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

in competition with SN1,248-249 leaving groups for, 249-25 1 orientations in, 249-250

reactivity order in, 249 rearrangements in, 250-25 1, 632-633 scope of, 248-251

E2 mechanism, acid catalyzed, 251 with alcohols, 630

alkene mixtures from, 245 alkoxides for, 615

of alkyl compounds, 241-248 antarafacial character of, 245-248 antarafacial route, 245-247

basic reagents and, 241-244 competition with S,2, 241 as concerted reaction, 241 concerted vs. stepwise, 247 of ethenyl halides, 243 kinetics of, 241

leaving groups for, 242 orbital model of, 247 orientation effects in, 245 with phosphate esters, 634 reactivity orders for, 242-244 reagents for, 241-245

solvent effects on, 242 stereochemistry of, 245-248 stereospecificity of, 247-248 steric effects and, 242-243 structural effects on, 242-244 suprafacial route, 246-248 temperature effects on, 244

of tetraalkylammonium salts, 242, 1126 in Williamson ether synthesis, 615

references for, 252

1,3-Elimination reactions, in amines with nitrous acid, 1131

cyclopropanes from, 564 Embalming compound, 775 Emulsion, 930

Enamines, alkylation of, 764-765 from amines, 1122

in biological aldol, 760-76 1 formation of, 702

Michael additions of, 845 rearrangement of, 703

Enantiomers, asymmetric synthesis of, 893-894 of 2-butanol, 119

definition of, 115

and diastereomers, 135-139

mechanisms for interconversion of, 895-897 and meso compounds, properties of, 137-138 physical properties of, 119120

racemization of (see Racemization) resolution of, 866-872

rotation of polarized light by, 119-120 sawhorse drawings of, 127

separation of (see Resolution) Enantiotopic groups, definition of, 888 Enantiomeric purity, definition of, 870-87 1

determination of, by gas chromatography, 871 by nmr spectroscopy, 871-873

Endo-exo isomerism, 496-497 Endothermicity, definition of, 76 Ene reaction, of singlet oxygen, 1392

Energy transfer, in chemiluminescence, 1395-1396 definition of, 1374

diphenylmethanone to naphthalene, 1376-1377 ketones to alkenes, 1385-1386

in visual process, 1417

Enolate anions, addition reactions of, 749-75 1, 757-758, 770

ambident nature of, in aldol additions, 751 in nucleophilic substitutions, 762

enols from, 738-739 formation of, 736-738

in halogenations, 742-747

nucleophilic displacements with, 761-763, 833-834

resonance stabilization of, 650 Enols, acidities of (table), 736-738

acidity of, 649-65 1

from enolate ions, 738-739

from hydration of alkynes, 383-384 resonance stabilization of, 650 stabilities of, 648-65 1, 740-741

Enthalpy, definition of changes in, 76

of organic compounds, reference works for, 105-106

Entropy, and carboxylic acid ionizations, 801-802 concept of, 85-87

definition of, 85

effect in methane-steam gas reaction, 410 of gases, 86

and heat of reaction, 84-85 and molecular disorder, 85-86

of organic compounds, reference works for, 105-106

of ring formation, 87 of solids, 86

Enzymes, cell-wall hydrolysis with, 1254 cellulose hydrolysis with, 1270 cleansing uses of, 1270

for decarboxylation, 1285 denaturation of, 1270

disaccharide configurations with, 930

in hydration of trans-butenedioic acid, 371-372 immobilization of, 1270

induced fit in, 1261-1262 inhibition of activity of, 1269-1270 lock-and-key fit, 1261 mechanisms of operation of, of

carboxypeptidase, 12631265 intermediates in, 12621266 serine in, 1265-1266

substrate complexes, 12601262 nomenclature of, 1260

peptide hydrolysis with, 12311234 properties of, 12601266 proteolytic, 1260, 1263-1266 regulation of activity of, 1269 ynthetases and, 1270-127 1 technology of, 12701271

x-ray structure determinations of, 12611262

Eosin, 1392

Epichlorohydrin, in epoxy resins, 14441445 preparation of, 541-542

Epinephrine, 1099

Epoxidation of alkenes, 435-437, 662 Epoxides (see Oxacyclopropanes) Epoxy resins, chemistry of, 1444-1445

epichlorohydrin for, 542

Equatorial positions (see Cyclohexane) Equilenin, structure and occurrence of, 1472 Equilibrium constants, and reactivity, 81-88 Equilibrium control, of additions to alkenes,

374-376

in carbocation rearrangements, 633 Ergosterol, structure and occurrence of, 1472

vitamin D from, by irradiation, 1394 Erythro, definition of, 883 Erythromycin A, 1482

D-Erythrose,properties and occurrence of, 904, 907 D-Erythrulose,structure and configuration of, 906 ESCA (electron spectroscopy for chemical

analysis), 1358

Esr spectroscopy, of biological reactions, 1368 elements of, 267, 13661367

exchange effects on, 1367-1368

of radicals and radical ions, 1366-1367 Essential oils, 1462

Ester interchange, 821

Esterification, acid catalysis of, 615-6 18 equilibrium of, 618

mechanism of, 616-6 18 thermodynamics of, 616

Esters (see Carboxylate esters, Sulfonate esters, etc., as appropriate)

Estradiol, structure and occurrence, 1472 Estrogenic hormones, 1462, 1479 Estrone, contraceptives from, 1479

methyl ether of, 1479

structure and occurrence of, 1472

Ethanal, aldol additions of, 749-752, 755, 759 ammonia addition to, 700

electronic absorption, 795 from ethanol oxidation, 639 from hydration of ethyne, 383 infrared spectrum of, 794 pentaerythritol from, 754 physical properties of, 679 polymerization of, 696

