NDEX

A b initio calculations, for ethene, 180- 182 for hydrogen, 981-982

Abietic acid, 1469 Absolute configuration (see also Chirality), of

amino acids, 877 definition of, 874-877 Fischer projections and, 875-877 of glyceraldehyde, 875 optical rotation and, 874-875 optical rotatory dispersion and, 892-893 of tartaric acid, 876

Absorption spectra (see Infrared, Nmr, Raman, etc.)

Accelerators of vulcanization, 1429- 1430 Acenaphthene, from coal tar, 1080 Acetaldehyde (see Ethanal) Acetaldol (see 3-Hydroxybutanal) Acetals, from alcohols and carbonyl compounds,

62 1-624 equilibrium in formation of (table), 624 as ethers, 667 hydrolysis of, 624 mechanism of formation of, 622-624 protecting groups for carbohyl functions,

715-716 as protecting groups for OH, 652-653

Acetamide (see Ethanamide) Acetanilide (see N-Phen ylethanamide) Acetic acid (see Ethanoic acid) Acetic anhydride (see Ethanoic anhydride) Acetoacetate decarboxylase, characteristics of, 1285 Acetoacetic acid (see 3-Oxobutanoic acid) Acetoacetic ester ketone synthesis, 833-834 Acetoacetic ester synthesis (see 3-Oxobutanoic

esters)

Acetoacetic esters (see 3-Oxobutanoate esters) Acetogenins, 148 1- 1482 Acetone (see 2-Propanone) Acetone cyanohydrin (see 2-Hydroxy-2-

methylpropanenitrile) Acetonylacetone, properties and reactions of, 778 Acetophenone (see Phenylethanone) Acetyl bromide (see Ethanoyl bromide) Acetyl chloride (see Ethanoyl chloride) Acetyl coenzyme A (see Ethanoyl coenzyme A) Acetyl nitrate, 1043 Acetylacetone (see also 2,4-Pentanedione),

properties and reactions of, 737-777 Acetylcholine chloride, 1099 Acetylcholinesterase, serine function in, 1265- 1266 Acetylene (see Ethyne) Acetylenes (see Alkynes) N-Acetylglycine, 1222 Acetylketene (see Diketene) Achiral, definition of, 1 16 Aci forms of nitro compounds, 1195-1196 Acid anhydrides (see Carboxylic acid anhydrides) Acid catalysis, of acetal and ketal formation,

622-624 of alcohol dehydrations, 630-632 of alcohol reactivity in S, reactions, 232-234 of aldehyde and ketone halogenations, 742-745 of alkene hydration, 368-371 of alkene polymerizations, 393-395 alkyl halides from alcohols and, 626 of alkylarene rearrangements, 1050 of alkylation of arenes, 1048 of amide hydrolysis, 1182 of amine hydrogen exchanges, 1105-1 106 of amine rearrangements, 11;2

of aromatic substitution, 1041 of carboxylic acid reactions, 805-808 of deuterium exchange of arenes, 1052 of elimination reactions, 25 1 of en01 and keto equilibrium, 828 of enolization, 739 of ester formation, 6 15-6 18 of hemiacetal and hemiketal formation, 622-624 of imine formation, 697-699 of mercuration of arenes, 1058 of nitration, 1042 of nitrile hydrolysis, 1178 of oxacyclopropane ring openings, 664-665 of N-substituted arenamines, 1 139- 1 140

Acid chlorides (see Acyl chlorides) Acid halides (see Acyl halides) Acid strength, correlation with leaving-group

reactivity, 232-233 Acid strengths, of inorganic acids in various

solvents, 370-37 1 Acid-base equilibria, 41-42, equations for,

209-2 1 1 formulation of, 208-2 1 1

Acidity, of hydrocarbons (table), 1322 Acids, carboxylic (see Carboxylic acids) ACP, 1481 Acridine dyes, 1406 Acridine, from coal tar, 1080 Acrolein (see 2-Propenal) Activated complex (see Transition state) Activation energy, and bond energies, 96-97

concept of, 82-83 and heat of reaction, 96-98

Acyl azides, amides from, 1177-1 178 tert-butoxycarbonylation of amines with, 1 160 in Curtius degradation, 1 156 as functional derivatives of carboxylic acids, 818 preparation of (table), 858

Acyl carrier protein, 1481 Acyl chlorides, from carboxylic acids, with

phosphorus chlorides, 809 with thionyl chloride, 809

with Grignard reagents (table), 579, 583-584 Acyl groups, IUPAC rules of nomenclature for, 196 Acyl halides, acyl azides from, 858

in acylation of arenes, 1051-1053 acylation of enolate anions, 835 acylation of ferrocene with, 1506 from acyltetracarbonylferrates, 15 16 from acylzirconocenes, 15 14 alcohols from, with Grignard reagents, 609

by hydride reduction, 824-825 aldehydes from, by Rosenmund reduction, 728 amides from, 858, 1121-1 122, 1177-1 178 amines from, by Curtius degradation, 1 150,

1153, 1156 with amino acids, 1222 anhydrides from, 857 carboxylic acids from, 855 carboxylic esters from, 856 with diazomethane, 692-693, 1200 esterification of, 6 15-6 18

as functional derivatives of carboxylic acids, 8 18 with Grignard reagents, 823-824 l~ydrolysis of, 820 infrared frequencies, 680 IUPAC rules of nomenclature for, 198 ketones from, with alkylcadmiums, 584

from alkylcoppers, 584 with alkylzirconocenes, 15 14- 15 15 with cadmium alkyls, 73 1

preparation of (table), 557 Ti-) reduction to aldehydes, 719

Acyl hydrazides, amines from, by Curtius degradation, 1 150, 1 156

Acyl nitrates, with arenes, 1043 Acyl nitrenes, in Curtius degradation, 1156

in Hofmann degradation, 1 155- 1 156 Acyl peroxides, decarboxylation of, radicals

from, 812 Acyl phosphates, in biochemical esterifications,

636-637 Acylation, of amines, 1 121- 1 122

of arenes, 105 1-1053 Acyltetracarbonylferrates, 15 16 Acylzirconocenes, preparation and reactions of,

1514-1515 Adamantane, structure of, 701 Addition, definition of, 42 Addition polymerization (see Polymerization,

addition) Addition reactions, to alkenes (see also

Alkenes), reagents for (tables), 379-380, 389 of carbon-carbon multiple bonds, reactivity in,

358-359 energies of, 358-359

to carbonyl compounds (see Aldehydes, Esters, etc.)

1,4-Additions, to alkadienes, 489-490 Michael type of, 770, 844-845 to unsaturated acids, 840-841

Adenine, adenosine from, 926 as DNA component, 1272-1277 in prebiotic evolution, 1283-1284 in RNA, 1278

Adenosine, in prebiotic evolution, 1283-1284 structure of, 926

Adenosine diphosphate, in coenzyme A, 838 Adenosine phosphate esters, formation and

hydrolysis, 635-637 in biochemical esterifications, 635-637

Adenosine triphosphate, from adenosine diphosphate, 649

in photosynthesis, 941-943 with vitamin B,,, 1526

Adipic acid (see Hexanedioic acid) ADP (see Adenosine phosphate esters) Adrenal cortex hormones, 1473 Adrenalin, 1099 Affinity chromatography, for protein

separations, 1248 Aflatoxin B 1, as carcinogen, 1 164 Aflatoxins, 1163 Aglycones, 925-928

Alanine, chiral forms of, 132 properties of, 1208

Alathon, 1432 Alcohols, acetal protecting groups for, 652-653

acetals and ketals from, 621-624 acid-base equilibria of, 41 acidic properties of, 6 12-613 acidities of (table), 736-738 addition to alkenes, 379 from aldehydes and ketones by reduction

(table), 705-710 aldehydes from, by oxidation, 727 from aldol addition products, 759 alkenes from, 630-632 from alkenes, by hydration, 608-609

by hydroboration, 608 by hydroformylation, 723

alkoxides from, 6 1 1-6 12 alkyl halides from, with hydrogen halides,

625-627 with phosphorus halides, 627 with thionyl halides, 626-627

from alkylzirconocenes by oxidation, 15 14 amines from, 1 125-1 126 with amino acids, 122 1- 1222 in arene alkylations, 1048 basic properties of, 613-614 biological oxidation of, 644-646 carbon-oxygen bond cleavage of, 625-637 from carbonyl compounds, by borane

reduction, 610 and Grignard reagents, 608-609, 823-824 by hydride reduction, 610, 824 by hydrogenation, 6 1 1 by Meerwein-Ponndorf-Verley reduction, 6 1 1

chiral, racemization mechanisms of, 897 chromic acid oxidation of, 640-642 dehydration of, acid catalyzed, 25 1, 632-633

rearrangements in, 632-633 with diazomethane, 1199 electronic spectra of, 605 electrophilic reactions of, halide formation,

625-627 1,2-elimination reactions of, 630-632 ester protecting groups for, 652 esterification of, 615-618 esters from, with acyl halides and

anhydrides, 822 with ketene, 771

from esters, by hydrogenation, 825 by sodium and alcohol reduction, 825

ether protecting groups for, 651-652 ethers from, 655 from Grignard reagents, 577-58 1 from Grignard reagents and oxygen, 586-587 from halides, by S,1 and SN2 displacement,

213-217 hydrogen bonding of, 600-605 hydrogen exchange of, 605 industrial preparation of, 607 infrared spectra of, 602-604 infrared stretching frequencies for, 276-277

IUPAC rules of nomenclature for, 191 ketones from, by oxidation, 730 mass spectra of, 607 in natural products, 599 nucleophilic reactions of, acetal and ketal

formation, 62 1-624 with alkyl halides, 6 14-6 15 ester formation by, 6 15-6 18

from organoboranes, 427-430 from oxacyclopropanes, and Grignard

reagents, 609 by hydride reduction, 610

oxidation of, industrial uses of, 639 types and products of, 638-646

permanganate oxidation of, 643 phosphate esters of, biochemical derivatives

of, 635-637 formation of, 634-635 hydrolysis of, 635-637

physical properties of (table and graph), 73, 600-602

preparative methods for (table), 607-612 protecting groups for OH of, 520-530,

65 1-653 proton exchange in, 3 11-313, proton nmr spectra of, 605 radical-chain addition to alkenes and

akynes, 389 by reduction of carbonyls, Grignard reagents

and, 582 resolution of chiral forms of, 868-869 sulfate ester formation from, 628-629 sulfonate ester formation from, 629 uses of, 599 as water derivatives, 600 water solubilities of, 73, 600-602

Aldaric acids, 9 12 Aldehyde-ammonia adducts, 700 Aldehydes, acetal formation from, 621-624

from acyl halides, by hydride reduction, 728 by Rosenmund reduction, 728

addition reactions to alkenols and alkenones, 769

additions to, of alcohols, 694 of carbon nucleophiles, 689-693 of enolate anions, 749-754 general characteristics of (table), 685-689 of Grignard reagents, 577-580 of hydrogen halides, 703-704 of hydrogen sulfite, 695 of nitrogen nucleophiles (table), 697-703 table of examples, 688-689 of thiols, 695 of water, 646-647, 673-674, 694 of ylides, 691-692

from alcohol oxidations, with chromic acid, 640-64 1

by Oppenauer method, 727 with methylsulfinylmethane, 7 18-7 19 with oxygen, 639

alcohols from, by Meerwein-Ponndorf-Verley reduction, 6 1 1

with Grignard reagents, 608-609 by reduction, 6 10-61 1

from alcohols, and aluminum alkoxides, 727 and chromic acid, 640, 727 by Meerwein-Ponndorf-Verley, 727 by oxidation, 639-640, 718, 727

from aldehyde derivatives, by hydrolysis, 729 aldol additions of, 749-752, 755-757, 759-761 from 1,2-alkanediols, by oxidation, 7 17, 727

by rearrangement, 720 from alkenes, by carbonylation of alkylboranes,

725-726 by hydroboration and carbonylation, 729 by hydroformylation, 722-723, 729, 15 18- 1520 with ozone, 727

from alkyl halides, by methylsulfinylmethane oxidation, 7 18

from alkynes, by hydration, 729 from amides, by hydride reduction, 728 amines from, 1148, 1154 amino acids from, 1225 with amino acids, deamination of, 1224

decarboxylation of, 1223- 1224 ammonia addition to, 700 azines from, 698 benzoin condensation of, 1324- 1325 bond angles in, 171-172 borane reduction of, 707-708 borohydride reduction of, 705-708 carboxylic acids from, 855 carboxylic esters from, 856 chloroethers from, 704 diazomethane reactions with, 692-693 difluoromethyl derivatives from, 13 18 from N,N-dimethylrnethanarnide, and Grignard

reagents, 729 electronic excitation of, 1375-1376 electronic spectra of, 68 1 enamines from, 702 en01 and enolate reactions of, 735-763 enolization of, acid induced, 739

base induced, 736-738 equilibrium for, 736-738, 740-741 by Grignard reagents, 582 in haloform reaction, 746-747 in halogenation, 742-745 in nucleophilic reactions, 749-754

excited states of, 1375-1376 fluorescence and phosphorescence of, 1375-1376 general characteristics of, 671-678 halogenation of, base and acid catalyzed,

