esters of, in gluconeogenesis, 955
in prebiotic evolution, 1283
properties and occurrence of, 907
structure and configuration, 904
Ribosomal RNA, 1278
Ribosomes, 1278, 1282
D-Ribulose, phosphate esters of, in
gluconeogenesis, 955
in photosynthesis, 94 1-942
structure and configuration of, 906
Ritter, J., and discovery of ultraviolet
radiation, 287
Ritter reaction, amides and amines from, 1149,
1178-1179
RNA, composition of, 1277-1278
in protein synthesis, 1277-1280
mRNA, 1279-1282
rRNA, 1278
tRNA, anticodon loop of, 1280-1281
function of, 1280-1282
in protein synthesis, 1280- 1282
structure of, 1279-1280
Roberts, J. D., and benzyne mechanism, 560
Robinson, R., and steroid synthesis, 1477-1478
Rodinal, 1311
Rose bengal, 1392
Rosenmund reduction, aldehydes from, with acyl
halides, 719, 728
Roses, oil of, 1466
Rotational barrier, of biphenyls, 5 11
of butane, 123-124
of ethane, 121-123
measurement of, 1345-1347
in N-substituted amides, 1172-1 173
Rotational isomers, in ethane derivatives, 7
Rubber vulcanization, 1429-1430, 1435
Rubbers (see also Polymers, elastomeric), 505-508,
1428-1430
Ruthenium, homogeneous alkene hydrogenation
catalysts from, 417
Ruzicka, L., and isoprene rule, 1462
Sabinene, 1464
Saccharic acids, structures and names of, 912
Saccharin, 1328
Sachse, H., strainless cyclohexane theory of,
464, 480
Salicylaldehyde (see
2-Hydroxybenzenecarbaldehyde)
Salicylic acid (see 2-Hydroxybenzenecarboxylic
acid)
Sandmeyer reactions (table), 1134-1 136, 1138
Sandwich compounds, 1505-1506
Saponification, 82 1
Saponins, digitogenin as, 1473
Saturated hydrocarbons (see also Alkanes), ethane
as example of, 14-15
Savin, oil of, 1464
Sawhorse projections, 125-126
Schiemann reaction, 1135
Schiff bases, 1122
retinal pigment as, 1416-1417
Schmidt degradation, mines from, 1150,
1153, 1156
Schwartz, J., and zirconocene chlorohydride,
1512-1515
Sea pansy, 1398
Secobarbital, 1098
Secondary structures, of peptides, 1228
Sedoheptulose, properties and occurrence of, 907
Selinene, 1464
Semicarbazones, from aldehydes and ketones, 698
Semiempirical quantum calculations, 179- 182
Semiquinones, 1307
Sensitizers, photochemical 1376-1377, 1385-1387,
1392- 1393
photographic, 1310, 1411-1412
Separation techniques, 257-258, 259-262, 1248
Sequence determination of peptides, 1299-1234
Serine, at enzyme active sites, 1265- 1266
genetic code for, 1277
properties of, 1208
Serotonin, 1099
Serturner, F. W. A., and alkaloid isolation, 1097
Sesquiterpenes, alcohols of, 1468
definition of, 1463
hydrocarbon, of, 1468
Sevin, 1328
Sex attractants, of insects, 141
Sex hormones, 1472-1473, 1479
Shark liver, oil of, 1464
Sheehan, J. C., and penicillin synthesis, 1492
Sigma (a) constants (table), 1330-1337
Sigma (a) orbital, definition of, 156
Sigmatropic rearrangements, Claisen ally1 ether
rearrangement and, 1298
Cope rearrangement and, 1006
definition of, 1006
and Hiickel rule, 1006, 1010-1012
inversion in, 1012
Mobius transition states for, 1006, 1010- 1012
in photochemical, in vitamin D formation, 1394
retention in, 1012
stereospecificity of, 1012
Silanes, radical-chain addition to alkenes and
alkynes, 389
Silk fibroin, pleated-sheet structure of, 1253
Silk moth hormone, 1473