2-Ethanamidofluorene, 1162, as carcinogen, 1162 Ethanamine, physical properties of, 1101 Ethane, acidity of, 439-440

atomic-orbital model of, 162 bond distances in, 37 bromine cleavage of, 359 conformations of, 121-123 electronic spectrum of, 289

energies of conformations of, 121-122 from ethene reduction, 411-412

Ethane, fluorination of, 97

from photolysis of 2-propanone, 1379 reaction with bromine, 14

rotational barrier of, 121-123

saturated character of, 14-15 single bond in, 31 space-filling model of, 38

Ethanedial, from benzene and ozone, 1078 reactions of, 744-775

1,2-Ethanediamine,physical properties of, 1101 Ethanedioate esters, in Claisen condensations, 832 Ethanedioic acid, decarboxylation of, 847

esters of, chemiluminescencein perhydrolysis of, 1396

properties and uses of, 847 1,2-Ethanediol,as automotive antifreeze, 437

ethers of, 654-656 polyesters from, 1433 polymerization of, 1423

Ethanedioyl dichloride, acyl halides from, 857 Ethanenitrile, bonding in, 31-32

physical properties of, 239

in Ritter reactions, 11781179 synthesis of, 1185

Ethanoic acid, acidity of (table), 736-738 in alkaloid biosynthesis, 1489 ammonia addition to, 700

in aromatic ring biosynthesis, 1481-1482 bonding in, 31-32

in cholesterol biosynthesis, 1486-1488 from ethanol oxidation, 639

in fatty acid biosynthesis, 1480-148 1 infrared spectrum of, 794

ketene from, 772

physical properties of, 239, 792

in terpene biosynthesis, 1483-1485 in vinegar, 49

Ethanoic anhydride, with 1,4-benzenedione, 1311-13 12

with glycine, 1222

Ethanol, acidic properties of, 612-6 13 alkoxide from, 612-613

azeotrope with water, 607 dehydration of, ethene from, 630-63 1

ethoxyethane from, 630-63 1 drying of, 607

formation of, 12

from hydration of ethene, 361 with hydrogen bromide, 13

infrared spectra, hydrogen bonding and, 602-604

nrnr spectrum of, characteristics of, 295-296 exchange effects on, 311-3 13

oxidation of, ethanal from, 639 ethanoic acide from, 639

physical properties of, 601 space-filling model of, 38 from starch, 935

Ethanoyl coenzyme A, acyl transfer with, 837-840 in carbohydrate metabolism, 944, 949-953

and fatty acid biosynthesis, 14801481 Ethanoyl nitrate, 1043 N-Ethanoylaminoethanoic acid, 1222 Ethanoylbenzenamines, base strengths of, 1116 2-Ethanoyloxybenzenecarboxylicacid

(aspirin), 1328

Ethene, ab initio calculations of, 180-182 acidity of, 439-440

addition to 1,3-butadiene, 493 atomic-orbital model of, 165167 ball-and-stick models of, 35 bond angles of, 35-36

bond distances in, 37

bromine addition to, 14-16, 359 carbon monoxide copolymer of, 1453 copolymer with propene, 396

as "cycloethane," 463, 467 1,3-cyclopentadieneadduct of, 526-527 dimerization of, 502

double bond in, 31

electronic spectrum of, 289-290 from ethanol dehydration, 630-63 1 ethanol from, by hydration, 607 heat of hydrogenation of, 415 hydration of, 361

hydroboration of, 420 hydrogenation of, 411-4 12

molecular-orbital treatment of, 964-965 oxacyclopropane from, with oxygen, 437 oxidation of, 43

photoelectron spectrum of, 1357 polymerization of, Ziegler mechanism for, 1446 polymers from (see also Polyethene),

physical properties of, 1425-1427, 1430, 1434-1435

radical-chain polymerization of, 395-396 reaction with bromine, 14-16

resonance structures for, 176 rotation about double bond of, 167 space-filling model of, 38 thermodynamic stability of, 359 valence-bond treatment of, 965-966

Ethenol, rearrangement to ethanal, 648 Ethenone (see Ketene)

Ethenyl cations, formation of, 549 Ethenyl ethanoate, copolymer with

chloroethene, 1435 polyvinyl alcohol from, 1433 preparation of, 649

Ethenyl trifluoromethanesulfonate, S, 1 solvolysis of, 549

Ethenylbenzene (styrene), anionic polymerization of, 1451-1452

block polymer from, 1452 chlorotrifluoroethene adduct of, 1313 copolymer with 1,3-butadiene, 506 copolymers from, 1452-1453 electronic absorptions of, 1030-1033 in fiberglass, 1440

with oxygen, 1453

polymers of, 391, 1430, 1433 radical polymerization of, 1447-1448

Ether (see Ethoxyethane) Ethers, acid cleavage of, 656-657

from alcohols, 655

and diazomethane, 1199

by Williamson synthesis, 614-615, 655 from alkenes, 655

aryl, cleavage of, 1295 preparation of, 1294, 1297-1298

autoxidation of, 658-659 block polymers of, 1454

boron trifluoride complexes of, 656 chloro, formation and reactivity of, 704 classification of, 654-656

complexes with Grignard reagents, 577 cyclic, Hantzch-Widman nomenclature for,

659-660

IUPAC rules fo nomenclature of, 659-661 metal complexes of, 665-666

electronic spectra of, 605

infrared stretching frequencies for, 276

IUPAC rules of nomenclature for, 192, 654-656 mass spectra of, 607

oxonium salts from, 656-657 peroxides from, 658-659

phenylmethyl, as protecting group for OH, 651-652

physical properties of, 654-656 preparation of (table), 655 reactivity of, 600, acids and, 656-657

bases and, 656 oxygen and, 658-659 radicals and, 658-659

as solvents for organometallic reactions, 571-572, 577

spectroscopic properties of, 656 trimethylsilyl, as protecting group for OH,

651-652

unsaturated, protecting group formation with, 529-530

Williamson synthesis for, 614-6 15, 655 Ethoxyethane, boron fluoride complex of, 656