742-745 mechanism of, 742-745

hemiacetal formation from, 621-624 hydration of, 647, 673-674 hydrazones from, 698 by hydroformylation, 15 18- 15 19 from hydroperoxides by rearrangement, 721-722 imines from, 697-699 infrared frequencies, 680-68 1 infrared stretching frequencies for, 276

IUPAC rules of nomenclature for, 192-193 mass spectra of, 684 Meerwein-Ponndorf-Verley reduction of,

709-710 nitriles from, 11 85 from nitriles, by hydride reduction, 728, 824 nmr spectra of, 684 from organoboranes, 428-429 oxidation of, Baeyer-Villiger, 7 13-7 14

oxygen, 7 12-7 13 permanganate, 712 peroxycarboxylic acids, 7 13-7 14 silver oxide, 712

oximes from, 698 from ozonization of alkenes, 43 1-433 physical properties of (table), 678-679 polymerization of, 696 preparative methods for (table), 717-729 protecting groups for, 7 15-7 16 proton chemical shifts, of, 3 11 radical-chain addition to alkenes and

alkynes, 389 reactivity of, and bond polarity, 674-678

and electronegative substituents, 678 reduction of, with aluminum alkoxides, 709-710

Cannizzaro reaction, 707-709 Clemmenson, 7 1 1 by Grignard reagents, 582 with hydrides (table), 705-708 by hydrogenation, 7 10 Wolff-Kishner, 71 1-7 12

semicarbazones from, 698 with sulfur tetrafluoride, 705 from triethoxymethane, and Grignard

reagents, 729 unsaturated (see also Alkenals), addition

reactions of, 768-770 1,4-additions of organometallics to, 585-586 electronic spectra of, 767 spectral properties of, 767-768

Alder, K., and [4+2] cycloadditions, 492 Aldohexoses (see Glucose, Mannose, etc.) Aldoketenes (see also Ketenes), 771 Aldol addition, alkenones from, 755-757

arnbident nature of, 75 1 in annelation reaction, 1478 cyclic products from, 758 definition and general characteristics of,

749-750 dehydration of products of, 755-757 donor and acceptor in, 753 equilibria in, 75 1-753 mechanism of, 750 methanal and benzenol, 1442 of nitro compounds, 1196 in photosynthesis, 941-943 in steroid syntheses, 1478 synthetic uses of, 757-759 thermodynamics of, 75 1-753

Aldolase, 760, 947-948 Aldonic acids, 912

Aldopentoses (see also Arabinose, Ribose, etc.), 903-908

Aldose-ketose interconversions, 9 18-9 19 Aldoses, structures and occurrence of, 903-908 Aldotetroses, determination of configurations of,

909-9 12 Alduronic acids, 912 Alginates, 937 Alkadienes, cis-trans isomerism of, 114

general characteristics of, 488-489 heats of hydrogenation of (table), 415-416 photochemical cyclization of, 1387- 1389 photochemistry of, 1387- 1389 photoelectron spectra of, 1357-1358

1,2-Alkadienes (also see Allenes), chiral forms of, 508-5 10

R,S-convention for, 884 stereochemistry of, 508-509

1,3-Alkadienes, electrophilic additions to, bromine by 1,2 and 1,4 modes, 489

hydrogen chloride by 1,2 and 1,4 modes, 489-490

kinetic vs. equilibrium control in, 490 radical addition to, hydrogen bromide in, 491

Alkadiynes, from oxidative coupling of 1 -alkynes, 44 1

Alkaloids, biosynthesis of, 1489 definition of, 1097 examples of, 1097

1,2-Alkanedials, reactions of, 774-775 Alkanedioic acids (see Dicarboxylic acids) I, 1-Alkanediols, stability of, 646-647 l,2-Alkanediols, aldehydes and ketones from, by

oxidation, 717, 727, 730 by rearrangement, 720

preparation of, 647 Alkanediols, from alkene oxidation, 6 1 1, 643

infrared spectra of, 605 properties of, 646-648 urethane foams kom, 1454- 1455

1,2-Alkanediones, reactions of, 774-775 1,3-Alkanediones, acidities of (table), 736-738

properties and reactions of, 776-777 1,4-Alkanediones, reactions of, 778 Alkanepolyols, properties of, 646-648 Alkanes, acid strengths of, aryl substituted

(table), 1322 additions to alkenes, 380 from aldehydes and ketones by reduction,

71 1-712 from alkenes, by zirconocene chlorohydride

reduction, 15 14 alkynyl halides from (table), 548, 588-589 atomic-orbital models of, 162 boiling points of (table), 70-72 bromination of 99, 100-102 chiral, racemization mechanisms for, 897 chlorination of, with tert-butyl hypochlorite,

103-104 light induced, 91-95 with sulfuryl chloride, 102- 103, 108

from coal by Fischer-Tropsch process, 723 combustion of, 74-76 densities of, 70-71 electronic spectra of, 291-292 fluorination of, 99 halogen substitution of (table), 548, 588-589 halogenation of, mechanism and procedures

for, 81-104 selectivity in, 100- 102

heats of combustion of, 76-80 heats of formation of, 86 hydrogen-transfer reactions with carbocations,

397-398 infrared stretching frequencies for,

275-276, 278-280 "iso-" names for, 54 isomerism of, 44-46 isomers of, 45-46 melting points of, 70-72 nitration of, 105, 1187 nmr spectra of, 333-334 "normal," 52 number of isomers of, 45-46 from organoboranes, 427-428 as paraffins, 73-74 physical properties of (table), 70-72 polychlorination of, 100 proton chemical shifts of, 3 10-3 1 1 reactivity of, general considerations, 73-74 as saturated hydrocarbons, 73-74 substitution on, 81

1,2,3-Alkanetriones, carbon monoxide from, 779 hydration of, 779

Alkanoic acids (see Carboxylic acids) 1,2,3-Alkatrienes, cis-trans isomers of, 5 1 1 Alkenals, addition reactions of, 585-586, 768-770

1,4-additions of organometallics to, 585-586 dipole moments of, 768 spectral properties of, 767-768

Alkene dismutation, 1520- 152 1 Alkene metathesis reaction, 1520- 152 1 Alkene oxides (see Oxacycloalkanes) Alkenes, addition of proton acids to, 367-376

addition reactions of, definition of, 350 hydrogen peroxide, 72 1

addition reactions to (tables), 379-380, 389 from alcohol dehydrations, 630-632 alcohols from, by hydration, 608

by hydroboration, 608 aldehydes and ketones from, by oxidation, 717 aldehydes from, by carbonylation of

alkylboranes, 725-726, 729 by hydroformylation, 722-723, 729, 15 18-15 19 with ozone, 727

alkane alkylation of, hydrogen transfer in, 397-398

mechanism for, 397-398 1,2-alkanediols from, with permanganate, 643 from alkynes, by reduction, 1075 allylic bromination of, with N-bromobutanimide,

542-543

4 534 l ndex

amides from, 858, 1149, 1178-1 179 mines from, 1149 atomic-orbital models of, 165- 167 bromine addition to, mechanism of,

362-364, 367 stereochemistry of, 362, 365-366

bromine substitution on, with N-brombutanimide, 103- 104

carbene additions to, 565 carboxylic acids from, 855 characteristics of additions to, 359-361 charge-transfer complexes from, 367

I

cis isomers, from hydrogenation of alkynes, 413-414

cis-trans isomers of, E,Z-convention for, 886 kinds of, 112-1 13 photochemical isomerization of, 1384- 13.86

common names for, 59-61 coupling with arenediazonium salts, 1136 electronic spectra of, 353 electrophilic additions to, mechanisms of,

359-38 1 orientation in, 373-38 1 reagents for (table), 379-380

epoxidation of, 662 equilibrium control of additions to, 374-376 ethers from, 655 excited states of, reactions of, 1387 from Grignard reagents and carbonyls, 582 halogen-substituted, orientation in additions

to, 380-381 homogeneous hydrogenation of, mechanism of,

1517-1518 hydration of, 366-372 hydroboration of, with alkyl- and dialkyl-

boranes, 423 general characteristics of, 420-424

hydroformylation, 15 18- 15 19 hydrogen bromide addition to, stereochemistry

of, 368 hydrogen chloride addition to, 367-368 hydrogenation of, catalysts for, 4 1 1-4 14,

1517-15 19 with diimide, 418-419 heats of (table), 415 homogenous catalysis of, 4 17-418, 15 17- 15 19 mechanism of, 411-413, 1517-1519 selectivity in, 4 13-414

hydroperoxides from, 72 1 hydroxylation of, reagents for, 434-437

stereochemistry of, 434-436 hypohalous acid additions to, 360, 377-378 infrared spectra of, 35 1-353 infrared stretching frequencies for, 276, 284 isomerization of, organoboranes and, 424-426 ketones from, by oxidation, 730 nmr spectra of, 353 nomenclature of, 59-61 nucleophilic addition to, characteristics of,

384-386 as olefins, 59 from organoboranes, 427

orientation in electrophilic additions to, 373-382

osmium tetroxide reaction with, 434 oxacyclopropanes from, 662 oxidation of, 43 1-437 ozonization of, 43 1-433 peroxidation mechanism of, 456 with peroxycarboxylic acids, 435-436 from phosphate esters, 634 photochemical cycloadditions of, dimeriza-

tions, 1389 with ketones, 1389 [2 + 21 type, 503

photochem~cal isomerization of, 1384-1386 photoelectron spectra of, 1357- 1358 physical properties of (table), 35 1-352 pi (n) bonds in, 165-167 pi (n) complexes from, 367 polymerization of, anionic mechanism for,

392-393 cationic mechanism for, 393-395 coordination mechanism for, 396-397, 1446 general characteristics of, 390-397, 1420,

1446- 1453 monomers for (table), 39 1, 1432- 1433 radical-chain mechanism for, 395-396,

1446- 1449, 1452- 1453 uses of products of (table), 391,

1432-1433 proton chemical shifts of, 310-3 11 radical-chain addition to, hydrogen bromide in,

386-389 orientation in, 386-389 reagents for (table), 389 stereochemistry of, 388

Raman spectra of, 284-286 reduction of, comparisons of procedures

(table), 428 with zirconocene chlorohydride, 15 14

resonance structures for, 176 Ritter reaction of, 1149, 1178-1 179 rotation about the double bond of, 167,

1384- 1386 spin-spin splittings in, 320, 325-326 sulfate esters from, 369-371 sulfuric acid addition to, 369-37 1 thermodynamic control of additions to,

374-376 triplet states of, geometry of, 1385 with zirconocene chlorohydride, 15 12-1 5 14

Alkenic hydrogens, definition of, 60 Alkenols, alkenones from, by chromic acid oxi-

dation, 642 properties of, 648-65 1

Alkenones, addition reactions of, 768-770 1,4-additions of organometallics to, 585-586 from alkenols, by chromic acid oxidation, 642 electronic spectra of, 68 1 infrared frequencies of, 68 1 spectral properties of, 68 1, 767-768

