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

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, 102103, 108 thermal, 99, 101

of alkenes, by radical mechanism, 543-544 of arenes, 10441046

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 chloro-

methylation, 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, 13921393 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, 14751476 Cholestanol, 1477

Cholesterol, biosynthesis of, 1486-1488 occurrence of, 1471

with ketones, 832 limitations of, 830-83 1 with methanoate esters, 831 mixed, 831-832 thermodynamics of, 829

triphenylmethylsodium as base for, 831 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, 10791080

oxygen and sulfur compounds from, 10791080 production of, 74, 1079

Cobalt, vitamin B1 2and, 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, 14801481 structure of, 838

Coenzyme Q, 1309

Coenzymes, B vitamins as, 1267-1268 functions of, 12671269, 15251526 thiamine pyrophosphate as, 1267-1269 types of, 1267-1269

vitamin B12as, 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, 13991400, 1409 and electronic absorptions, 13991404 sensation of, 13991400, 1409

visible wavelengths, 13991400 Color-forming reactions, 1411-1414

Color photography, color transparencies, chemistry of, 1410-1415

instant color prints from, 14141415 subtractive process of, 1410

Complementary colors, 13991400, 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, 471-472

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, 471-472 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, 13451347 of proteins, 1249-1259

and reactivity, 245-247, 466-468 sawhorse representations for, 125126 skew, 124

and spin-spin splittings, 320-32 1 staggered, definition of, 121 syn, 124

torsional angles of, 121124 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, 14521453 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, 15021503

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, 10471050

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, 13241325 Cyanides (see Nitriles)

Cyanine dyes, 1412 Cyanoacetic acid, 793, 811

Cyanoacetic esters, acidity of, 826 Cyanobenzenamines, base strengths of, 1116 Cyanoborohydride, 1154

Cyanocobalamin (see Vitamin B,,) Cyanoethanoate esters, acidity of, 826 Cyanoethanoic acid, 793, 811

Cyanogen bromide, addition to alkenes, 379 Cyanohydrin formation, 689-690

Cyanohydrins, in Kiliani-Fischer synthesis, 911 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, 10891090

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, 781 of cyclopropenone, 781

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, 10131014, 1389, 1392-1393

polar mechanism for, 10231024 possible concerted examples of, 1002 1,2-propadiene dimerization, 502 with 1,2-propadiene, 1002

radical mechanism for, 1014-1017 stepwise mechanism for, 10141017 stereospecificityof, 10141017 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, 9991000, 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, 112113

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, 291-292 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, 851-852 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, 510 Cycloalkyl halides, physical and chemical prop-

erties of, 550-55 1 Cycloalkylidenes, chiral forms of, 510

Cycloalkynes, from gem-dichlorides, 704-705 Cyclobutadiene, angle strain in, 991

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-Cyclobutene- 1,2-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, 471-472

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,

10741075

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, 10721073 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, 451-453 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, 10851086 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, 10071008, 10131014 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, 15041508,

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, 719 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, 551 Cyclopropylmethyl halides, SN1 and SN2reactivity

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, 12531254 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, 811-8 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, 13931394

Deoxyribonucleosides, definition of, 926 Deoxyribose, DNA component, 1272-1274

furanoside structure of, 1274 phosphates of, 12721274

Desoxycholic acid, 14751476 Detergents, action of, 803-804 biodegradation of, 1057

sodium alkylbenzenesulfonates as, 10561057 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, 12011202 Diazanes, azides from, 1202

preparation and reactions of, 1194, 1197 Diazirenes (see Diazacyclopropenes) Diazirines, 1201-1202

Diazo compounds, preparation of, 1199 reactions of, 11991200

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, 11291131 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, 15061507 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, 851-852 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, 12401241, 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 alkoxycarbonylcycloalkanoneswith, 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, 418-4 19 mechanism of hydrogenation with, 419 self-destruction of, 419

stereochemistry of hydrogenations with, 419 thermochemistry of, 418

Diisobutylene (see also 2,4,4-Trimethyl-1-butene), formation of, 394-395

2,4-Diisocyano-1-methylbenzene, 14541455 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-Dimethylpropylhalides, 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, 11871189 2,4-Dinitrobenzenol, 1-chloro-2,4-dinitrobenzene

from, 1295

2,4-Dinitrofluorobenzene, in peptide sequencing,

12291230

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, 13841386 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, 12741275 helical structure of, 1273-1275 molecular weights of, 1271-1272 replication of, 12761277

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, 13841386

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, 14051408 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-Eliminationreactions, 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, 10051009

definition of, 1005

disrotation in, 10061009, 1014 energy charge of, 1005

equilibration by, in fluxional molecules,

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, 813 Electromagnetic radiation, energy of, 269

wavelengths of, 265-268

Electromagnetic spectrum, frequency units for, 266, 268

spectroscopic uses of, 265-267 Electron contours, 180182, 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, 10301034

auxochromes and, 10301031 Beer-Lambert law in, 291, 293 benzene chromophore and, 10301034 of benzene derivatives, 10321033 benzenoid band in, 10321034

of carboxylic acids (table), 793, 795 /3-carotene, 1401

of charge-transfer complexes, 11921193 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, 10331034 of phenanthrene, 1034

of phenols, 1288

n to n'x transitions in, 288-293 of polyenes, 291-292

of polynuclear aromatic hydrocarbons, 1033-1034

prediction of band positions, 293 of pyrene, 1034

reference works for, 348

and resonance stabilization, 14011404 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, 10531055 alkene additions and, 10371040 alkylation, limitations of, 10491050

mechanism of, 10471050 procedures for, 1047-1048 rearrangements in, 10491050

of anthracene, 1069, 1072 of arenamines, 11281129

in arene alkylations, 10471050 of azulene, 1084

of benzene (table), 1037-1040 catalysts for, 1041

chlorination by, cyclodextrin effect on, 935-936

meta-directing groups (tables), 1060-1062 ortho-para directing groups (tables),

10601064

patterns of (table), 1059-1060

steric effects of substituents in, 1064 structure proofs for, 1058-1059

transition state and, 10601064, 10661072 of phenanthrene, 1069, 1071

of phenols, 1296-1300

of polynuclear arenes, 1069-1072 scope and mechanism, 1037-1040 sulfonation, procedures for, 10551057

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, 251

with alcohols, 631-632

amines with nitrous acid, 11301131, 1133 carbocations in, 249-25 1, 631-633