3om ethanol dehydration, 630-63 1, 650-65 1 physical properties of, 239, 654 triethyloxonium salts from, 657

Ethyl acetate (see Ethyl ethanoate)

Ethyl acetoacetate (see 3-Oxopropanoate esters) Ethyl alcohol (see Ethanol)

Ethyl aminoethanoate, diketopiperazine from, 1222 ethyl diazoethanoate from, 1223

with nitrous acid, 1223

Ethyl benzenecarboxylates, hydrolysis rates and Hammett equation, 1329-1330

Ethyl bromide (see Bromoethane) Ethyl chloride (see Chloroethane) Ethyl cyanoacetate, acidity of, 826

Ethyl diazoethanoate, preparation of, 1223 Ethyl ether (see Ethoxyethane)

Ethyl hydrogen sulfate, in dehydration of ethanol, 630-63 1

Ethyl iodide (see Iodoethane)

Ethyl malonate (see Propanedioate esters) Ethyl nitroacetate (see Ethyl nitroethanoate) Ethyl nitroethanoate, acidity of, 826

synthesis of, 1191

Ethyl orthoformate (see 1,1,1-Triethoxyethane) Ethyl oxalate (see Ethanedioate esters)

Ethyl 3-phenylpropenoate (ethyl cinnamate), Michael additions of, 844

Ethylene (see Ethene)

Ethylene chlorohydrin (see 2-Chloroethanol) Ethylene glycol (see also 1,2-Ethanediol),

industrial perparation of, 647 properties of, 647

uses of, 647-648

Ethylene oxide (see Oxacyclopropane) Ethylenediamine (see 1,2-Ethanediamine) N-Ethylethanamine, nmr spectrum of, 1105 2-Ethyl-1-hexanol, industrial perparation of, 759 Ethyne, acidity of, 437-440

atomic-orbital model for, 167-168 ball-and-stick models of, 35 bond angles of, 35

bond distances in, 37 bromine addition to, 359

cycloaddition with 1,3-cyclopentadiene, 1314 cyclooctatetraene from, 990 1,3-cyclopentadiene adduct of, 526-527 dimerization to butenyne, 44 1

electrophilic addition to, bromine in, 382 characteristics of, 382-384

water in, 383-384

ethanoic acid addition to, 649 ethenyl esters and ethers from, 649 explosive decomposition of, 359 methanol addition to, 649 photoelectron spectrum of, 1357 physical properties (table), 446 polymerization of, 393 spectroscopic properties of, 446-448 thermodynamic stability of, 359

in welding, 359

Ethynyl cations, formation of, 549 Ethynylbenzene, infrared spectrum of, 356

nmr spectrum of, 357 17-Ethynylestradiol, 1479 Eucalyptus, 1,8-cineole from, 1466 Eugenol, rearrangement of, 1327

structure of, 1304 vanillin from, 1327

-Eutectic mixtures, definition of, 258 Exclusion principle, 153-1 55 Exo-endo isomerism, 496-497 Exothermicity, definition of, 76

Explosives, nitro compounds as, 11911192 Eye chemistry, 1416-1417

FAD (see Flavin adenine dinucleotide) Faraday, M., 10

Farnesene, 1464, 1468

Farnesol, as insect hormone, 1468 pyrophosphate of, 1485, 1488 squalene from, 1485, 1488

as terpene alcohol, 1468

Farnesyl pyrophosphate, 1485, 1488 Fats, soaps from, 790

Fatty acids, biosynthesis of, 14801481 characteristics of, 789-79 1 metabolism of, 837-840

Favorskii rearrangement, 748-749 Fehling's solution, 913 Fenchone, 1467-1468 Fermentation, in glycolysis, 949

of starch, 935

Ferric bromide, catalysis of arene bromination with, 10441046

Ferric chloride, with phenols (color test), 1294-1295

Ferricinium ion, 1506

Ferrocene, discovery of, 15041505 electronic configuration of, 15051506 physical properties of, 15041506 reactions of, 1504-1506

structure and conformations of, 15051506 Fiberglass, 1440

Field effect, and carboxylic acid ionizations,

Fischer, E., and determination of sugar configurations, 909-9 12

Fischer, E. 0 . H., 418

Fischer, H., and heme synthesis, 1257-1258 Fischer, O., and mauveine structure, 1406 Fischer-Tropsch process, 723

Flavin adenine dinucleotide, as biological oxidizing agent, 646

in carbohydrate metabolism, 946

Flavin mononucleotide, in biological oxidations, 13081309

Flavone, structure as prototype, 14611462 Flavonoids, 14611462

Flax, 933

Flower pigments, 1403 Fluoranthrene, from coal tar, 1080 Fluorene, acid strength of, 1322

from coal tar, 1080

Fluorescamine, with aminoacids, 1217 Fluorescein, 1392

Fluorescence, of benzene, 1375 definition of, 1374

Fluorination, of alkanes, 99 difluoromethylbenzenes from, 1318 trifluoromethylbenzenes from, 1318