Alkenyl groups, nomenclature of, 59-60 Alkenyl halides, coupling with metals, 572-573

organometallic compounds from, 572-573 physical properties of (table), 537-538 preparation of (table), 548, 588 reactivity of (table), 589

Alkenyloxyarenes, preparation of, 1297-1298 rearrangement of, 1298

Alkoxyarenes, cleavage of, 1295 preparation of, 1294

Alkyd resins, 1439- 1440 Alkyl cyanides (see Nitriles) Alkyl halides, from alcohols, 625-627

alkylation of arenes with, 1056 from alkylzirconocenes, 15 14 amines from, 1125-1 127, 1148 azides from, 1202 with benzenolate anions, 1294 from carboxylic acids, silver salts with bromine,

813-814 carboxylic acids from, 854 carboxylic esters from, 856 chiral, racemization mechanisms of, 896 conformations of, and nmr spectra, 1345-1347 coupling and disproportiona60n with metals,

572-573 electrophilic catalysis of S, reactions of, 234 elimination reactions of, mechanisms, reagents

and stereochemistry for, 240-25 1 ethers from, 655, 1294 Grignard reagents from, 57 1-575 from Grignard reagents and halogens, 586-587 methylsulfinylmethane oxidation of, 7 18 nitrile alkylation with, 1185 nitriles from, 1 184-1 185 nitro compounds from, 1 187, 1 190- 1 19 1 nmr shifts of, 308-310 nomenclature of, 56 nucleophilic reactions of, with alcohols, 614-615

mechanisms, reagents and stereochemistry of, 213-239

Williamson ether synthesis and, 6 14-6 15 organomagnesium compounds from, 576-577 organometallic compounds from, 572-573

by halogen-metal exchange with halides, 573-574

physical properties of (table), 537-538 reactions of, 539-54 1 reactivities of (table), 539, 589 reactivity in SN1 and S,2 reactions, 224-230 reduction of, with tin hydrides, 109 silver ion catalysis of S, reactions of, 234 S,2 displacements of, with enamines, 764-765

with enolate anions, 762-763 with sulfur-stabilized carbanions, 765-766

syntheses for (table), 541, 587-589 with tetracarbonylferrate, 15 16

Alkyl phosphates (see Phosphate esters) Alkyl radicals, names for, 53 Alkyl shifts, with alkyl transition metal com-

pounds, 1510-1516, 1518-1520, 1522-1526

Alkyl sulfate esters, from alcohols, 628-629 Alkyl sulfates, in alcohol dehydrations, 630-63 1

as detergents, 628 preparation of, 629

Alkyl sulfonate esters, from alcohols, 628-629 Alkylation, of carbanions and enolate anions,

761-766 of alkenes, mechanism and uses of, 397-398 of arenes, kinetic vs. equilibrium control in, 1066 of nitriles, 1185

Alkylbenzenes, by acylation and reduction of arenes, 1052- 1053

from arene alkylations, 1047- 1050 detergents from, 1056- 1057 industrial syntheses based on, 1083 ipso nitration of, 1067-1068 from petroleum, 1079- 1083 rearrangement of, 1050

Alkylboranes, alcohols from by oxidation, 427-430 aldehydes from, with alkenes, 729 alkanes from, 427-428 amines from, 427, 430-43 1 carbonylation of, 724-726 reduction of carboxylic acids with, 810-81 1

Alkylcadmium compounds, from Grignard reagents, 584

ketone synthesis with, 584 Alkylcopper compounds, 1,4-addition of alkenones

and alkenals, 585-586 ketone synthesis with, 584 from lithium compounds, 584

Alkylmercury halides, from alkylzirconocenes, 15 14 Alkyltetracarbonylferrates, preparation and

reactions of, 1516 Alkylzirconocenes, preparation and reactions of,

1512-1515 Alkynes, acidity of I-alkynes, alkynide salts from,

437-440 in ammonia solutions, 438 gas phase vs. solution, 437-438 solvation effects and, 438-439 synthetic reactions derived from, 440-441

aldehydes from, by hydration, 729 by l~ydroboration-oxidation, 427-429

alkenes from 414, 1075 from alkynide-salt nucleophilic reactions,

440-44 1 atomic-orbital model for, 167-168 from azides, 1202 carbene additions to, 565 coupling reactions of, 44 1 electronic spectra of, 356 electrophilic addition to, bromine in, 282

characteristics of, 382-384 hydrogen fluoride in, 382 reactivity compared to alkenes in, 382 water in, 383-384

with Grignard reagents, 578 heats of hydrogenation of tiable), 4 15-4 16 hydroboration of, 422-423 hydrogenation of, Lindlar catalyst for, 414

stereochemistry of, 413-414 infrared spectra of, 356 infrared stretching frequencies for, 276

from isomerization of 1,2-alkadienes, 512-513 ketones from, by hydroboration-oxidation,

427-429 mass spectra of, 356-357 nomenclature of, 6 1-62 nucleophilic addition to, methanol in, 385 organometallics from, 574 oxidative coupling of, 441 physical properties (table), 351-352 proton chemical shifts of, 3 11 radical-chain addition of HBr, stereochemistry

of, 390 radical-chain additions to (table), 389-390 reduction to alkenes, 414, 1075

Alkynide anions, formation of, 437-441 as nucleophiles, 440-44 1

Alkynyl groups, nomenclature of, 62 Alkynyl halides, physical properties of (table),

537-538 preparation of (table), 548, 588-589 reactivity of (table), 549, 589 S,2 reactions of, 550

Allene (see 1,2-Propadiene) Allenes, cycloadducts of, 502-503

general reactions of, 5 12-5 13 hydration of, 5 12 isomerization of, 5 12-5 13 stability of, 5 12-5 13

D-Allose, structure and configuration, 905 Allyl aryl ether rearrangement, 1298 Allyl bromide (see 3-Bromopropene) Allylic halides, preparation of (table), 541-544, 588

reactivities of (table), 544-546, 589 rearrangements in reactions of, 545

Allylmagnesium bromide, nmr spectrum of, 1524 Allylnickel complexes, chemistry of, 1525- 1524 Alpha helix, peptides and, 125 1-1252 D-Altrose, structure and configuration, 905 Aluminum alkoxides, aldehydes from, with

alcohols, 727 ketones from, 730

Aluminum bromide, as catalyst of bromine addition, 16

Aluminum chloride, in acylation of arenes, 1051-1053

in alkylation of arenes, 1047-1050 ketone complexes of, 1052

Aluminum isopropoxide, in Meerwein-Ponndorf- Verley reduction, 6 1 1

Aluminum, in Ziegler polymerization, 1444 Ambrette seed, oil of, 1468 Ameripol, 1433 Amides, from acid derivatives (table), 1 176-1 178

acidity of, 1175-1 176 from acyl halides, 1177- 1178 aldehydes from, by hydride reduction, 708, 728 from alkenes, 1178 as m i n e protecting group, 1159 amines from, by hydride reduction, 824-825

by Hofmann degradation, 1 150, 11 53, 1155-1 156

by hydrolysis, 1 154

by reduction, 824-825, 1147, 1 154 from amines, with acyl halides and

anhydrides, 822 and carboxylic acid derivatives, 1 12 1-1 122,

1176-1 177 with ketene, 771

from azides, 1 177- 1 178 basicity of, 1176 from Beckmann rearrangement, 1180-1 18 1 from carbonate esters, 1177 carboxylic acids from, 854, 1177-1 178 cis-trans isomers of, 1171-1 173 coupling reactions for, with N,N-dicyclohexyl-

carbodiimide, 1240- 124 1 in peptide synthesis, 1240- 124 1

dipole moments of, 1168 from esters, 1177-1 178 geometry of, 1 167-1 168 with Grignard reagents (table), 579, 823-824 hydrogen bonding of, 11 68 hydrolysis of, 820-82 1, 1 182- 1 183 infrared spectra of, 680, 1 170-1 17 1 IUPAC rules of nomenclature for, 199, 1169 from ketones, by Haller-Bauer cleavage, 747 nitration of, 1 188- 1 190 nitriles from, 1185 from nitriles, 1178-1 179 N-nitroso compounds from, 1183, 1163 with nitrous acid, 1183 nmr spectra of, 1 172- 1 175 from oximes, 1 180- 1 18 1 in peptide structures, 1227-1228 from phenyl esters, 1177-1 178 physical properties of, 1168 planarity of, 1168 polarity of, 1168 polymers of, 118 1, 1441, 1456-1457 preparation of (table), 858, 1121-1 122,

1176-1181, 1236-1247 radical-chain addition to alkenes and

alkynes, 389 reactions of (summary), 1183 reduction to aldehydes, 708, 727 reduction to amines, 824-825, 1146- 1147 resolution of chiral forms of, 868 from Ritter reaction, 1149, 1178- 1179 solvent properties of, 1168 stabilization energy of, 1159, 1168 synthesis of, from acid derivatives (table),

1176-1 178 types of, 1 169

Amidol, 131 1 Amine oxides, alkenes from, 1143

azanols from, 1143 chiral forms of, 1143 preparation of, 1143

Amine salts, IUPAC rules of nomenclature of, 1102

Amines, acid-base equilibria of, 41 acidities of, 1095, 1120 acidities of salts of, 11 12 acylation of, 1 12 1- 1 122

alcohol comparisons with, 1095-1096 from alcohols, 1 125- 1 126 aldehyde additions of, 697-699, 702 alkylation of, 1125-1 127 from alkylation of amines and ammonia, 1149 amides from, 771, 822, 1121-1 122 from amides, by hydrolysis, 1154 m i n e function as leaving group, 1096 arnine oxides from, 1143 from ammonia and alkyl halides, 1125-1 126 base constants of (tables), 1 10 1, 11 1 1- 1 1 18 basicities of, alkanamines and, 1095- 1096,

1112-1113 arenamines and (table), 1 1 13-1 1 16 azarenes and, 1 1 17-1 1 18 cycloalkanamines and, 1 1 12-1 1 13

from Beckmann rearrangement, 1149 with benzenesulfonyl chloride, 1 122- 1 123 benzoylation of, as protecting group, 1159 benzyloxycarbonylation of, as protecting group,

1159-1160 tert-butoxycarbonylation of, as protecting group,

1159-1160 carcinogenic, 1 16 1- 1 162 chiral forms of, 1 109- 1 1 10 chiral, as resolving agents, 866-867 from Curtius degradation, 1 150, 1 156 electronic spectra of, 1105 enarnines from, 1122 enamines with aldehydes and ketones, 702 ethanoylation of, as protecting group, 1159 from Gabriel synthesis, 1148 Hinsberg test for, 1123 from Hofmann degradation, 1 150, 1155 hydrogen bonding of, 1103 imines from, 1122 infrared spectra of, 277, 1104 inversion of, 1 109- 1 1 10 IUPAC rules of nomenclature of, 200-201,

1100-1 102 ketone additions of, 697-699, 702 mass spectra of, 1106- 1108 metal salts of, benzyne generation with, 1120

enolate salt generation with, 1120 nomenclature of, 1120 as nucleophiles, 1 126- 1127 preparation of, 1120

from nitriles, by hydride reduction, 824-825 nitro compounds from, by oxidation, 1144 with nitrous acid, diazonium salts from,

1129-1 133 differentiation by, 1129 nitrogen as leaving group in, 1096 N-nitrosamines from, 1129-1 130, 1136

nmr spectra of, chemical shifts in, 1105 and hydrogen exchange, 1105 nitrogen- 14 relaxation effects on, 1 106

as nucleophiles, 1096, 1121-1 129 odors of, 1103 oxidation of, 1141-1145 phenylmethoxycarbonylation of, as protecting

group, 1159- 1160

physical properties of (table), 1 101-1 103 preparation of, by alkylation of amines,

