Roberts, Caserio - Basic Principles of Organic Chemistry (2nd edition, 1977)
.pdf1,2-hydrogenshifts in carbocations, 250 ketones from, of 1,2-alkanediols, 731 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, 117118
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, 11131115 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, 11921193 and Cold War politics, 11
and color, 1401-1404
concepts of, 172179, 961-964, 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, 961-963 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,
10601072 in phenols, 1288
of 2-propenyl cation,. 978-979 and reactivity, 177-178 representations for, 175178 rules for, 175-177
stabilization energies (table), 985-986 stabilization of carbocations by, 228-229 and tropolone, 13141315
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, 417-418, 15171518 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, 941-942 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, 12801282 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, 511 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, 821
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, 179182 Semiquinones, 1307
Sensitizers, photochemical 1376-1377, 1385-1387, 13921393
photographic, 1310, 1411-1412
Separation techniques, 257-258, 259-262, 1248 Sequence determination of peptides, 1299-1234 Serine, at enzyme active sites, 12651266
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, 10101012
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, 155164, 168172 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, 10561057
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, 921-922
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, 12441245
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, 10061012
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, 14771479
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, 12601262 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, 931-932 synthesis of, 931
Sulfanilamide, 11231124
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, 513-530
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, 135139 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, 14481449 Terpenes (see also Sesquiterpenes, Diterpenes,
etc.), alcohols, 1465-1466 aldehydes, 1465-1466
as essential oils, 1462 examples of (table), 14621464 isoprene rule, 1462-1463 ketones, 14661467
oxygenated derivatives, 14651466 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, 415-4 16 trans-2,2,5,5-Tetramethyl-3-hexene,heat of
hydrogenation of, 415-4 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, 751-752 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, 12671269
in glucose metabolism, 1269 hydrogen exchange of, 1268
Thiazine dyes, 1406
Thin-layer chromatography, for amino acids, 1219 Thioesters, of coenzyme A, 837-840, 14801481 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, 12721277 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, 913
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, 10981099 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, 15041508,
1512-1515
and ferrocene, 15041505 metallocenes as, 1504-1508, 1512-15 15 nitrogen fixation by, 1508
nucleophilic types, 1516, 1520, 15251526 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,
15251526
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, 13031304
1,2,3-Trihydroxypropane (glycerol), manufacture of, 542
lndex
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, 14041406 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, 13221324 reactions of, 1323 resonance and, 13231324
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, 167168 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, 14581459
Tropolone, acidity of, 1314-13 15 aromatic reactions of, 1315 copper salt of, 1314 derivatives of, 13141316 synthesis of, 1314
Tropylidene (see 1,3,5-Cycloheptatriene) Tropylium anion, and Hiickel rule, 997-998 Tropylium cation, from 1,3,5-cyclohepta-
triene, 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, 12651266
Trypsinogen, 1269
Trytophan, properties of, 1210
Tschudi, G., and morphine synthesis, 1499 Tungsten catalysis, of alkene metathesis, 15201521 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, 13451346
and Mossbauer spectroscopy, 1360 and nmr line widths, 1343-1344
Unimolecular reactions, 216-2 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, 14431444 Urethane foams, 14541455 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, 961-964
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, 14261429 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, 511 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, 15251526 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, 14291430, 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, 162164 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, 614-6 15 Willstatter, R., and chlorophyll structure, 1258
cyclooctaetraene synthesis of, 990
Windaus, A., and structures of steroids, 1476-1477 Wintergreen, oil of, 13271328
Wittig, G., an ylide reaction, 692 Wohl degradation, 910 Wohl-Ziegler bromination, 542-543
Wolff-Kishner reduction, of aldehydes and ketones, 711--712
of Huang-Minlon modification, 711-710
Wood, 933
Woodward, R. B., cortisone synthesis, 1495-1497 and orbital symmetry rules, 1005
and reserpine synthesis, 15001502 and vitamin B,,, 1490
Wool, chemistry of, 14571458 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, 515-5 17
Ylides, additions to aldehydes and ketones, 691-693
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, 12631264 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