Fluoroacetic acid, 792

Fluoroarenes, from arenediazonium salts, 1134-1135

Fluorocarbons, as blood replacements, 569 definition of, 568

development of, 568

physical and chemical properties of, 569 physiological properties of, 569

Fluorochloromethanes, 567

1-Fluoro-2,4-dinitrobenzene,peptide sequencing, 1229-1230

Fluoroethanoic acid, 792 2-Fluoroethanol, toxicity of, 569

Fluoroethene, polymer of, 391, 14301432

Fluoromethane, 18

ion-cyclotron resonance studies of, 1365 Fluxional molecules, 10891090

Folic acid, structure and biochemical formation, 1123-1 124

sulfanilamide effect on, 11231124 Formal bonds, in resonance treatment, 973 Formaldehyde (see Methanal)

Formic acid (see Methanoic acid) Formose, and prebiotic evolution, 1283 Formulas, molecular, determination of, 3-4

N-Formylaminomalonic ester synthesis of amino acids, 1226

Four-center reactions, hydroboration as, 424 Franck-Condon principle, definition of, 1372

in singlet excitation, 13721374 Free energy, definition of, 84

of organic compounds, reference works for, 105-106

standard, 84-85 values for, 85, 87

Free radicals (see Radicals)

Free rotation, concept of, 7-8, 121-123 Friedel, C., and acylation of arenes, 1051-1053

and arene alkylation, 10471050 Friedel-Crafts alkylation of arenes, 1047-1050 Friedel-Crafts ketone synthesis, 10511053 Friedman, L. J., and cantharidin synthesis,

1497-1498

Front-side approach, 219-223

D-Fructose, 1,6-diphosphate, from biological aldol reaction, 760-76 1

in glycolysis, 947-948 in photosynthesis, 943

hemiacetal form of, 621 osazone from, 924

6-phosphate, conversion to mannose

6-phosphate, 919 in glycolysis, 947-948

properties and occurrence of, 907 structure and configuration of, 906

Fructoside, definition of, 925

Functional derivatives, of carboxylic acids (table), 817-820

Functional groups, classification of, 39-42 reactions of, 41-42, 524-525

table of, 40

Furan (see Oxa-2,4-cyclopentadiene)

Furanose rings, 920-922 Furfural, 938

g factors, in esr spectroscopy, 1367 Gabriel synthesis, amines from, 1127, 1148

imides in, 1176

D-Galactose, properties and occurrence of, 907 structure and configuration, 905

Galactoside, definition of, 925

L-Galacturonic acid, 937 Gallic acid, 1304 Gammexane, 1076 Gasoline, composition of, 74

Gates, M., and morphine synthesis, 1499 Gattermann aldehyde synthesis, 1053-1055 Gattermann-Koch aldehyde synthesis, 1053 Gauche conformation, definition of, 124 Gel filtration, 1248

Gel polymers (see Polymers, gel) gem, definition of, 647

Generalized theory of acids and bases, 208-211 Genetic code, 1271, 12761277

Genetic control, DNA in, 1271, 1274-1275 Gentiobiose, amygdalin and, 1327

Geon, 1432 Geranial, 14651466 Geraniol, 114115

Geranyl pyrophosphate, 1484-1485 Gibbs free energy (see Free energy) Ginger, oil of, 1464

D-Glucaric acid, 913 Gluconeogenesis, 955-956

D-Glucose, absolute configuration of, 876-877 aldehyde derivatives of, 913-914

aldehyde form of, equilibrium with, 917 aldehyde reactions of, 913-9 14

a and ,B forms of, 914-918 amine derivatives of, 936-937 with amines, 923

amygdalin and, 1327 anomers of, 914-9 18

carbon-13 nmr spectrum of, 917-9 18 configuration of, 908-909 conformation of, 915-9 16 D-glucaricacid from, 913 glucosylamines from, 923

in glucovanillin, 925-926 hemiacetal form of, 621 metabolism of, 944-950, 955-956 methanol reaction of, 914 methylation of, 921-922

mutarotation of anomers of, 917-9 18 occurrence of, 908

osazone from, 924

periodate oxidation of, 921-923 with phenylhydrazine, 924

(;-phosphate, in gluconeogenesis, 955-956 in glycolysis, 947-948

properties and occurrence of, 907 pyranose ring in, 920-922

reanangement to fructose and mannose, 918-919

as reducing sugar, 913

ring-size determination of, 921-923 sodium periodate oxidation of, 921-922 sorbitol from, 913

structure and configuration, 905 tetramethyl derivative of, 921-922

Glucosidase, 930, 935 Glucoside, definition of, 925 Glucosylamines, 923

Glucovanillin, 925-926

Glutamic acid, in carboxypeptidase, 1263-1264 properties, 1209

synthesis of, 1226 Glutamine, hydrolysis of, 1229

properties, 1209

Glutaric acid (see Pentanedioic acid) Glutathione, 12421243

Glyceraldehyde, chiral forms of, 132-133 D-Glyceraldehyde, absolute configuration of,

875-876

in gluconeogenesis, 955 in glycolysis, 947-948

3-phosphate, biological aldol reaction of,

760-76 1

in photosynthesis, 942-943 properties and occurrence of, 907 structure and configuration, 904