1125-1 126 from amides, 824-825, 1 146-1 147, 1 150,

1154-1 156 Gabriel synthesis for, 1127 from nitriles, 1 146- 1 147 from nitro compounds, 1146-1 147, 115 1 by sulfonamide synthesis, 1127

protecting groups for, acylation for, 1158- 1160 alkylation for, 1157-1 158 protonation for, 1 157 sulfonylation for, 1 16 1 table of, 1236-1239

pro ton exchange in, 3 1 1-3 13 protonation of, as protecting group, 1157 from reduction, amides, 1146-1 147, 1154-1 155

azides, 1146, 1150 imines, 1146, 1148, 1154 nitriles, 1 146- 1 147 of nitro compounds, 1146- 1147, 115 1 oximes, 1146, 1148

from reductive alkylation, of aldehydes and ketones, 1148, 1154

from Ritter reaction, 1149, 1179 Schiff bases from, 1122 from Schmidt degradation, 1150, 1156 stereochemistry of, 1108-1 1 10 sulfonamides from, 1 122- 1 123 sulfonylation of, as protecting group, 1161 synthetic routes to (table), 1145- 1156 triphenylmethylation of, as protecting

group, 1158 vitamins as, 1099 water solubility of (table), 1101, 1103

Amino-acid sequencing of peptides, 1229-1234 Amino acids, abbreviations for, 1207-1210

acid-base properties of, 12 12-1215 acidic type, 1207 with aldehydes, 1223-1225 from amination of halo acids, 1225 analysis of, fluorescamine, 12 17- 12 18

ion-exchange chromatography, 12 19 ninhydrin, 1216-1218, 1221 paper chromatography and, 12 18- 12 19 thin-layer chromatography, 12 19

azarene types, 1207-1210 azlactones from, 1222 basic type, 1207 chiral, 1207 configurations, D,L conventions for, 132 configurations of, naturally occurring, 1207 deamination of, 1223- 1224 decarboxylation of, 1223- 1224 diketopiperazines from, 1222 dip-olar forms of, 12 12- 12 15 electronic spectra of, 1216 from enolate anion alkylations, 1225- 1226 equilibria of, 12 10-1215 esters from, 1221-1222 fluorescamine, reaction, 12 17 imines from, 1223- 1224

infrared spectra of, 12 15 ion-exchange chromatography, 12 19- 1220 isoelectric points of (table), 1208-1210, 12 12 isolation of, 1227 malonic ester syntheses of, 1225-1226 mass spectra of, 1216 melting points of, 12 15 metabolism of, 1224- 1225 from Michael additions, 1226 ninhydrin reaction, 12 16-1217 with nitrous acid, 1223 nonprotein examples, 12 1 1 paper chromatography, 1218-12 19 in peptides, conventions for, 1228

peptide bond of, 1228 physical properties (table), 1208-12 10, 12 15 pK values of (table), 1208-12 10 protecting groups for, in peptide syntheses,

1236- 1247 as protein constituents (table), 1206-1210 purification of, 1227 with pyridoxal phosphate, 1224-1225 reactions of, 122 1- 1225 resolution of, 1227 and tRNA, 1281-1282 solubility characteristics of (table),

1208-1210, 1215 Strecker synthesis for, 1225 substituent groups on, 1207 sulfur containing, 1207-1209 synthesis of, 1225- 1227 thin-layer chromatography of, 1219

Aminoacyl-tRNA, 128 1-1282 4-Aminobenzenesulfonamide, 1 123-1 124 4-Aminobenzenol, from phenylazanol, 1 140

as photographic developer, 13 1 1 physical properties of, 1290

4-Aminobutanoic acid, and nerve impulses, 121 1 l-Aminoethanol, 700 Aminophenols (see Aminobenzenols) Aminophenylethanoic acid, synthesis of, 1225 4-Aminostilbene, as carcinogen, 1 162 Ammonia, bond angles of, 163, 168

physical properties of, 19, 239, 1101 in prebiotic evolution, 1282-1284

Ammonium polysulfide, nitro group reduction with, 1151

AMP (see Adenosine phosphate esters) Amphetamine, 867, 1098 Arnygdalin, 926, 1327 Amylase, 935 Amylopectin, 934-935 Amylose, 934 Anaesthetics, 1099 Analgesic drugs, 1098, 1328 Androsterone, structure and occurrence, 1473 Angle strain, Bredt's rule and, 484

and carbonyl reactivity, 677-678 in cycloalkanes, 448-449, 462-467 in cycloalkenes, 474-476 in cycloalkynes, 475-476

in polycycloalkanes, 482-485 Aniline (see Benzenamine) Aniline Black, 1145, 1406 Anionic polymerization, of alkenes, 392-393 Anisole (see Methoxybenzene) Annelation reaction, 1477- 1478 [IgIAnnulene, nmr spectrum of, ring current

effects on, 1034-1035, 1088 Annulenes, "bond fixation" in, 1090

bond lengths of, 1090 equilibration of, 1088 nmr spectra of, 1035, 1088 nomenclature of, 1087 substitutions of, 1088

Anomers (see also individual sugars), of D-glucose, 9 14-9 18

Antarafacial elimination, definition of, 245-246 Anthocyanins, as flower pigments, 925, 1403 Anthracene, bromination of, 1072

from coal tar, 1080 Diels-Alder additions to, 1077 electronic spectra of, 1033 physical properties of, 1027 reduction of, 1074 stabilization energy of, 985

9,lO-Anthracenedione, as dye component, 1407 Anthr aquinone, 1407, 1409 Anti conformation, definition of, 124 Antibiotics, 1097- 1099 Antibonding orbital, definition of, 156 Anticodons, of tRNA, 1279-1282 Antihistamine, 1328 Antirachitic hormone, 1472 Apoprotein, 1256 Aprotic solvents, 238 D-Arabinose, structure and configuration, 904 L-Arabinose, properties and occurrence of, 907 Arenamines, from amides, by hydrolysis, 1154

arenols from, 1293 from aryl halides, with activating groups,

1128, 1152 by benzyne mechanism, 1120, 1128, 1152

basicities of, Harnmett correlation of, 1334 table of, 11 13-1 1 16

from Beckmann rearrangement, 1153 from benzidine rearrangement, 1 153 from Bucherer reaction, 1295- 1296 as carcinogens, 1 16 1- 1 162, 1 164 from Curtius degradation, 1153, 1156 from Hofmann degradation, 1153, 1155 from nitro compounds, 1193 nitro compounds from, 1 187- 1 19 1 N-nitroso, rearrangements of, 1139-1 140 with nitrous acid, diazonium salts from, 1133

N-nitrosamines from, 1136 ring nitroso substitution in, 1136

oxidation of, 1 144- 1 145 from phenols, 1295- 1296 as polymerization inhibitors, 1449 protecting groups for, 1 157-1 16 1 quinones from, 1145

from reduction, of nitro compounds, 1 15 1 resonance in, and base strengths of, 11 13- 11 15 ring substitution reactions of, 1128-1 129 from Schmidt degradation, 1153, 1156 N-substituted, rearrangements of, 1139-1 140

Arene polyols, 1303- 1305 Arenediazonium salts (see Benzenediazonium

salts) Arenes (see also Benzene, Methylbenzene,

Naphthalene, etc.), acid strengths of alkyl (table), 1322

alkyl substituted, from coal tar and petroleum, 1079-1081

from arenediazonium salts, 1 134, 1 138 charge-transfer complexes of, 1 192- 1 193 in chlorination of alkanes, selectivity effects, 102 from coal tar, 1079-1083 cycloaddition reactions of, 1077 electronic spectra of, benzene chromophore

and, 1030-1034 benzenoid band in, 1032- 1033

halides from, 1044- 1046 halogen addition to, 1076 and Hammett equation, 1329-1337 hydrogen exchange of, 1057 hydrogenation of, 4 14 infrared spectra of, 276, 1027-1029 IUPAC rules of nomenclature for, 1024-1026 ketones from, 105 1-1053 nitration of, 1041-1043, 1058-1072, 1187-1190 nrnr spectra of, ring currents and, 1034-1035

spin-spin splittings in, 1036-1037 nomenclature of, 62-64 oxidation of, with oxygen and vanadium

catalysts, 1077-1078 from petroleum by catalytic reforming,

1079-1081 physical properties of (table), 1026-1027 picrates of, 1 192 proton chemical shifts of, 3 11 reactivity correlations of, 1329- 1337 reduction of, Birch procedure for, 1074- 1075

by hydrogenation, 1022- 1024 with sodium in alcohol, 1073-1074

side-chain derivatives of, 1316-1328 side-chain halogenation of, 546-547, 1046,

1317-1318 side-chain substituted, 1287, 1327-1328 spectral properties of, 1027- 1036 toxicity of, 1026

Arenols {see also Phenols), properties of (table), 1288-1291

Arginine, properties, 1209 Arndt-Eistert synthesis, 1200 Aromatic character, and benzene, 10, 173-174,

957-968 of dibenzenechromium, 1507 of ferrocene, 1504- 1507 of nonbenzenoid cyclic polyenes, 98 1-995,

1084-1089, 1090 Aromatic halides (see Aryl halides)

Aromatic hydrocarbons, production and uses of (tables), 1079-1083

Aromatic substitution (see Electrophilic or Nucleophilic aromatic substitution)

Aryl azides, from arenediazonium salts, 1139 Aryl ethers, cleavage of, 1295

preparation of, 1294 Aryl halides, from arene halogenations, 1039,

1044- 1046, 1070- 1072 from arenols, 1295 from benzenediazonium salts, 1134-1 136 benzyne from, 1120 nitriles from, 1 184- 1 185 nucleophilic substitution of, radical mechanism

for, 573 organomagnesium compounds from, 576-577 organometallic compounds from, by

halogen-metal exchange, 574 with metals, 572-573

physical properties of (table), 537-538 preparation of (table), 55 1-552, 589 uses of, 561

Aryl nitro compounds (see Nitrobenzene) Arylmethanes, acid strengths of (table), 1322 Arynes (see also Benzyne), from aryl halides,

558-559 Ascaridole, 1466 L-Ascorbic acid, properties of, 650

structure of, 938 Asparagine, codon for, 1282

hydrolysis of, 1229 properties, 1209

Aspartic acid, ionization equilibria of, 1214 properties, 1209

Asphalt, 74 Aspirin, 1328 Asymmetric synthesis, in aldol addition, 893-894

in biological reactions, 894 principles of, 893-894

Atactic polymers, 1430-1435 Atomic energy states, 268-269 Atomic-orbital models, ab initio calculations with,

179-182 of alkanes, 162 alkyne-alkane acidity and, 439-440 for benzene, 172- 175, 967-968 of carbonyl bonds, 675 of E2 transition state, 247 of ethane, 162 of ethene, 165-167 of ethyne, 167-168 of hydrogen, 962-963 of methanol, 164-165 for methide anion, 169 for methyl carbocation, 169 for methyl radical, 169- 170 of 1,2-propadiene, 508-509 for 2-propenyl radical, 178-178 for S, transition states of, 221, 223

Atomic orbitals, bond formation with, 155- 157, 960-966

for carbon, 154-155 designations for, 15 1 - 152 electron pairing in, 153- 154 electron probabilities and, 15 1-152 energies of, 15 1 - 153 ground-state electronic configurations of,

153-155 hybrid, sp-type, 159, 167-168

sp2-type, 160-161, 165-166 sp3-type, 160, 162

hybridization of, 159- 16 1 hydrogenlike, 151-152 order of filling, 153-155 overlap of, in bond formation, 155-161, 962-966

and bond strengths, 159-160 phases of, 156 pi (T) overlap, 165-167 promotion of electrons in, 158-160, 163-164 quantum numbers of, 15 1-152 shapes of, 151-152 sigma (o) overlap, 156-165 tau (7) bonds with, 165-167 for unshared electrons, 162-165, 168-172 valence state configurations, 158-160, 163, 168

Atomic weights, determination of, 4 ATP (see Adenosine phosphate esters) Atropine, 1097 Autoxidation, of benzenecarbaldehyde, 7 12-7 13

of ethers, 658-659 of (1-methylethyl)benzene, 72 1

Autumn crocus, 1316 Auxochromes, definition of, 1030

substituent effects of, 1402-1404 Avogadro, A., 4 Axial positions (see Cyclohexane) Azabenzene, in alkyl halide formation, 627

base strength of, 11 17-1 118 from coal tar, 1080 physical properties of, 239, 1101 stabilization energy of, 985 in sulfonate ester formation, 629