Silver bromide, in color films, 1410-1415
in photographic development, 1310-13 11
Silver ion, catalysis of S, reactions of halides, 234
Silver nitrite, with alkyl halides, 1191
Silver oxide and aldehydes, 712
Simmons, H. E., and carbene generation, 566
Simmons-Smith generation of carbenoid
species, 566
Single bonds, formulation of, 155- 164, 168- 172
Singlet states (see also Photochemistry, singlet
states in), 1372-1375
Sitosterol, 1474
Skew conformation, definition of, 124
S,l reactions (see Nucleophilic displacement
reactions, S, 1 mechanism)
S,2 reactions (see Nucleophilic displacement
reactions, SN2mechanism)
Snarol, 696
Soaps (see also Detergents), detergent action
of, 803
from fats, 790
preparation of, 803
Sodium alkylbenzenesulfonates, as detergents,
803-804, 1056-1057
preparation of, 1056- 1057
Sodium amide, carbanion formation with, 1322
Sodium benzenolate, 1032, 1293-1294, 1298-1299
Sodium bisulfite (see Sodium hydrogen sulfite)
Sodium borohydride, reduction of aldehydes and
ketones with (table), 705-708
Sodium cyanoborohydride, 1154
Sodium dodecanyl sulfate, 628
Sodium fluoroethanoate, toxicity of, 569
Sodium hydride, enolate anion formation with, 835
Sodium hydrogen sulfite, additions to aldehydes
and ketones, 695
in Bucherer reaction, 1296
Sodium hypochlorite, singlet oxygen from,
1392-1393
Sodium naphthalenide, esr spectrum of, 1367-1369
in "living" polymerizations, 1451
Sodium nitrite, with alkyl halides, 1190-1 191
as preservative for meat, 1163
Sodium pento thal, 1098
Sodium periodate, 1,2-alkanediol oxidation
with, 727
oxidation of sugars with, 92 1-922
Sodium phenaxide, 1032, 1293-1294, 1298-1299
Sodium tetracarbonylferrate, 1516
Sodium trifiuoroethanoate, toxicity of, 569
Solid-phase peptide synthesis, general procedure,
1242-1247
supports for, 1244- 1245
Solvation effects, and carboxylic acid ionizations,
801-802
nucleophilicity and, 236
on phenol alkylations, 1297-1298
Solvation energies, of ions, 438-439
Solvents, ionizing power of, 237-239
properties of (table), 237-239
Solvolysis (see Nucleophilic displacement
reactions)
D-Sorbose, structure and configuration of, 906
Soybean sterol, 1472
Space-filling models, 37-39, 451-455
and predictions of reactivity, 89-90, 93
Specific rotation, 865-866
Spectroscopic techniques for structure analysis
(table), 267
Spectroscopy, reference works for, 347-349,
1369-1370
wavelength conventions for, 265-268
Spin-orbit coupling, 1397
Spin-spin splitting (see Nmr spectra, spin-spin
splitting in)
Spiranes, chiral forms of, 510
IUPAC rules of nomenclature of, 478
Spiro[2.2]pentane, physical properties and strain
energy of (table), 482-483
Squalene, biosynthesis of, 1485, 1488
from farnesol, 1485, 1485
as isoprenoid hydrocarbon, 1464
lanosterol from, 1486--1488
oxide of, 1486-1487
Squaric acid, 1313
Stability, definition of, 991
Stabilization energies (tables), 984-986
Staggered conformations (see Conformations,
staggered)
Standard states, use of, 84
Starch, biological function of, 934-935
maltose from, 934
properties and occurrence of, 908
structure of, 934-935
uses of, 935
Staudinger, H., and polymer structures, 1419
Stearic acid, 789-790
Stereochemical control (see Asymmetric synthesis)
Stereochemistry, in additions to alkynes, 382