D-Glyceric acid, phosphates of, in photosynthesis, 942

phosphates of, in glycolysis, 949 Glycerides, hydrolysis of, 790 Glycerol (see 1,2,3-Propanetriol) Glycin, 1311

Glycine, in carboxypeptidase, 12631264 from chloroethanoic acid, 1225

in collagen, 1458 diketopiperazine from, 1222 with ethanoic anhydride, 1222

ethyl ester of, diketopiperazine from, 1222 ethyl diazoethanoate from, 1223

with nitrous acid, 1223 forms of, 1212-1213 ionizations of, 1212-1213 isoelectric point of, 1212 properties of, 1208

Glycols (see appropriate diols) Glycolysis, mechanism of, 946-950 Glycosides, structures of, 925-937 Glymes, 656

Glyoxal, 774-775, 1078 Glyptal resins, 14391440

Goddard, W. A., 111, and GVB orbital theory, 180-182

and ozone structure, 433

Gomberg, M., and triphenylmethyl radical, 1323 Gout, 1316

Graft polymers, 14541455 Grape flavor, 1328

Graphite, properties and structure of, 17-18 Greek letters, and substitution positions, 225 Grignard, V., and organomagnesium

compounds, 576 Grignard reagents (see

Organomagnesium compounds) Griseofulvin, 536

Guanidine, base strength of, 1118 Guanine, as DNA component, 1272-1277

in RNA, 1278

Guanosine diphosphate, in citric acid cycle, 951-954

structure of, 953

D-Gulose, structure and configuration, 905 L-Guluronic acid, 937

Gutta-percha, 507, biosynthesis of, 1485, 1488 GVB method, for benzene, 983-984

of ethane C-H bond, 439-440 of ethene bonding, 180-182. of ethyne C-H bond, 439-440 of ozone, 433

Gyromagnetic ratio, 297

Hair curling, 1458

Haller-Bauer cleavage of ketones, 747 Hallucinogens, 1098

Haloalkanes, physical properties of (table), 537-538

Haloalkynes (see Alkynyl halides)

Haloarenes (see also Aryl halides), from arenediazonium salts (table), 1133-1 135, 1138

Halocycloalkanes (see Cycloalkyl halides) Haloform reactions, with alkenones, 747

ethanoylarenes to arenecarboxylic acids with, 1317

mechanism of, 746-747 synthetic uses of, 746-747

Halogen-metal exchange, preparation of organometallic compounds by, 573-574

Halogenation, selectivity in, of alkanes, 98-102 Halogenation of arenes (see also Electrophilic aromatic substitution), 10441045,

10701072

Halogens, additions to alkenes, 360-367 with Grignard reagents, 586-587

a-Haloketones (see Ketones, a-halo) Halomethanes, radical-chain addition to alkenes

and alkynes, 389

Hammett, L. P., and reactivity correlations, 1329-1337

Hammett equation, formulation of, 1330-133 1 limitations of, 1336-1337

scope of, 1335

Hammett rho ( p ) constant (table), 1330-1337 Hammett sigma (o) constants (table), 1330-1337 Hashish, 1305

Hassel, O., and conformational analysis, 124, 450 Haworth, W. N., and oligosaccharide structures,

928-929

Haworth projections, 915 Heart poison, 1473

Heat of reaction, calculation of, 76-80 definition of, 76

reference works for, 105-106 Heat of solution, of ions, 212-2 13

Heats of formation, of alkanes, 86-87 Heats of hydrogenation, of alkenes (table)

415-416

Heavy-metal salts, electrophilic catalysis of halide S, reactions, 234

Index

Heisenberg, W., uncertainty principle of, 1343-1346

Heme, structure of, 1257

Hemiacetals (see also Memiketals), from alcohols and carbonyl compounds, 621-624

D-glucoseas, 913-9 18

mechanism of formation of, 622-624 Hemicelluloses, 937-938

Hemiketals (see also Hemiacetals), from alcohols and carbonyl compounds, 621-624

from cyclopropanones, 780-78 1 mechanism of formation of, 622-624

Hemoglobin, function, 1249-1250, 1254-1259 as oxygen carrier, 1258-1259

properties, 1250 Hemp, 933

Henderson-Hasselbalch pH equation, 209 Heparin, 936-937

Heptanedioic acid, properties and uses of, 849 Heptoses, properties and occurrences of, 907 Herbicides, nitro compounds as, 1195

Herschel, W., discovery of infrared radiation, 271 Heterocyclic compounds, Hantzsch-Widman

nomenclature for, 659-66 1

IUPAC rules of nomenclature for, 659-661 Heterogeneous catalysis, of alkene hydrogenation,

410-414

of reduction of nitrogen to ammonia, 410-41 1 Heterolytic reactions, definition of, 207

kinds of, 207 Hexachlor, 1076

Hexachlorocyclopentadiene, in [4+21 cycloadditions, 493

Hexachloroethane, bond distances in, 37 Hexachlorophene, 561

1,4-Hexadiene,copolymers of, 1432, 1435 1,5-Hexadiene,from di-T-propenylnickel, 1522 Hexafluoroacetone hydrate, 647 Hexafluoropropene, copolymers of, 568, 1432

elastomer with 1,1-difluoroethene, 568 Hexamethylenetetramine, formation of, 700

nitration of, 701 structure of, 700

1,6-Hexanediamine,polymer from, 1433, 1441 synthesis of, 1441

Hexanedioic acid, from cyclohexane and cyclohexanone, 1441

polymer from, 1433, 1441 "Hexaphenylethane," formation and structure

of, 1323 1,3,5-Hexatriene,benzene and, 967-968

with bromine, 968, 971

electrocyclic reactions of, 10051012 with hydrogen, 968

molecular-orbital treatment of, bromine with, 971

with nitric acid, 968 with ozone, 968 reactions of, 967-968

with tetracyanoethene, 968

Hexoses, structures and configurations of, 904-907 Hi-fax, 1432

4 565

Hindered rotation (see Restricted rotation) Hinokitiol, 1314

Hinsberg test for amines, 1123 Histidine, in myoglobin, 1058

properties of, 1210

in proteolytic enzymes, 1266 Hodgkin, D., and vitamin B,,, 1490

and x-ray diffraction structure determinations, 1249

Hoffmann, R., and orbital symmetry rules, 1005 Hofmann degradation, amines from, 1150,