Azabenzene-chromic acid, alcohol oxidation with, 642

Azacycloalkanes, nomenclature systems for, 659-66 1

1-Aza-2-cycloheptanone, from cyclohexanone oxime, 1181

polymer from, 1181, 1433, 1441 Azacyclohexane, physical properties of, 1101 Azacyclohexanes, inversion rates of, 11 10 Aza-2,4-cyclopentadienes, from

1,4-alkanediones, 778 1-Aza-2-cyclopentanone, solvent properties

of, 1168 Azacyclopropanes, inversion rates of, 11 10 1-Azanaphthalene, base strength of, 11 18

from coal tar, 1080 Azane oxides (see also Amine oxides), 1143 Azanols, in arnine oxidations, 1 143- 1 144 Azanyl hydrogen sulfate, organoborane reactions,

427, 430-43 1 Azarenes, base strengths of, 1 1 17- 1 1 18

from diarylethanediones, 1326 Azeotropes, definition of, 258 Azides, from alkyl halides, 1202

mines from, 1146, 1148, 1150, 1153, 1156, 1202 from arenediazonium salts, 1139 explosive properties of, 1202 from hydrazines, 1197, 1202 reduction of, 1202

Azine (see Azabenzene) Azine dyes, 1406 Azines, from aldehydes and ketones, 698 Azlactones, from amino acids, 1222 Azo compounds, from arenediazonium

couplings, 1 137 from hydrazines, 1197 initiation of polymerization with, 1447 preparation of, 1 194, 1 198 radical decomposition of, 1198

Azobenzene, as dye component, 1407 preparation of, 1 194 reduction of, 1194 thermal decomposition of, 1198

Azobisisobutyronitrile, initiation of polymerization with, 1447

Azomethine dyes, 14 14 Azonia nomenclature, 1102 Azoxybenzene, from nitrobenzene, 1194 Azulene, basicity of, 1085

polarity of, 1084 rearrangement of, 1084 stabilization energy of, 985 substitution reactions of, 1084

Bachmann, W. E., and equilenin synthesis, 1495 Back bonding, 1509-15 10 Back-side approach, 2 19-223 Bactericides, aryl halides for, 56 1 Baeyer, A., and strain in cycloalkanes, 463-465 Baeyer-Villiger oxidation, of aldehydes and

ketones, 712-713 Bakelite resins, 1442-1443 Ball-and-stick models, of carbon compounds,

34-35 of cis-trans isomers, 1 12- 1 14 of conformations, 122-123, 449-452 Paterno and, 3

Bartlett, P. D., and carbocation hydrogen-transfer reactions, 397-398

Barton, D. H. R., and conformational analysis, 124, 450

Base catalysis, of aldehyde and ketone halogenations, 742-745

of aldol additions, 749-754 of aldose-ketose interconversions, 9 18-9 19 of chiral ketone racemization, 896 of dehydration of aldols, 755-756 of en01 and keto equilibria, 828

of enolization, 736-738 of hydrogen cyanide to aldehydes and ketones,

689-690 of nitrile hydrolysis, 1178 of unsaturated alkanoic acid rearrangements, 841

Base strengths, standard expressions for, 11 1 1-1 1 12 Bay, oil of, 1462, 1464 9-BBN, from 1,5-cyclooctadiene, 423 Beckmann rearrangement, amides from, 1149,

1153, 1180-1181 arnines from, 1149, 1153

Beer-Lambert law, 291, 293 Benadryl, 1328 Benzal chloride (see Dichloromethylbenzene) Benzal fluoride (see Difluoromethylbenzene) Benzaldehyde (see Benzenecarbaldehyde) Benzedrine, 1098 Benzenamine, from aryl halides, 557-558, 1 128

azo compounds from, 1194 ' basicity, electronic effects on, 1 113-1 1 16

Hammett correlation of, 1334 1,4-benzenedione from, 1 145 bromination of, 1128 from bromobenzene, 557-558 electronic absorptions of, 1030- 1033, 1402- 1403 hydrogenation of, 1073 from nitrobenzene, 1 193 oxidation of, 1 144- 1 145 physical properties of, 1 101 stabilization energy of, 986 substituted, basicities of (table), 11 14-1 116

Benzenamines, from aryl halides, 557-558, 1 128 Benzene, acylation of, 105 1-1053

alkyl substituted, nitration of, 1042-1043 alkylation of, 1047- 1050 atomic-orbital model of, 172-1 74, 968-969 benzenol from, 129 1- 1293 Birch reduction of, 1074- 1075 bond lengths in, 987 bromination of, 1044-1045 bromine addition to, 967-968 bromine substitution of, 552, 1044-1045 charge-transfer complexes of, 1 192-1 193 chlorine addition to, 1076 chlorobenzene from, 129 1 chloromethylation of, 1054, 13 19 chlorosulfonation of, 1056 chromium derivative of, 1506- 1507 as chromophore, 1402 1,4-cyclohexadiene from, 1074- 1075 delocalization energy of, 173- 176 derivatives of, IUPAC rules of nomenclature

for, 1024- 1026 spectral properties of, 1027-1037

deuterated, preparation of, 1057 Dewar resonance structures for, 175-176 electrophilic substitutions of (table), 1037- 1040 fluorescence and phosphorescence of, 1375 Friedel-Crafts alkylation of, 1047- 1050 general reactions of, 967-968 geometry of, 173, 966 GVB treatment of, 983-984

halogen additions to, 1046 heat of combustion of, 174, 967 heat of hydrogenation of, 967 hexachloride of, 1066 and 1,3,5-hexatriene, 967-968 hydrogen exchange of, 1057 hydrogenation of, 967-968, 1072- 1073 industrial syntheses based on, 1082 iodination of, 1044-1045 Kekuli: and, 10 ketones from by acylation, 105 1- 1053 mercuration of, 1058 molecular-orbital treatment of, 969-97 1 nitration of, 1041 with nitric acid, 967-968 nomenclature of, 62-64 oxidation of, with oxygen and vanadium

catalysts, 1077- 1078 with ozone, 967-968, 1078

from petroleum, 1079- 1083 photoelectron spectra of, 1357 physical properties of, 239, 1027 radical anion of, 1075 representations of, 974 resonance treatment of, 173-177, 972-974 sandwich compound of, 1506- 1507 stability of, 173-175 stabilization energy of, 967-968, 985 structure of, 10- 1 1, 966-967 structure problem presented by, 9- 11 substituted, orientation effects in, 1058-1068 substituting agents for, 1037-1058 sulfonation of, 1055-1057 with tetracyanoethene, 968 valence-bond treatment of, 972-975

Benzenecarbaldehyde, aldol addition of, with 2-propanone, 756

autoxidation of, 712-713 benzoin from, 1324 from chloromethylbenzene, 13 18 from dichloromethylbenzene, 13 18 difluoromethylbenzene from, 13 18 electronic absorptions of, 1030- 103 1 glycosides of, 926, 1327 Hammett reactivity correlations with, 1334 physical properties of, 679 with sulfur tetrafluoride, 13 18

Benzenecarboxylic acid, from oxidation of methylbenzene, 13 17

physical properties of, 792 substituted, acidities of (table), 1327-1333 from trichloromethylbenzene, 13 18

1,4-Benzenediamine, arenecarboxamide polymers from, 1456-1457

base strength of, 11 15 ladder polymers from, 1456- 1457 from phenyldiazane, 1 140

l,2-Benzenediarnines, quinoxalines from, 1326 1,4-Benzenediamines, as color developers,

1413-1414 Benzenediazonium salts, aryl azides from, 1138

azo compounds from, 1137

Index

copper catalysis of reactions of, 1134-1136 coupling to biaryls, 1138 coupling with alkenes, 1 135-1 136 cyanoarenes from, 1134 decomposition of, 1133 diazo coupling of, 1137- 1 138 diazotate salts from, 1139 hydrazines from, 1 138 with hypophosphorous acid, 1 189- 1 190 iodide reaction with, 1136 with I -naphthalenol, 1300 nitriles from, 1185 nitro compounds from, 1191 phenyl cations from, 1133, 1135 phenyl radicals from, 1 135- 1 136 preparation of, 1133 reactions of (table), 1138-1 139 reduction of, 1134, 1 138, 1 189- 1 190 triazenes from, 1137

1,2-Benzenedicarbonitrile, copper phthalocyanine from, 1408

1,2-Benzenedicarboxyhydrazide, 1 127 1,2-Benzenedicarboximide, acidity of, 1 176

hydrazine cleavage of, 1127 hydrolysis of, 1127 in Gabriel m i n e synthesis, 1127 synthesis of, 850

1,2-Benzenedicarboxylic acid, anhydride from, 847 properties and uses of, 849

1,3-Benzenedicarboxylic acid, polyesters from, 1440 1,4-Benzenedicarboxylic acid, 1,4-di-

(trifluoromethyl) benzene from, 13 18 epoxy resins from, 1444-1445 polyesters from, 1438 polymers from, 1433, 1456- I457 properties and uses of, 849 with sulfur tetrafluoride, 13 18

1,2-Benzenedicarboxylic anhydride, from naphthalene oxidation, 1078

polyesters from, 1439-1441 uses of, 1078

1,2-Benzenediol, 1,2-benzenedione from, 1303 from 1,2-dichlorobenzene, 1303 physical properties of, 1289

1,3-Benzenediol, from 1,3 -benzenedisulfonic acid, 1304

physical properties of, 1289 1,4-Benzenediol, 1,4-benzenedione from, 1303

from 1,4-benzenedione, 1306- 1307 electrode potential of, 1306 as photographic developer, 13 10-13 11 physical properties of, 1289 as polymerization inhibitor, 1449 substituted, from 1,4-benzenedione additions,

13 11-13 12 1,2-Benzenedione, from 1,2-benzenediol, 1303

as quinone, 1305 1,4-Benzenedione, additions to, of

1,3-butadiene, 1312 of ethanoic anhydride, 13 1 1 - 13 12 of hydrogen chloride, 13 11-13 12

from benzenamine, 1145, 1303

from 1,4-benzenediol, 1303 1,4-benzenediol from, 1303 from benzenol, 1300- 130 1 complex with 1,4-benzenediol, 1307 electrode potential of, 1306 with hydroquinone, 1307 in photographic development, 13 11 quinhydrone from, 1307 reduction of, 1306- 1308 semiquinone from, 1307

1,3-Benzenedisulfonic acid, 1,3-benzenediol from, 1304

Benzenesulfonic acid, from benzene, 1055, 129 1 benzenol from, 1291 preparation of, 1055-1056

Benzenesulfonyl chloride, m i n e protecting groups from, 1161

benzenesulfonic acid from, 1056 in Hinsberg test for arnines, 1123 preparation of, 1056 sulfonamides from, 1 122- 1 123 sulfonate esters from, 629

1,2,4,5-Benzenetetracarboxylic acid, ladder polymers from, 1456

polyimides from, 1456 1,2,4,5-Benzenetetracarboxylic dianhydride,

polyesters from, 1440 1,2,3-Benzenetriol, from

2,3,4-trihydroxybenzenecarboxylic acid, 1304 1,2,5-Benzenetriol, ethanoate ester, 13 12 1,3,5-Benzenetriol, from

2,4,6-trinitrobenzenecarboxylic acid, 1304 Benzenol, acidity of (table), 736-738, 1293-1294

aldol type reactions of, 1300 Bakelite resins from, 1442- 1443 from benzene, 129 1-1292 from benzenediazonium salts, 1 133, 1 136 14-benzenedione from, 1300- 130 1 from benzenesulfonic acid, 129 1 bromination of, 1296- 1297 carboxylation of, 1297- 1298 from chlorobenzene, 557, 1291 from coal tar, 1081, 1291 with diazomethane, 1294 with dichlorocarbene, 1299 electronic absorptions of, 1030- 1032, 1402- 1403 as enol, 651 esters from, 1294 ethers from, 1294 hydrogenation of, 1073 from hydroperoxide rearrangement, 721-722 2-hydroxybenzenecarbaldehyde from, 1299 2-hydroxybenzenecarboxylic acid from,