of alkene hydrogenation, 4 12-4 14
of amines, 1108-1 110
of diimide reductions, 419
of E2 eliminations, 245-248
of electrocyclic reactions, 1006- 1012
of halogen additions to alkenes, 362, 365-366
of homogenous hydrogenation, 4 17
of hydroboration, 422-424
hydrogenation of alkenes with, 418-419
of oximes, 887, 1181
of polymers, 504-505, 507, 1430-1435
of proton acids to alkenes, 368
of radical-chain additions, 390
of sigmatropic rearrangements, 1012
of S,1 and S,2 displacements, 219-224
Stereoisomerism (see Cis-trans isomerism and
Isomerism)
Stereoisomers, definition of, 110
Stereospecificity, biological, in enzyme-catalyzed
reactions, 371-372, 930, 1236,
1260-1262, 1487
biological, of sense of taste and smell, 140-141
Steric hindrance, in aromatic substitution, 1064
in cyclohexane conformations, 450, 454-456,
458-460, 480-48 1
definition of, 23
in ester formation, 807-808
and Hammett correlations, 1336
in methane chlorination, 89-90
and nucleophilic displacements, 224-225, 229
in polymer chains, 507
Steroids, biosynthesis of, 1486-1488
definition of, 1471
examples (table), 1471-1474
numbering system for, 1474
synthesis, 1477- 1479
Sterols (see Steroids)
Stigmasterol, structure and occurrence of, 1472
Stilbene (see also 1,2-Diphenylethene), cis-trans,
photochemical isomerization of, 1384-1386
Stimulants, 1098
Stork, G., and cantharidin synthesis, 1497-1498
and cedrene synthesis, 1498
Strain energies, of cycloalkanes, 464-465
Strecker synthesis of amino acids, 1225
Structural formulas, development of, 4- 16
Structural isomers, 45
Structure determinations, 3
by physical methods, electron diffraction
and, 265
electron microscopy and, 262-263
neutron diffraction and, 265
x-ray diffraction and, 262-265
by reaction product studies, 12-16
Strychnine, 867
Styron, 1433
Substituent constants, of Hammett equation,
1330-1337
Substitution, definition of, 42
Substitution method for proof of structure, 8-9, 14
Substitution reactions (see Nucleophilic
displacement, Electrophilic aromatic
substitution, etc.)
Substrate-enzyme complexes, 1260- 1262
Subtilisin, histidine function in, 1266
serine function in, 1265-1266
Subtraction colors, 1399-1400, 1409-1415
Succinic acid (see Butanedioic acid)
Succinimide (see Butanimide)
Sucrose, properties and occurrence of, 907
reactions of, 930-93 1
structure and configuration of, 929-93 1
structure determination of, 93 1-932
synthesis of, 93 1
Sulfanilamide, 1123- 1124
Sulfate esters, from additions to alcohols, 369-371
from alcohols, 628-629
Sulfenyl chlorides, additions to alkenes, 380
Sulfolane (sulfur dioxide and 1,3-butadiene
adduct), 500-501
,
Sulfonamide synthesis of amines, 1127
Sulfonamides, acidity of, 1123
as amine protecting groups, 1161
amines from, 1127
as antibacterial agents, 1123-1 124
in Hinsberg test, 1123
in peptide-sequence determinations, 1230
preparation of, 1122-1 123
reductive cleavage of, 1161
Sulfonate esters, from acyltetracarbonylferrates, 1516
from alcohols, 628-629
of oximes, 1180
with tetracarbonylferrate, 1516
Sulfonation of arenes (see Electrophilic aromatic
substitution)
Sulfonyl halides, radical-chain addition to alkenes
and alkynes, 389
Sulfur, with Grignard reagents, 586-587