1153, 1155 Hofmann elimination, 1126

Holding groups, and E2 reactions, 468 stabilization of conformations with, 458-460

Homo, definition of, 1211 HOMO orbitals, 98 1 Homocysteine, 1211

Homogeneous catalysis, of alkene hydrogenation, 417-418, 1517-1518

Homogeneous catalysts, stereochemistry of hydrogenation of alkenes with, 417

Homology, definition and uses of, 71-73 and physical properties, 7 1-73

Homolytic reactions, definition of, 206-207 Homopolymer, definition of, 505 Homoserine, 1211

Huckel, E., aromaticity rule, and cyclic ions, 996-998

and cyclic polyenes, 989-995

Huckel, W., and cis and trans isomers of decalin, 480-48 1

Huckel orbital systems, energy levels of, 993 Hiickel rule, and cycloaddition reactions,

999-1005, 1010-1014

and electrocyclic reactions, 10051014

and sigmatropic rearrangements, 1006, 10101012 and tropylium cation, 1315

Hughes, E. D., and nucleophilic substitution mechanisms, 22 1

Hund's rule, of electrons in degenerate orbitals, 153-155, 992-993

Hunsdiecker reaction, 813

Hybrid orbitals (see Atomic orbitals) Hybridization, of atomic orbitals, 159161

and bond lengths (table), 987-988 Hydration of alkenes, 608

Hydrazides, in Curtius degradation, 1150, 1153, 1156

as functional derivatives of carboxylic acids, 819 preparation of (table), 858

Hydrazine, oxidation to diimide, 419 Hydrazines, aldehyde additions of, 698

from arenediazonium salts, 1138 azides from, 1197, 1202

ketone additions of, 697-699, 702 preparation of, 1194, 1197 reactions of, 11941197

uses of, 1197

Hydrazobenzene, rearrangement of, 1140 Hydrazoic acid, in Schmidt degradation, 1150, 1153 Hydrazones, from aldehydes and ketones, 698

Hydride reductions, alcohols from, 610 Hydride shifts, in transition-metal complexes,

1510-1514, 1517-1519, 1526 Hydroboration, of alkenes, alcohols from, 608

with alkyl and dialkylboranes, 422-424 with 9-BBN, 423

of 1,5-cyclooctadiene, 423 mechanism of, 425

orientation in additions to alkenes, 42 1-424 stereochemistry of, with alkenes, 422-424

Hydrocarbon acids, strengths of (table), 1322 Hydrocarbon alkylation, mechanism of, 397-398 Hydrocarbons (see Alkanes, Alkenes, etc., as

appropriate) Hydroforming, 10791083

Hydroformylation, aldehydes from, with alkenes, 729

of alkenes, 722-723, 1518-15 19 industrial alcohol syntheses by, 759 mechanism of, 1518-1519

Hydrogen, calculations of bond energy of, 982-983

Hydrogen bonding, in alcohols, concentration effects on, 311-3 12

infrared spectra and, 602-604 of alcohols, 600-605

and alpha helix, 1152-1 153 of amides, 1168

of amines, 11031105 of carboxylic acids, 791

in DNA structure, 1275-1277 of enols, 740, 776

in enzyme reactions, 12621263, 1266 ethanol, infrared spectra and, 602-604 and hydrogen fluoride, 20

infrared stretching frequencies for, 277 intramolecular hydrogen bonding, of

2,4-pentanedione, 740-742 of phenols, 1288-1291

in phenols, 1288

and pleated sheet, 1252-1253 in proteins, 1251-1253, 1259

and proton nmr spectra, 311-313, 741-742, 1291-1292

in tRNA structure, 1279-1282

Hydrogen bromide, addition to alkenes, 379 radical-chain addition to alkenes, 386-389 Hydrogen chloride, addition to alkenes, 379 Hydrogen cyanide, addition to alkenals and

alkenones, 768

addition to aldehydes and ketones, 689-690 physical properties of, 239

in prebiotic evolution, 1282-1284 Hydrogen fluoride, addition to ethyne, 382

additions to alkenes, 368, 379 physical properties of, 19-20, 239

Hydrogen halides, additions to alkenes, 367-368, 370-371, 373-376

Hydrogen molecule, bonding in, 960-964 Hydrogen molecule-ion, bonding in, 156

- Hydrogen peroxide, addition to alkenes, 434-437

Index

in nitrile hydrolysis, 1178

oxidation of amines with, 11431144

Hydrogen sulfate esters, from additions to alkenes, 369-371

Hydrogen sulfide, bond angles of, 172 Hydrogen sulfite, additions to aldehydes and

ketones, 695

Hydrogenation, of aldehydes and ketones, 710 of alkenes, heats of (table), 415-4 16

of alkynes, 413-414

of arenes, 414, 1072-1074 of benzenols, 1300

of carbon monoxide, 612

of carbonyl compounds, 611

catalysts for, 411-414, 417-418, 1517-1518 homogeneous, mechanism for rhodium catalyst,