1298- 1299 from isopropylbenzene, 1293 IUPAC rules of nomenclature for, 191 Kolbe-Schmitt reaction of, 1298-1299 with methanal, 1300, 1442-1443 from methylbenzene, 1292- 1293 oxidation to quinone, 1300- 130 1 physical properties of, 1289, 1291 quinone from, 1300-1301

radical from, 1301 sodium salt, electronic absorptions of, 1032 stabilization energy of, 986, 1293

Benzhydrol (see Diphenylmethanol) Benzhydryl derivatives (see Diphenylmethyl

derivatives) Benzidine, as carcinogen, 1162

from hydrazobenzene, 1140 rearrangement of, 1140

Benzil, as 1,2-dione, 774-775 formation of, 1325 quinoxalines from, 1326 rearrangement of, 775, 1325-1326

Benzilic acid rearrangement, of diarylethanediones, 775, 1326

Benzocaine, 1328 Benzoic acid (see Benzenecarboxylic acid) Benzoin, formation of, 1324-1325

oxidation to benzil, 1325 Benzoin condensation, 1324- 1325 Benzophenone (see Diphenylmethanone) Benzopinacol, 1382- 13 83 Benzoquinone (see 1,4-Benzenediol) Benzotrichloride (see Trichloromethylbenzene) Benzotrifluoride (see Trifluoromethylbenzene) Benzoyl chloride (see Benzenecarbonyl chloride) Benzoyl nitrate, 1043 Benzoyl peroxide, initiation of polymerization

with, 1447 Benzyl alcohol (see Phenylmethanol) Benzyl bromide (see Bromomethylbenzene) Benzyl chloride (see Chloromethylbenzene) Benzyl halides (see Phenylmethyl halides) Benzyloxycarbonyl groups, as protecting group for

mines, 1159- 1160, 1237- 1239 Benzylpenicillin (see Penicillin G) Benzyne, from amine salts, with aryl halides, 1120

from 2-benzenediazoniumcarboxylate, 559 cycloadditions of, 559 1,3-cyclopentadiene addition, 576 as intermediate in aryl halide reactions, 557-559 nucleophilic additions to, 558-559 from organometallic reactions, 575

Bercaw, J. E., and nitrogen fixation by zirconocene, 1508

Bergamot, oil of, 1468 Bernal, J. D., and structures of steroids, 1476-1477 Beryllium hydride, bonding in, 157- 159

properties of, 19 BHC, 1076 Biacetyl, 774 Biaryls, from arenediazonium salt couplings, 1138

chiral forms of, 5 10-5 1 1 Bicyclo[l. l.O]butane, from 1,3-butadiene, 1389

physical properties and strain energy of (table), 483

Bicyclo[4.4.0]decane (see Decalin) Bicyclo[2.2.1]-2,4-heptadiene (see Norbornadiene) Bicyclot2.2. llheptane, exo-endo isomerism of

derivatives of, 497 synthesis of, 526-527

Bile acids, 1475- 1477

Bimolecular reactions, 2 16 Bioluminescence, 1397- 1399 Biosynthesis, of alkaloids, 1489

of aromatic rings, 148 1-1482 of cephalosporins, 1492 of cholesterol, 1486-1488 of fatty acids, 1480-1481 of penicillins, 1492 of prostaglandins, 1493- 1494 of terpenes, 1483-1485

Biotin, in fatty acid synthesis, 1483 Biphenyl, electronic absoprtions of, 103 1

from Grignard coupling, 1505 quinone of, 1306 stabilization energy of, 985

4,4'-Biphenyldione, as quinone, 1306 Biphenylene, stabilization energy of, 985 Biphenyls, chiral forms of, 5 10-5 1 1 Biradical intermediates, in [2 + 21 cycloadditions,

1014-1017 Birch, A. J., and acetogenin hypothesis, 148 1-1482

and reduction of arenes, 1074-1075 Bisabolene, 1468 Bis(cyclooctatetraene)uranium, 1508 Bis(pentenylnickel), 1508 Bisphenol A, epoxy resins from, 1444- 1445

polyesters from, 1439 Bisulfate (see Hydrogen sulfate) Bisulfite (see Hydrogen sulfite) Bloch, K., and fatty acid biosynthesis, 1480 Block polymers, 1452, 1454-1455 Bohr frequency condition, 269 Bombykol, structure and activity of, 141 Bond angles, C-C-C in simple compounds,

34-36 in carbocylic rings, 448, 462-465, 484 and electronic repulsions, 157-164, 169-172

Bond energies (see also Bond-dissociation energies), accuracy of, 79-80, 465

average values of, 78-80 and chlorination of methane, 85 of cycloalkanes, 465 definition of, 76-79 and reactivity, 96-97 resonance effect on, 177-178 tables of, 77, 92, 674

Bond formation, with atomic orbitals, 155- 157 by pi (n) overlap, 165-167 by sigma (o) overlap, 156-165

Bond lengths, and bond energies, 960-961 of carbon-carbon bonds, 36-37 of carbon-chlorine bonds, 37 of carbon-hydrogen bonds, 37 and double-bond character, 987 and hybridization (table), 987-988

Bond strengths, correlation with leaving group reactivity, 232-233

Bond-dissociation energies, definition of, 93 table of, 92

Borane, reduction of carbonyl compounds with (table), 707-708

Borane reductions, alcohols from, 6 10

Boranes, additions to alkenes, 380, 420-429 carbonylation of, 724-726 oxidation of, 427-43 1

Boron hydrides (see Hydroboration) Boron trifluoride, ether complexes of, 656 Bragg, W. and L., and x-ray diffraction structure

determinations, 1249 Bredt's rule, and polycycloalkenes, 484 Bridgehead double bonds, Bredt's rule and, 484 Bright scarlet, 1407 Bromination, of alkanes, selectivity in, 101-102

of arenes, 1044-1045, 1070-1072 of hydrocarbons, with N-bromobutanimide,

103-104 Bromine, addition to ethyne, 382

additions to alkenes, 360-367, 379 aluminum bromide catalysis of addition of, 16 azide of, addition to alkenes, 379 radical-chain addition to alkenes and

alkynes, 389 N-Bromoamides, in Hofmann degradation,

1155-1 156 Bromobenzene, amination of, 557-558

from benzene and bromine, 552 physical properties of, 538

N-Bromobutanimide (NBS, N-bromosuccinimide), in additions to alkenes, 379

allylic bromination of alkenes with, 542-543 bromination of hydrocarbons with, 103-104 and hydrogen fluoride, in additions to

alkenes, 379 with methylbenzene, 13 17

Bromocyclohexane, conformational equilibria of, 454, 457

Bromoethane, hydrolysis of, 12 structure of, 3-6

Bromoform, 746 Bromomethane, electronic spectrum of, 289

SN2 reactivity and nucleophile structure (table), 235

(Bromomethyl)benzene, from methylbenzene and tert-butyl hypobromite, 106

from methylbenzene and bromotrichloromethane, 104

l-Bromo-2-methylpropane, from hydrogen bromide and 2-methylpropene, 374-376

2-Bromo-2-methylpropane, from hydrogen bromide and 2-methylpropene, 374-376

Bromonium ions, in bromine additions to alkenes, 365-366

from l-bromo-2-fluoroethane, 366 l-Bromo-2-phenyl- l-propene, photochemical

isomerization of cis-trans isomers of, 1386 2-Bromopropane, E2 reaction of, 241

SN2 reaction of, 241 3-Bromopropene, from propene and

N-bromobutanimide, 104 N-Bromosuccinimide (see N-Bromobutanimide) Bromotrichloromethane, radical-chain addition to

alkenes and alkynes, 389 Br$nsted, J. N., and acid-base theory, 208

Brown, C., 5 Brown, H. C., and hydroboration, 421 Brucine, 867, 1097 Bucherer reaction, 1295-1296 Bullvalene, 1089- 1090 Burgstahler, A. W., and cantharidin synthesis,

1497-1498 1,3-Butadiene, with l,4-benzenedione, 13 12

bond distances in, 37 bromine addition by 1,2 and 1,4 modes, 489 chlorine addition to, 1441 cis-trans isomers of polymer of, 505 copolymerization of, with ethenylbenzene

(styrene), 506 with propenenitrile (acrylonitrile), 506

[4 + 41 cycloaddition of, 1004 dimerization of, 1004 electrocyclic reactions of, 1005-10 14 electronic spectrum of, molecular-orbital

treatment of, 980-98 1 transitions of, 289-29 1

ethene addition to, 492 heat of hydrogenation of, 415 1,6-hexanediamine from, 144 1 homopolymerization of, 504-505 hydrogen bromide addition to, by radical

mechanism, 49 1 hydrogen chloride addition to, by 1,2 and 1,4

modes, 490, 542 iron tricarbonyl complex of, 1523 molecular-orbital treatment of, 475-477 molecular orbitals of, 976 nickel complexes of, 1523 photochemical additions and cycloadditions

of, 1388 photochemical reactions of, 1388- 1389 rotational conformations of, 495 s-cis-trans isomers of, 495 stabilization energy of, 986 sulfur dioxide cycloadduct, 500-501 tetrduoroethene cycloadducts of, 502, 1014-1017 valence-bond treatment of, 977

1,3-Butadiyne, from oxidative coupling of ethyne, 441

Butanal, electronic absorption of, 795 by hydroformylation of propene, 722-723 physical properties of, 679

Butane, bond distances in, 37 conformational energies of, 123-125 conformations of, 123- 125 heat of combustion of, 79 rotational barrier of, 123-124

Butanedioic acid, anhydride from, 847 in citric acid cycle, 951-954 properties and uses of, 847

Butanedioic anhydride, polyesters from, 1440 2,3-Butanedione, from photolysis of

2-propanone, 1379 physical properties of, 679

Butanimide, acidity of, 850-85 1 N-bromo derivative of (see N-Bromobutanimide)

Index

resonance in, 850-85 1 synthesis of, 850

Butanoic acid, electronic absorption of, 795 physical properties of, 792

I-Butanol, industrial preparation of, 759 2-Butanone, alkylation of, 763

halogenation of, 745 infrared spectrum of, 273 mass spectrum of, 340-341 physical properties of, 679

2-Butenal, physical properties of, 679 preparation of, 755-756

1-Butene, heat of hydrogenation of, 4 15 infrared spectrum of, 353

2-Butene, allylic chlorination of, 543 bond distances in, 37 cis-, heat of hydrogenation of, 415 cis-trans isomers of, 11 1-1 12 from ethene, by metathesis, 1520-152 1 trans-, heat of hydrogenation of, 4 15

cis-Butenedioic acid, anhydride from, 847 properties and uses of, 849

trans-Butenedioic (fumaric) acid, biological hydration of, 371-372

in citric acid cycle, 951-954 properties and uses of, 849

Butenedioic anhydride, from benzene oxidation, 1077-1078

copolymerization of, 1452 as dienophile, 496-498, 1077 in fiberglass, 1440 naphthalene addition of, 1077 polyesters from, 1440

3-Buten-Zone, electronic spectrum of, 289 in Robinson annelation, 1477-1478

1-Buten-3-yne (vinylacetylene), bond distances in, 37

from dimerization of ethyne, 441 nmr spectrum of, 1353

tert-Butoxycarbonyl protecting groups, in peptide syntheses, 1237- 1247

Butter Yellow, as carcinogen, 1162 from diazo coupling, 1137

Butyl alcohol tert-Butyl alcohol (see 2-Methyl-2-propanol) Butyl Carbitol, 656 tert-Butyl hypobromite, bromination of

hydrocarbons with, 106 tert-Butyl hypochlorite, in additions of alkenes, 379

for hydrocarbon chlorinations, 103- 104 with methylbenzene, 13 17

Butyl rubber, 506, 508, 1432 N-tert-Butylalkanamides, from Ritter reaction,

1178-1 179 tert-Butylcyclohexane, conformational equilibria of

derivatives of, 458-460 tert-Butylhydroperoxide, alkylzirconocenes

oxidation with, 15 14 2-Butyne, bond distances in, 37

hydrogenation of, 4 13-4 14 Butyric acid (see Butanoic acid)