vulcanization of elastomers with, 505,
1429-1430, 1435
Sulfur dioxide, 1,3-butadiene cycloadduct, 500-501
physical properties of, 239
as solvent, 238
Sulfur stabilized carbanions, 765-767
Sulfur tetrafluoride, with aldehydes and ketones,
705, 1318
with carboxylic acids, 705, 1318
Sulfur trioxide, in arene sulfonations, 1055
Sulfur ylides, 692
Sulfuric acid, addition to alkenes, 379
Sulfuryl chloride, for alkane chlorination,
102-103, 108
with methylbenzene, 1317
Suprafacial, definition of, 246
Surface catalysis (see Heterogeneous catalysis)
Symmetry center, and meso compounds, 139
Symmetry plane, and meso compounds, 137-138
Syn conformation, definition of, 124
Syndiotactic polymers, 1431-1434
Synthesis, and natural products, 1461
principles in planning of, 5 13-530
Synthesis gas, 723
Synthetases, 1270-127 1
Szwarc, M., and "living" polymers, 1451
2,4,5-T, 561
D-Tagatose, structure and configuration of, 906
D-Talose, structure and configuration, 905
Tanning of leather, 1459
Tannins, 1304
D-Tartaric acid, absolute configuration of, 876
Tartaric acid, biochemical resolution of, 869
conformations of, 135- 139
isomers of, 135-138
optical activity of, 118
physical properties of (table), 137-139
racemic form of, 118
resolution of, 118
Taste and stereoisomerism, 140
Tau (7)bonds, 165-167
Tedlar, 1432
Teflon, synthesis and uses of, 568, 1432
Terephthalic acid (see 1,4-Benzenedicarboxylic
acid)
Termination, of radical polymerization, 1448- 1449
Terpenes (see also Sesquiterpenes, Diterpenes,
etc.), alcohols, 1465-1466
aldehydes, 1465-1466
as essential oils, 1462
examples of (table), 1462- 1464
isoprene rule, 1462-1463
ketones, 1466- 1467
oxygenated derivatives, 1465- 1466
Terpinol, 1466
Terramycin, 1482
Tertiary structures, of peptides, 1228
Terylene, 1433
Testosterone, structure and occurrence, 1473
Tetraalkylammonium salts, elimination reactions
of, 1126
formation of, 1125-1 126
nomenclature of, 1102
Tetracarbonylferrate, 1516
2,2,3,3-Tetrachlorobutane,
nmr spectrum of,
1345-1346
1,1,2,2-Tetrachloroethane,as polypropene
solvent, 1431
Tetrachloroethene, Raman spectrum of, 285-286
reaction with bromine, 16
unsaturated character of, 16
Tetrachloromethane, from chlorination of
methane, 100
physical properties of, 239
radical-chain addition to alkenes and
alkynes, 389
toxicity of, 563
uses of, 562-563
Tetracyanoethene, charge-transfer complex of,
1192-1 193
in [4+21 cycloadditions, 495
Tetrafluoroethene, biradicals from, 1014-10 17
bond energy of, 1017
1,3-butadiene cydloadducts of, 502
polymerization of, 568
polymers from, 391, 568, 1430, 1432
preparation of, 568
Tetrafluoromethane, 18
Tetrahydrocannabinol, 1305
Tetrahydrofuran (see Oxacyclopentane)
Tetramethylammonium salts and hydroxide,
1125-1 126
N, N, N', N' -Tetramethyl-1,4-benzenediamine,
oxidation of, 1307
Wurster's Blue from, 1307
2,2,3,3-Tetramethylbutane,
heat of combustion
of, 79
Tetramethylene glycol (see 1,4-Butanediol)
cis-2,2,5,5-Tetramethyl-3-hexene,
heat of
hydrogenation of, 4 15-4 16
trans-2,2,5,5-Tetramethyl-3-hexene,
heat of
hydrogenation of, 4 15-4 16
2,2,4,4-Tetramethyl-3-pentanone,
photochemistry
of, 1381
N, N, N', Nf-Tetramethyl-1,4-phenylenediamine (see
N, N, N', N'-Tetramethyl- 1,4-benzenediamine)