1517-1518

homogeneous catalysts for, 417-418 Hydrogen-deuterium exchange, of arenes, 1057 Hydroperoxides, from alkenes, with hydrogen

peroxide, 721

from Grignard reagents and oxygen, 587 ketones from, by rearrangement, 721-722, 732 rearrangements of, to carbonyl compounds,

721-722, 732

Hydroquinone (see 1,4-Benzenediol) Hydroxamic acids, from esters, 858

as functional derivatives of carboxylic acids, 819 2-Hydroxyalkanoic acids, lactides from, 843 3-Hydroxyalkanoic acids, from ketones and esters,

835-836

from Reformatsky reaction, 836 from unsaturated acids, 841-842 unsaturated acids from, 843

4-Hydroxyalkanoic acids, lactones from, 843

2-Hydroxybenzenecarbaldehyde, from benzenol, 1299

hydrogen bonding in, 1288 physical properties of, 1290

4-Hydroxybenzenecarbaldehyde, physical properties of, 1288, 1290

2-Hydroxybenzenecarboxylic acid, from benzenol,

12981299

ethanoate ester of (aspirin), 1328 hydrogen bonding in, 1288 , methyl ester of, 1327-1328

4-Hydroxybenzenecarboxylic acid, from benzenol,

1298-1299

3-Hydroxybutanal (aldol), dehydration of, 755-756 preparation of, 749-75 1

2-Hydroxybutanedioic (malic) acid, from biological hydration of trans-butenedioic acid, 371-372

as intermediate in citric acid cycle, 951-954

2-Hydroxybutanoic acid, oxidation of, NAD+ and, 645

Hydroxycyclobutenediones, 1313 2-Hydroxy-1,2-diphenylethanone,formation and

reactions of, 1324-1325 Hydroxyketones, by acyloin reaction, 852-853

by aldol addition, 752-753, 756-758, 760-761

Hydroxylaminesulfonic acid (azanyl hydrogen sulfate), organoborane reactions, 427, 430-43 1

Hydroxylysine, properties, 1209

2-Hydroxy-6-methylbenzenecarboxylic acid, biosynthesis of, 14811482

2-Hydroxymethyl-2-methyl- 1,3-propanediol, polyesters from, 1440

3-Hydroxypentanoic acid, from 2-oxobutanoic acid, 840

N-(4-Hydroxyphenyl)aminoethanoic acid, 1311 4-Hydroxphenylmethanol, from benzenol, 1300 11-Hydroxyprogesterone, from progesterone by

microbial oxidation, 1478 Hydroxyproline, and alpha helix, 1252

in collagen, 1458 with ninhydrin, 1217 properties of, 1210

2 - ~ ~ d r o x ~ ~ r o ~acid,n oincgluconeogenesis, 955-956

in glycolysis, 949-950 oxidation of, NAD+ and, 645

2-Hydroxypyrimidine, lactam-lactim isomerism of, 1273

Hyperconjugation, definition of, 228 and stability of carbocations, 228

Hyperfine interactions in esr spectra, 1369-1360 Hypochlorous acid, additions to alkenes, 360,

378-379

Hypoiodous acid, addition to alkenes, 379

I-effect (see Inductive effecl)

D-Idose, structure and configuration, 905 Imidazole (see 1,3-Diazacyclopentadiene)

Imides, acidity of, 1176

as functional derivatives of carboxylic acids, 818 ladder polymers of, 1456

Imines, amines from, 1146, 1148, 1154 formation of, 696-699

rearrangement of, 1122

in visual process, 1416-1417 1,2,3-Indanetrione (see Ninhydrin) Indanthrene Brilliant Orange, 1407 Indene, acid strength of, 1322 Indigo, 1403

Indole, alkaloids related to, 14611462 structure as prototype, 1461-1462

Inductive effects, amine basicities and, 1114-1 116 in aromatic substitution, 10601064

and carboxylic acid ionization, 798-800 Infrared spectra, of alcohols, hydrogen bonding

effects on, 604

of alkanediols, hydrogen bonding effects on, 604 of alkenes, 351-352

of alkynes, 356

of amides, 1170-1171 of amines, 1104

of amino acids, 1215 of arenes, 1027-1030

bending vibrations in, 272-282

of carbonyl compounds (table), 680-681 of carboxylic acids, 281-282, 793-794 conjugation effects on, 292

of diatomic molecules, 272 elements of, 267

of ethanol, 602-604 of ethers, 656

fingerprint region of, 278

hydrogen bonding effects on, 277, 281, 602-604, 793, 1104, 1171

of nitriles, 1184

of nitro compounds, 1187 overtones in, 352-353 practice of, 273-274 reference works for, 347-348

stretching vibrations in, and atomic masses, 274-275

and bond types, 275 energy changes in, 277 force constants for, 274-275

general considerations, 272-284 and rotational transitions, 275-277 table of, 276-277

structure determination with, 28 1-282, 313-3 14 Infrared spectrum, of 3-bromopropene, 324

of 2-butanone, 273 of I-butene, 351-353

of cyclohexanamine, 1104 of cyclooctane, 280

of cyclopropanecarboxylic acid, 28 1-282 of dimethylbenzenes, 1029

of N,N-dimethylmetl~anamide, 1171 ethanal in tetrachlorometlzane, 794 ethanoic acid in tetrachloromethane, 794 ethanol in tetrachloromethane, 794