C-alkylation, of enolate anions, 762-763 of ester anions, 833-835 of phenols, solvent effect on, 1297-1298

C-carboxylation, in Kolbe-Schmitt reaction, 1299 of ribulose, 941-942

Cadmium alkyls, ketones from, with acyl halides, 73 1

Caffeine, 1097 Cahn-Ingold-Prelog convention for configurations,

879-884 Calvin, M., and path of carbon in photosynthesis,

94 1-943 Camphene, 1464 Camphor, as isoprenoid, 1466- 1467

synthesis of, 1467 Cancer chemotherapy, 1 163 Cane sugar (see Sucrose) Cannabinols, 1305 Cannizzaro, S., aldehyde oxidation-reduction

reaction of, 707-709 and atomic weights, 4

Cannizzaro reaction, of ethanedial, 775 Cantharidin, synthesis of, 1497 Caprolactam (see I-Aza-2-cyclopentanone) Carbamic acids, from tert-butoxycarbonyl group

hydrolysis, 1 160 from isocyanates, 1 155- 1 156 polyurethane foams and, 1455

Carbanions (see also Enolate anions), bonding and geometry of, 169

C- vs. 0-alkylation of, 762-763, 833-835, 1297-1298

sulfur, nitrogen, and phosphorus stabilized, reactions of, 691-693, 765-767

Carbazole, from coal tar, 1080 Carbene, carbon-hydrogen insertion of, 1200

from diazomethane, 1200 dichloro- from trichloromethane, formation and

reactions of, 563-564 Carbenes, complexes with transition metals, 1512,

1520-1521 cyclopropanes and cyclopropenes from, 565 electronic structure of, 564 formation of (table), 563-566 reactions and reactivity of, 563-567 rearrangement of, 567 singlet and triplet, 564 in tetrduoroethene preparation, 568

Carbenium ions (see Carbocations) Carbitols, 656 Carbocations, in alcohol dehydrations, 63 1-633

in alkene hydrations, 368-37 1 from alkyldiazonium salts, 1 130-1 13 1 in arene alkylations, 1047- 1050 aryl, from arenediazonium salts, 1133-1 136 atomic-orbital model of, 223 bonding and geometry of, 169 in halide formation, from alcohols, 626 in halogen additions to alkenes, 361-367 hydrogen-transfer reactions with alkanes,

397-398

Index

hyperconjugation and, 228 methyl groups and stability of, 375 rearrangement of, in alcohol dehydrations,

632-633 relative rates of, 25 1 S,l and E l reactions, 250-251, 632-633, 1010

in Ritter reaction, 1178-1 179 in S,1 reactions, 215-217 stability order of, 226-228 stereochemistry of, 222-223 steric hindrance and, 229 in terpene and steroid biosynthesis, 1484-1489 thermochemistry of formation of, 2 12-2 13 tropylium ion and, 13 15

Carbohydrates, classification of (table), 902-908 definition of, 902 determination of configurations of, 909-9 12 enzymatic hydrolysis of, 930 furanose ring in, 920-922 hemiacetal and hemiketal structures of, 903-906 Kiliani-Fischer cyanohydrin synthesis of, 9 1 1 metabolism of, 944-956 nomenclature of, 903-908 occurrence of (table), 907-908 from photosynthesis, 939-943 physical properties of (table), 907-908 properties of, 909 pyranose ring in, 920-922 ring sizes in, 920 Wohl degradation of, 9 10

Carbon, bonding of, 18-19, 30-34, 162-168, 179-182, 964-968

oxidation states of, 405-409 tetrahedral, 6-7, 34-36, 160-161 valence of, 4-5, 34-36, 160, 405-409

Carbon-carbon bond formation, reactions for (table), 5 18

Carbon-carbon bonds, lengths of (table), 36-37 Carbon-chlorine bonds, lengths of (table), 37 Carbon dioxide, equilibration with water, carbonic

anhydrase for, 1260 fixation in photosynthesis, 939-943 with organometallic compounds, 570-57 1,

579, 583 with phenols, 1298-1299

Carbon disulfide, physical properties of, 239 Carbon-hydrogen bonds, lengths of (table), 37 Carbon monoxide, with alkylzirconocenes, 15 14

with arenes in Gattermann-Koch synthesis, 1053 copolymer with ethene, 1453 with di-n-propenylnickel, 1522 in hydroformylation, 722-723, 15 18- 15 19 insertion reactions of, 15 12, 15 14, 15 16, 15 18 methanol from, by hydrogenation, 612 from photolysis of 2-propanone, 1379 with transition-metal compounds, 15 12- 15 16,

1518-1520, 1522-1524 Carbonate esters, amides from, 1177- 1 178 Carbonate ion, and resonance, 176- 177 Carbonic anhydrase, 1260 Carbonium ions (see Carbocations) Carbonyl bond, alkene bond comparision, 673-674

atomic-orbital model, 675 dipole moment, 674-675 energies (table), 674 hydration of, 673-674 polarity of, 674-678

Carbonyl compounds (see Aldehydes, Ketones, Carboxylic acids, and so on)

Carbonyl group, addition reactions to, 577-586, 685-7 12

electronic spectra of, 681 genera1 characteristics of, 671-678 infrared properties of (table), 680-68 1 reactivity of, 674-678

Carbonylation, of alkylboranes, 724-726 of methanol, 1520

Carbowax, 662 Carboxylate anions, IUPAC rules of nomenclature

for, 195 Carboxylic acids, from acetoacetic ester acid

synthesis, 854 acid-base equilibria of, 4 1 acyl chlorides from, with phosphorus

chlorides, 809 with thionyl chloride, 809

acyl halides from, 857 acyl phosphate derivatives of, in biochemical

esterifications, 636-637 from acyltetracarbonylferrates, 15 16 from acylzirconocenes by oxidation, 15 14 from alcohol oxidations, 639, 643, 855 alcohols from, by hydride reduction, 6 10,

809-8 1 1 aldehydes from, by hydride reduction, 719,

810-81 1 from aldehydes, Baeyer-Villiger, 7 13-7 14

Cannizzaro, 707-709 with oxidizing agents, 855 oxygen, 7 12-7 13 permanganate, 7 12 silver oxide, 712

from 2-alkanones, 855 alkene additions of, 379, 808 from alkene oxidations, 855 amides from, 858, 1177-1 178 from amides, 854 anhydrides from, 771, 857 from Arndt-Eistert synthesis, 855, 1200 biosynthesis of, 1480-1482 borane reduction of, 707-708 bromination of, Hell-Volhard-Zelinsky reaction

and, 814-815 from Cannizzaro reaction, 855 carboxylic esters from, 856 chiral, as resolving agents, 867-869 chlorination of, 8 15 decarboxylation of, carboxylate radicals and,

812-813 electrolytic, 8 13 with lead tetraethanoate, 8 14 with mercuric oxide, 8 14 silver salts and bromine, 8 13-814 thermal, 8 1 1-8 12

Index

with diazomethane, 1199 from dicarboxylic acid decarboxylations, 847 dimers of, 791 electronic spectra of (table), 793, 795 esterification of, with alkenes, 808

mechanism and practice of, 6 15-6 18, 807-808 side reactions in, 807-808 steric hindrance and, 807-808

from esters, 854 as fatty acids, 789-791 functional derivatives of (table), 817-820 general characteristics of, 788-791 general reactions of, 796 a-halo, nucleophilic reactivity of, 8 15-8 17

synthetic uses of, 8 15-8 17 P-halo, from unsaturated acids, 841-842 from haloform reaction, 855 halogenation of, Hell-Volhard-Zelinsky reaction

and, 8 14-8 15 hydrogen bonding of, 791 hydroxy, dehydration of, 843

lactones from, 843 synthesis of, 835-836 thermal reactions of, 843 from unsaturated acids, 841-842

infrared frequencies, 276-277, 680 infrared spectra of, 28 1-282, 793-794 ionization of, constants for (table), 792

electrostatic interpretation of, 799-800 entropy and, 801-802 inductive effects and, 798-800 relative to other acids, 789, 796-797 resonance and 796-798 solvation effects on, 801-802 substituent effects on, 798-802

IUPAC rules of nomenclature for, 195 from ketones, by Baeyer-Villiger oxidation, 855

by Favorskii rearrangement, 748-749 by haloform reaction, 746-747

by Kolbe-Schmitt reaction, 1298-1299 from malonic ester acid synthesis, 854 metabolism of, 837-840 from nitriles, 854 nmr spectra of, 793 nucleophilic attack on, 805-806 from organometallics, 854 from oxidation of alkyl aryl ketones, 1317 from oxidation of alkylarenes, 1317 from 3-oxobutanoic esters, 834, 854 from ozonides and methanol, 432 from phenols, 1298-1299 physical properties of (table), 79 1-792 preparation of (table), 854-855 from propanedioate esters, 834, 854 protecting groups for (table), 1236- 1239 protonation of, 6 17 radical-chain addition to alkenes and

alkynes, 389 reduction of, to aldehydes, 8 10-8 1 1

with diborane, 8 10-8 1 1 with metal hydrides, 809-8 10

resolution of chiral forms of, 866-867

with sulfur tetrafluoride, 705 trifluoromethyl derivatives from, 13 18 unsaturated, 1,4-additions to, 840-841

in [4 + 21 cycloadditions (table), 493-494 hydration of, 841-842 hydrogen bromide addition to, 841-842 lactones from, 842-843 rearrangement of, 841 synthesis of, 836

Carboxylic anhydrides, acylation of arenes with, 1051, 1054

alcohols from, with Grignard reagents, 609 by hydride reduction, 824-825

amides from, 858, 1121-1 122, 1177-1 178 with amino acids, 1222 carboxylic esters from, 615-616, 856 from carboxylic acids, with ketene, 771 from dicarboxylic acids, 847 esterification of, 615-618, 856 as functional derivatives of carboxylic acids, 8 18 hydrolysis of, 820 infrared frequencies, 680 as intermediates in enzyme-induced reactions,

1263- 1265 IUPAC rules of nomenclature for, 198 preparation of (table), 557, 857 unsaturated, in [4 + 21 cycloadditions (table),

493-494 Carboxylic esters, acidities of (table), 736-738

from acids with diazomethane, 1199 acyl halides from, 857 acyloin reaction of, 852-853 from acylzirconocenes, 15 14 from alcohols and acyl halides, 616-617, 856 from alcohols and anhydrides, 616-617, 856 from alcohols and carboxylic acids, 6 15-6 18,

806-808, 856 alcohols and ketene, 77 1 alcohols from, with Grignard reagents, 609

by hydride reduction, 824-825 sodium and alcohol reduction, 825

from alcohols, thionyl chloride and carboxylate salts, 855

aldol additions of, 835 from alkyl halides and carboxylate salts, 856 amides from, 858, 1121-1 122, 1177-1 178 mines from, by Curtius degradation, 1150 biochemical formation of, phosphate esters

and, 635-637 carboxylic acids from, 854 from carboxylic acids, with alcohols, 615-618,

806-808, 856 with alkenes, 808 with diazomethane, 856, 1199

Claisen condensation of, 829-832 enolate anions from, 835-836 by ester interchange, 856 as functional derivatives of carboxylic acids, 818 from Grignard reagents (table), 579, 583 with Grignard reagents, 823-824 hydrazides from, 858 a-hydrogen acidity, 737, 825-826

l ndex

hydrolysis of, 820-82 1 Harnmett correlation of, 1329-1330,

1334, 1336 hydroxaniic acids from, 858 hydroxy, synthesis of, 835-836

unsaturated esters from, 836 infrared frequencies, 680 interchange reaction of, 82 1 IUPAC rules of nomenclature for, 197-198 from ketones, Baeyer-Villiger, 7 13-7 14

by Favorskii rearrangement, 748-749 mechanism of formation of, 6 15-6 18 from nitriles, 856 preparation of (table), 856 as protecting groups for OH, 652 reactivity correlation of, 1329- 1330 soaps from hydrolysis of, 790 unsaturated, 1,4-additions to, 844-845

in /4 + 23 cycloadditions (table), 493-494 cycloadditions with diazomethane, 1200 Michael addition of, 844-845 rearrangement of, 841 synthesis of, 836