Tetramethylthiuram disulfide, 1429
1,1,2,2-Tetraphenyl-l,2-ethanediol,
1382-1383
Tetraterpenes, ,&carotene as example of, 1469
Tetrodoxin, 599
Tetroses, structures and configurations of, 904-907
Tetryl, 1192
Thallium salts, additions to alkenes, 380
Thermodynamic control, of additions to alkenes,
374-376
of aldol additions, 75 1-752
carbocation rearrangements, 633
of Claisen condensations, 829-832
Thermodynamics, applications to organic
chemistry, 23, 76-88, 96-97
Thermoplastic polymers (see Polymers)
Thermosetting polymers (see Polymers)
THF (see Oxacyclopentane)
Thiacycloalkanes, nomenclature systems for,
659-66 1
Thiamine chloride, 1099
Thiamine pyrophosphate, in Calvin cycle, 1269
decarboxylation function of, 1267- 1269
in glucose metabolism, 1269
hydrogen exchange of, 1268
Thiazine dyes, 1406
Thin-layer chromatography, for amino acids, 1219
Thioesters, of coenzyme A, 837-840, 1480- 1481
Thioglycolic acid, with wool, 1458
Thiohydantoins, in peptide sequence determinations, 1230
Thiolase, 838-839
Thiols, from Grignard reagents and sulfur, 586-587
radical-chain addition to alkenes and
alkynes, 389
Thionyl chloride, in acyl chloride formation, 809
alkyl halides from alcohols and, 626-627
Thiophene, from coal tar, 1081
Threo, definition of, 883
L-Threonine, absolute configuration of, 877
chiral isomers of, 133-135
physical properties (table), 135-136
properties of, 1208
D-Threose, structure and configuration, 904
Thrombin, serine function in, 1265-1266
Thujaplicin, 1314
Thujone, 1467
Thymine, as DNA component, 1272- 1277
lactam-lactim isomerism of, 1273
photochemical dimerization of, 1394
Thyroxine, 535-536
Tin hydrides, reduction of halides with, 109
Titanium, in Ziegler polymerization, 1444
Titanocene, 1508
TNT, 1042, 1192
Todd, A., and vitamin B,,, 1490
Tollen's reagent, 9 13
Toluene (see Methylbenzene)
Toluene-2,4-diisocyanate, 1454-1455
Toluenesulfonic acid and esters (see corresponding
derivatives of 4-Methylbenzenesulfonic
acid)
Toluidines (see Methylbenzenamines)
Torsional angle, definition of, 121
Tranquilizers, 1098- 1099
Transamination, of amino acids, 1224
Transfer RNA, 1279-1282
Transition state, and activation energy, 96-97
in aromatic substitution, 1041, 1061
definition of, 96
for pericyclic reactions, 495-499, 999-1017
for SN reactions, 22 1
Transition-metal organic complexes, alkyl shifts
in, 1511, 1513-1514, 1517-1519
bonding in, 1509-15 10
hydride shifts in, 1511, 1513-1514, 1517-1519
n-to-o rearrangements of, 1510-15 11,
1513-1514, 1517-1519
Transition-metal organic compounds, alkyl
groups in, 1510-1526
carbene type, 1512, 1521
with carbon monoxide, 1512, 1514-15 16,
1518-1520, 1522-1524
carbon monoxide binding in, 1512
catalytic functions of, 1517-152 1, 1523, 1526
cyclopentadiene derivatives, 1504- 1508,
1512-1515
and ferrocene, 1504- 1505
metallocenes as, 1504-1508, 1512-15 15
nitrogen fixation by, 1508
l ndex
nucleophilic types, 1516, 1520, 1525- 1526
pi ( 7 ~ ) complexes with, of cycloalkenes,
1510, 1523
with 2-propenyl groups, 1522-1524
as reagents, 1508, 1512-1516, 1521-1524
sigma (a) type, 1510-1511, 1513-1520,
1525- 1526
stability of, 1504-1508, 1510-151 1
2,4,6-Triaminobenzenecarboxylicacid, 1304