of ethynylbenzene, 356 N-methylbenzenamine, 1104 of methylbenzenes, 1028

of methylcyclohexane, 280 of octane, 279

of N-phenylethanarnide, 1171 of propanamide, 1171

of 2-propanone, 273

of 2,2,4-trimethylpentane, 279 of tropylium ion, 1315

Ingold, C. K., and nucleophilic substitution mechanisms, 22 1

Inhibitors, of chain reactions, 95 of radical polymerization, 1449

Insect pheromones, isomerism and activity of, 141 Insecticides, aryl halides for, 561

examples of, 1328 Insulin, function of, 1249

properties, 1250

Interelectronic repulsions, theoretical calculations and, 982

International Union of Pure and Applied Chemistry nomenclature (see IUPAC rules)

Intersystem crossing, definition of, 1374-1375 of diphenylmethanone, 1379

of methanal, 1374-1375 Inversion, of amines, 11091110

in S, reactions (see Nucleophilic displacement reactions)

Invertase, 930

Iodination, of arenes, 10441046

Iodine chloride, addition to alkenes, 379 Iodine, addition to alkenes, 379

addition to cyclohexene, 367

charge-transfer complex with cyclohexene, 367 Iodobenzene, electronic absorptions of, 1032-1033

preparation of, 10461047 N-Iodobutanimide and hydrogen fluoride, in

additions to alkenes, 380

1-Iodo-2,2-dimethylpropane,rearrangements in solvolysis of, 250

Iodoethane, nrnr spectrum of, 316-3 18 Iodoform, 746

Iodomethane, amines from, 1125 electronic spectrum of, 289

1-Iodopropane, microwave spectrum of, 271 Iodopsin, 1416-1417

Ion-cyclotron resonance, elements of, 267, 13641365

gas-phase acidities from, of alcohols, 1364 of alkynes and water, 437

of carboxylic acids, 802

halide displacement reactions in, 1365 nitrogen and xenon fixation in, 1365 uses of, 1364-1365

Ion-exchange chromatography, for amino acids, 12191220

for protein separations, 1248 synthesis of resins for, 1221

Ionization equilibria, of amino acids, 12121215 Ionizing power, of solvents, 237-239

Ions, solvation of, 237-238

Ipso substitution of arenes, 1066-1068

Iron compounds, ferrocene as, 1369, 15041506 Mijssbauer spectroscopy of, 1359

Iron tricarbonyl, 1,3-butadiene complex of, 152' cyclobutadiene complex of, 1359, 1507 cyclooctatetraene complex of, 1359 norbornadiene complex of, 1510

Isobutane (see 2-Methylp'ropane)

Isobutyl alcohol (see 2-Methyl-1-propanol) Isobutylene (see 2-Methylpropene) Isocitric acid, in citric acid cycle, 951-954

Isocyanates, carbamic acids from, 1155-1 156 in Curtius degradation, 1156

in Hofmann degradation, 1155-1 156 Isoeugenol, 1327

Isoleucine, properties of, 1208

Isomerism, cis-trans, 111114, 475-476, 511, 885-887

and sense of taste and smell, 140-141 configurational, 114

conformationd, examples of, 121-125, 448-463, 469-474, 480-48 1, 13451347

diastereomers, 133139

geometric, 111

optical, of 2-butanol, 119-120 configurations of, 119, 874-877 conventions for, 119, 879-884 D,L convention for, 131139 Fischer projections for, 128-159 isomer numbers, 134139

representations for, 119, 127, 128-139 resolution and determination of purity of,

866-873

and rotation of polarized light, 118-1 19, 862-866

and taste and odor, 140-141 of threonine, 133-135

types of, 44-45 Isomers, constitutional, 45

position, 44-46 structural, 45

Isoniazid, as carcinogen, 1164

Isonicotinic acid hydrazide, as carcinogen, 1164 Isooctane (see 2,2,4-Trimethylpentane) Isopentenyl pyrophosphate, as biological isoprene

unit, 1463, 1483-1485 Isophthalic acid, polyesters from, 1440 Isoprene (see 2-Methyl-1,3-butadiene)

Isoprene rule, basis of, 14621463, 14831488 definition of, 68

3-methyl-3-butenylpyrophosphate and, 1463, 1483-1485

Isoprenoid compounds, of animal origin, 1469 biosynthesis of, 14831488

structures and types of, 1462-1469 Isopropyl (see 1-Methylethyl) Isopropyl alcohol (see 2-Propanol)

Isopropylbenzene [see (1-methylethy1)benzene)l 4-Isopropyltropolone, 1314

Isotactic polymers, 1430-1435

Isotope effect (see Kinetic isotope effect)

IUPAC rules of nomenclature, for acyl halides, 198 for acids, 195

for alcohols, 191

for aldehydes, 192193

for alkanecarbonyl groups, 196 for alkanes, 51-57

for alkanoyl groups, 193 for alkenes, 59-61

for alkoxy groups, 192

for alkoxycarbonyl groups, 197198 for alkyl halides, 56

for alkyl radicals, 52-56 for alkynes, 61-62

for amides, 199, 1169 of amine salts, 1102

for amines, 200-201, 1100-1102 for amino groups, 201

for anhydrides, 198

of arenes, 62-64, 1024-1025

for benzene and its derivatives, 61-63, 10241025

for benzenols, 191 for carboxamides, 199

for carboxylate groups, 195