Roberts, Caserio - Basic Principles of Organic Chemistry (2nd edition, 1977)

1,2-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

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