2,4,6-Triaminotriazine, resins from, 1444
Triarylmethyl derivatives (see corresponding
Triphenylmethyl derivatives)
Triazenes, from benzenediazonium salts, 1137
Triazines, as dye component, 1407
2,4,6-Tribromobenzenamine, preparation of,
1128-1 129
2,4,6-Tribromophenol, from benzenol, 1296-1297
2,4,6-Tri-tert-butylbenzenol,oxidative reactions
of, 1301-1302
Trichloroacetic acid, 566, 792
Trichloroethanal, additions to, 647, 678
1,1,1-Trichlorethane, bond distances in, 37
Trichloroethene, preparation and uses of, 563
Trichloroethanoic acid, 566, 792
Trichlorofluoromethane, preparation and reactivity
of, 567
refrigerant and aerosol use of, 567
Trichloromethane, from methane, 100
dichlorocarbene from, 563-564
from haloform reaction, 746
with phenols, 1299
physical properties of, 239
uses of, 562
Trichloromethylbenzene, benzenecarboxylic acid
from, 1318
from methylbenzene, 1317
Tricresyl phosphate, 1435
Triethoxymethane, aldehydes from, with Grignard
reagents, 729
Triethyl phosphite ozonide, singlet oxygen
from, 1393
Triethylamine (see N,N-Diethylethanamine)
Triethyloxonium salts, preparation and reactions
of, 657
1,1,1-Trifluoroalkanes, from carboxylic acids, 705
Trifluoromethanesulfonate, as leaving group, 549
Trifluoromethyl hypofluorite, addition to
alkenes, 379
Trifluoromethylarenes, from carboxylic acids, 1318
4-Trifluoromethylbenzenamine,base strength
of, 1116
Trifluoromethylbenzenes, from arenecarboxylic
acids, 1318
Trifluoroperacetic acid (see Trifluoroperoxyethanoic acid)
Trifluoroperoxyethanoic acid, with alkenes, 662
Trifluralin, 1195
Triglyme, 656
Trihaloethanoates, dihalocarbenes from, 566
2,4,6-Trihydroxybenzenecarboxylicacid, 1303- 1304
1,2,3-Trihydroxypropane (glycerol), manufacture
of, 542
Trimethylamine (see N,N-Dimethylmethanamine)
1,3,5-Trimethylbenzene, charge-transfer complexes
of, 1192
Trimethylboron, bonding and bond angles of,
150-160
Trimethylene oxide (see Oxacyclobutane)
Trimethylenemelamine, as carcinogen, 1164
Trimethylethylene (see 2-Methyl-2-butene)
Trirnethyloxonium salts, preparation and reactions
of, 657
2,2,4-Trimethylpentane, from alkylation of
2-methylpropene, 397-398
from diisobutylene, 394-395
infrared spectrum of, 279
nmr spectrum of, 334
1,3,5-Trinitrobenzene, charge-transfer complexes
of, 1192
synthesis of, 1189
2,4,6-Trinitrobenzenecarboxylicacid, reduction
of, 1304
2,4,6-Trinitrobenzenol, arenes, picrates with, 1192
charge-transfer complex formation with, 1192
as explosive, 1192
physical properties of, 1289
2,4,6-Trinitro-1-methylbenzene, 1042, 1189, 1191
2,4,6-Trinitrotoluene (TNT), 1042, 1189, 1191
Trioses, structures and configurations of, 904-907
1,3,5-Trioxacyclohexane,696
1,3,5-Trioxane, 696
Triphenylmethane, acid strength of, 1323
anion from, 1321-1322
dyes derived from, 1404- 1406
Triphenylmethanol, triphenylmethyl cation
from, 1321
Triphenylmethyl cations, colors of, 1321
with 1,2,3-cycloheptatriene, 1315
ease of formation of, 1320-1321
sulfur dioxide as solvent for, 1320
from triphenylmethanol, 1321
from triphenylmethyl chloride, 1320
Triphenylmethyl chloride, amine alkylations
with, 1158
ionization of, 1320
triphenylmethyl radical from, 1323
Triphenylmethyl group, hydrogenolysis of, 1158
Triphenylmethyl peroxide, 1323
Triphenylmethyl radicals, dimerization of, 1323
discovery of, 1322- 1324
reactions of, 1323
resonance and, 1323- 1324
Triphenylmethylation, of amines, as protecting
group, 1158
Triphenylmethylsodium, formation of, 1321
Triphenylphosphine, as transition-metal ligand,
417, 1510, 1517-1519
Triphosphoric acid, esters of, formation and
reactions of, 634-637, 940-956, 1483-1485
Triple bonds, formulation of, 167- 168
Triplet states (see also Photochemistry, triplet
states in), 994, 1373-1375
Trisaccharides, definition of, 925
properties and occurrences of, 907
Triterpene, definition of, 1469
Trityl derivatives (see corresponding Triphenylmethyl derivatives)
Trityl protecting group for mines, 1158
Tropocollagen, 1458- 1459
Tropolone, acidity of, 1314-13 15
aromatic reactions of, 1315
copper salt of, 1314
derivatives of, 1314- 1316
synthesis of, 1314
Tropylidene (see 1,3,5-Cycloheptatriene)
Tropylium anion, and Hiickel rule, 997-998
Tropylium cation, from 1,3,5-cycloheptatriene, 1315
Huckel rule and, 997
hydroxide equilibrium with, 1315
from methylbenzene in mass spectrometer, 345
spectra of, 1315
Tropylium radical, esr spectrum of, 1369
Trypsin, in peptide sequencing, 1232-1233
precursor of, 1269
proteolytic properties of, 1260
serine function in, 1265- 1266
Trypsinogen, 1269
Trytophan, properties of, 1210
Tschudi, G., and morphine synthesis, 1499
Tungsten catalysis, of alkene metathesis, 1520- 1521
Turpentine, 1464, 1467, 1469
Tyrian purple, 1407
Tyrosine, in carboxypeptidase, 1263-1264
properties of, 1210
Ultraviolet spectroscopy (see also Electronic
spectra), elements of, 267
Uncertainty principle, and exchange lifetimes in
nmr spectra, 1345- 1346
and Mossbauer spectroscopy, 1360
and nmr line widths, 1343-1344
Unimolecular reactions, 2 16-2 17
Units for wavelengths of electromagnetic radiation,
265-268
Unsaturated carbonyl compounds (see Carboxylic
acids, unsaturated; Aldehydes, unsaturated,
etc.)
Unsaturated compounds (see respective Alcohols,
unsaturated; etc.)
Uracil, in RNA, 1278
Uranocene, 1508
Urea, resins from, 1443- 1444
Urethane foams, 1454- 1455
Uridine, in RNA, 1278
Urushiol, 1304
Usnic acid, 1304
Valence, elementary ideas of, 4
Valence-bond treatment (see also Resonance), ab
initio method and, 981-984
of benzene, 972-975
of 1,3-butadiene, 977
of ethene, 965-966
(;VB method and, 983-984
of hydrogen, 96 1-964
J and Q in, 974-975
of propenal, 977
of 2-propenyl cation, 978-979
Q and J in, 974-975
stabilization energies (table), 985-986
Valeric acid (see Pentanoic acid)
Valine, in penicillins and cephalosporins, 1492
properties of, 1208
van der Waals forces, and cyclohexane equilibria,
454-456
and polymer properties, 1422, 1426- 1429
van Tamelen, E. E., and cantharidin synthesis,
1497-1498
van't Hoff, J. H., and asymmetric carbon, 116
and cis-trans and chiral isomers of polyenes, 5 11
and free rotation, 8
and tetrahedral carbon, 118-1 19
Vanillin and vanilla, 925
synthesis of, 1327
Vapor-phase chromatography (see
Chromatography)
Vasopressin, 1242-1243
Verbena, oil of, 1462, 1464
Verbenone, 1467
Vibrational relaxation, 1374
Vicinal, definition of, 662
Victor Meyer method of molecular weight
determination, 27-28
Vinyl alcohols (see Enols, Ethenol, etc.)
Vinyl bromide (see Bromoethene)
Vinyl cations, formation of, 549
Vinyl fluoride (see Fluoroethene)
Vinylacetic acid (see 3-Butenoic acid)
Vinylacetolactone (see Diketene)
Vinylacetylene (see 1-Buten-3-yne)
Vinylamines (see Enamines)
Vinylite, 1435
Viscose rayon, 933
Visible spectroscopy (see also Electronic spectra),
elements of, 267
Vision, chemistry of, 1416-1417
Vistanex, 1432
Vitamin A, as diterpene, 1468-1469
structure of, 50
Vitamin B,, 1099
Vitamin B,, 1099
Vitamin B,,, alkylation of with ATP, 1526
biological function of, 1526
coenzyme form of, 1525-1526
methylpropanedioyl to butanedioyl coenzyme A
with, 1526
and pernicious anemia, 1489
reduction of, 1526-1527
structure and function of, 1489-1490
synthesis, 1490
as transition-metal compound, 1525- 1526
Vitamin C, structure of, 938
Vitamin D, from ergosterol on irradiation, 1394
Vitamin D,, structure and occurrence of, 1472
Vitamin K,, 1310
Viton, 568, 1432
Vol'pin, M., and nitogen fixation by
titanocene, 1508
von Laue, M., and x-ray diffraction structure
determinations, 1249
Vulcanization, 1429- 1430, 1435
Wacker process, 1528
Wald, G., and chemistry of vision, 1417
Walden, P., inversion in S , reactions, 219-223
Wallach, 0. and isoprene rule, 1462
Warfarin, as blood anticoagulant, 336
nmr spectrum of (carbon-13), 336
Water, addition to alkenes, 368-370
addition to alkynes, 383-384
atomic-orbital model of, 162- 164
bond angles of, 163-164
ionizing power of, 238
as leaving group, 232-234
nmr spectrum of, and paramagnetic ions, 1344
physical properties of, 60, 239
Watson, J. D., and DNA structure, 1249, 1275
Wieland, H., and structures of steroids, 1476-1477
Wilds, A. L., and equilenin synthesis, 1495
Wilke, G., and propenylnickel derivatives,
1521-1524
Wilkins, M. and x-ray diffraction structure
determinations, 1249
Wilkinson, G. homogenous hydrogenation catalyst
of, 417-418
and hydroformylation catalysis, 1519
Williamson ether synthesis, 6 14-6 15
Willstatter, R., and chlorophyll structure, 1258
cyclooctaetraene synthesis of, 990
Windaus, A., and structures of steroids, 1476-1477
Wintergreen, oil of, 1327- 1328
Wittig, G., an ylide reaction, 692
Wohl degradation, 910
Wohl-Ziegler bromination, 542-543
Wolff-Kishner reduction, of aldehydes and
ketones, 7 11--7 12
of Huang-Minlon modification, 7 11-710
Wood, 933
Woodward, R. B., cortisone synthesis, 1495-1497
and orbital symmetry rules, 1005
and reserpine synthesis, 1500- 1502
and vitamin B,,, 1490
Wool, chemistry of, 1457- 1458
Wurster's Blue, 1307
X-ray diffraction, and protein structures, 1249
reference works for, 347
structure determination by, 262-265
Xanthene dyes, 1406
Xylenes (see Dimethylbenzenes)
Xylenols, from coal tar, 1081
D-Xylose, furfural from, 938
in hemicellloses, 937-938
Yams, diosgenin from, 1478
Yeast sterol, 1472
Yellow dye, 1410-1414
Yields, in parallel vs. sequential reactions, 516-517
procedures for calculating, 5 15-5 17
Ylides, additions to aldehydes and ketones,
69 1-693
definition of, 691
Zeise's salt, 1509-15 10
Ziegler, K., catalysts for alkene polmerization,
396-397
Ziegler catalysts, copolymers from, 1435
Zinc, in carboxypeptidase, 1263- 1264
Zinc chloride, as catalysis for alkyl halide
formation, 626
in chloromethylation of arenes, 1319
Zingiberene, 1464
Zirconocene, decamethyl, nitrogen fixation
by, 1508
Zirconocene chlorohydride, with alkenes, 1513
structure and preparation of, 1513
synthetic reactions of, 1512-15 15
Zytel, 1433