Carboxypeptidase, mechanism of action of, 1262- 1265

in peptide sequencing, 123 1 precursor of, 1269 properties, 1250 proteolytic properties of, 1260

Carcinogens, aflatoxins as, 1 163 amines as, 1161-1162 arenes as, 1026 azo compounds as, 1162 chloroethene as, 549 N-nitroso compounds as, 1 163- 1 164

Cardiac poison, 1473 P-Carotene, electronic absorptions of, 1401

with singlet oxygen, 1393 structure of, 33 as vitamin A precursoi; 1469

Carotenes, biosynthesis of, 1485, 1488 Carvone, structure and odor, 140 CaryophyIlene, 1464 Catalysis (see also Acid catalysis, Base catalysis,

etc.) of alkene hydrogenation, heterogeneous metals

and, 410-414 homogeneous metal complexes and, 4 17-4 18,

1517-1521 mechanisms for, alkene metathesis, 1520-1 52 1

1,3-butadiene trimerization, 1523 homogeneous hydrogenation with rhodium,

1517-1518 hydroformylation, 15 18-15 19 of methanol carbonylation, 1520 methylpropandioyl to butanedioyl coenzyme

A, 1526 of 0x0 reaction, 1518-1519

Catalyst, definition of, 16 Catalytic re-forming, 1079- 1080 Catechol (see 1,2-Benzenediol) Cationic polymerization, of alkenes, 393-395

Cedar, oil of, 1498 Cedrene, synthesis of, 1498 Celery, oil of, 1464 Cellobiose, from cellulose, 933

structure and configuration of, 929 Cellosolves, 656 Celluloid, 933 Cellulose, biological degradation of, 934

derivatives, 933 enzyme induced hydrolysis, 1270 hydrolysis of, 933-934, 1270 properties and occurrence of, 908 structure of, 932-933 uses of, 933

Cellulose acetate, 933 Cellulose acetate butyrate, 933 Cellulose xanthate, 933 Cephalosporins, biosynthesis of, 1492

structure and function of, 1491 synthesis of, 1492

Cercropia moth hormones, 1469 Ceric ion, oxidation of

cyclobutadieneirontricarbonyl with, 1507 Charge relay mechanism, in proteolytic

enzymes, 1266 Charge transfer complexes, from alkenes and

halogens, 367 in arene halogenation, 1044- 1045 of arenes and nitro compounds, 1192-1 193 electronic spectra of, 1 192- 1 193 quinhydrone as, 1307 resonance and, 1 192- 1 193

Chemical Abstracts, indexes for, 5 1 Chemical evolution, 1282- 1284 Chemical synthesis, principles in planning of,

5 13-530 Chemically induced dynamic nuclear polarization,

1353-1356 Chemiluminescence, 1395- 1399 Chenopodium, oil of, 1466 Chiral centers (see Chirality) Chiral recognition, 869 Chirality, achiral and chiral environments, 120

of allenes, 508-5 10 of amines, 1109-1110 asymmetric synthesis and, 893-894 and biological specificity, of sense of taste and

smell, 140- 14 1 chiral centers, location of, 1 16- 1 17 compounds without chiral carbons, 508-5 1 1 of trans-cycloalkenes, 475-476, 5 1 1 of cycloalkylidenes, 5 10 D,L convention for, 13 1-139 definition of, 1 16 diastereotopic groups and, 889 enantiotopic groups and, 888-889 Fischer projection formulas for, 128-139 of hindered biphenyls, 5 10-5 1 1 meso compounds and, 135-139 optical rotation and, 865-866 prochirality and, 888-889 R,S convention for, 879-884

racemization mechanisms and, 895-897 of spiranes, 510

Chitin, properties and occurrence of, 908 structure of, 936

Chloral (see Trichloroethanal) Chloral hydrate, 647 Chlordane, 536 Chlordiazepoxide, 1098 Chlorination (see also Halogenation)

of alkanes, with tert-butyl hypochlorite, 103-104 mechanisms for, 88-98, 102-103 photochemical, 83, 91-95 selectivity produced by arenes, 102 with sulfuryl chloride, 102- 103, 108 thermal, 99, 101

of alkenes, by radical mechanism, 543-544 of arenes, 1044- 1046 with tert-butyl hypochlorite, 103-104 energy of, 81-83 of methane, 81-85, 88-96 of methoxybenzene, cyclodextrin effect on,

935-936 radical, of alkylarenes, 546, 13 17 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, 17 1-172

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, 1 164 Chloromethoxyme thane, as carcinogen, 1 164 Chloromethyl cation, in chloromethylation of

aenes, 1319 Chloromethyl ether, 704 bis-Chloromethyl ether, as carcinogen, 1164 Chloromethylation, of arenes, 1054, 13 19

mechanism of, 13 19 of resins for solid-phase peptide syntheses, 1245

Chloromethylbenzene, from benzene by chloro- methylation, 13 19

benzenecarbaldehyde from, 13 18 and Hammett correlation, 133 4 from methylbenzene, 104, 546, 13 17 from methylbenzene and tert-butyl hypo-

chlorite, 104 phenylethanenitrile from, 13 18 phenylmethanol from, 13 18

2-Chloro-2-methylbutane, E l reactions of, 249 E2 reactions of, 245

2-Chloro-2-methylpropane, E l reaction of, 248-249

S,1 reaction of, 248-249 Chloromethyloxacyclopropane (epichlorohydrin),

in epoxy resins, 1444-1445 Chloromethyloxacyclopropane, formation of, 542 1-Chloro-4-nitrobenzene, nucleophilic substitution

reactions of, 554-555 N-Chloro-N-phenylethanamide, rearrangement

of, 1140 Chlorophyll, in photosynthesis, 939

singlet oxygen from, 1392- 1393 structure of, 939

Chloroplasts, 939 Chloroplatinic acid, ether formation with, 655 Chloroprene, 506, 1433 3-Chloropropene, epichlorohydrin from, 541-542

hypochlorous acid addition to, 541-542 preparation of, 541, 543-544 S,2 transition state for, 545-546

N-Chlorosuccinimide (see N-Chlorobutanimide) Chlorosulfite esters, in alkyl chloride

formation, 627 Chlorosulfonic acid, sulfonyl chlorides from arenes

with, 1056 Chlorotrifluoroethene, ethenylbenzene adduct

of, 1313 polymers from, 391, 1432

Chlorpromazine, 1098 Cholestane, 1475- 1476 Cholestanol, 1477 Cholesterol, biosynthesis of, 1486-1488

occurrence of, 1471

reactions of, 1474- 1476 reduction products of, 1474-1477 structure and stereochemistry, 147 1- 1477 structure and determination of, 1475-1477

Cholic acids, 1475- 1476 Chromate esters, in alcohol oxidations, 640-641 Chromatographic separations, affinity, 262

gas-liquid, 259-260 high-pressure, 262 liquid-solid, 26 1-262

Chromatography, reference works for, 346-347 Chromic acid, aldehydes from, with alcohols, 727

azabenzene complex of, oxidation of alcohols with, 642

kinetic isotope effect in 641 mechanism of, 640-641 oxidation of alcohols with, 640-642 phenols to quinones with, 1300-1301

Chromic oxide (see Chromic acid) Chromophore, definition of, 1030 Chromophores, benzene derivatives as, 1402-1404 Chromosomes, DNA in, 1271 Chrysene, from coal tar, 1080 Chymotrypsin, histidine function in, 1266

in peptide sequencing, 1233 precursors of, 1269 properties of, 1250 proteolytic properties of, 1260 regulation of, 1269 serine function in, 1265- 1266

Chymotrypsinogen, 1269 CIDNP, 1353-1356 Cinnamic acid (see 3-Phenylpropenoic acid) Circular dichroism, 89 1 Cis-trans isomers, of 1,3-alkadiene polymers,

504-508 of alkadienes, 114 of 1,2,3-alkatrienes, 5 11 of amides, 1 17 1 of cycloalkanes, 1 13 definition of, 1 1 1- 1 12 interconversion of, of visual pigments, 1417 IUPAC rules of nomenclature for, 113-1 14 photochemical interconversion of, 1384- 1386

Citral, 1465- 1466 Citric acid (see also 3-Hydroxypentanoic acid)

- in citric acid cycle, 951-954 Citronella, oil of, 1464, 1466 Citronellal, 1465- 1466 Claisen ally1 ether rearrangement, 1298 Claisen condensation, biological equivalent of,

837-839 with carbonate esters, 83 1 Dieckmann variation on, 85 1-852 equilibrium of, 829-83 1 with ethanedioate esters, 831-832 in fatty acid biosynthesis, 1481 with ethyl benzenecarboxylate, 83 1 of ethyl ethanoate, 829-830 of ethyl 2-methylpropanoate, 830-83 1 ethyl 3-oxobutanoate from, 829-830

with ketones, 832 limitations of, 830-83 1 with methanoate esters, 83 1 mixed, 83 1-832 thermodynamics of, 829 triphenylmethylsodium as base for, 83 1

Clarke, F. H., Jr., and cedrene synthesis, 1498 Clemmenson reduction, of aldehydes and

ketones, 71 1 Cloves, oil of, 1464 Coal, distillation of, 74, 1079 Coal tar, arenes from, 1079-1080

azarenes from, 1079- 1080 oxygen and sulfur compounds from, 1079- 1080 production of, 74, 1079

Cobalt, vitamin B12 and, 1490, 1525-1526 Cobalticinium ion, 1506 Cocaine, 1097 Codeine, 1097 Codons, of messenger RNA Coenzyme A, ethanoyl derivative (see Ethanoyl

coenzyme A) and fatty acid biosynthesis, 1480- 148 1 structure of, 838

Coenzyme Q, 1309 Coenzymes, B vitamins as, 1267-1268

functions of, 1267- 1269, 1525- 1526 thiamine pyrophosphate as, 1267-1269 types of, 1267-1269 vitamin B12 as, 1525-1526

Cofactors (see Coenzymes) Coke, formation of, 74 Colchicine, 13 16 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, 15 16 Color, complementary, 1399- 1400, 1409

and electronic absorptions, 1399- 1404 sensation of, 1399- 1400, 1409 visible wavelengths, 1399- 1400

Color-forming reactions, 141 1-1414 Color photography, color transparencies, chemistry

of, 1410-1415 instant color prints from, 1414- 141 5 subtractive process of, 1410

Complementary colors, 1399- 1400, 1409-1415 Concerted reactions, [4 + 21 cycloadditions and,

498-499 formulation of, 88-89, 98 in methane chlorination, 90

Conformational analysis (see Conformations) Conformations, anti, 124

of 1,3-butadiene, 495 of butane, 123-125 of cis and trans isomers of decalin, 480-481 of cyclobutane, 462 of "cyc1oethane," 463 of cycloheptane, 47 1-472

of cyclohexane, 448-46 1 cyclohexane derivatives, equilibria and

equilibration of, 453-46 1 substituent effects, 457

of cyclononane, 473 of cyclooctane, 472 of cyclopentane, 462 of cyclopropane, 463 of cyclotetradecane, 47 1-472 drawings of, 125-126 and E2 reactions, 466-468 eclipsed, definition of, 12 1 energies of, 12 1-124

for butane, 125-126 equilibration of, nmr studies of, 1345-1347 of ethane, 121-123 gauche, 124 holding groups for, 458-460 Newman projections of, 125-126 nmr spectra of, 303-304, 1345- 1347 of proteins, 1249-1259 and reactivity, 245-247, 466-468 sawhorse representations for, 125- 126 skew, 124 and spin-spin splittings, 320-32 1 staggered, definition of, 121 syn, 124 torsional angles of, 12 1- 124 trans, 124

Conformer (see also Conformations) definition of, 124

Conjugate addition, definition of, 770 of organometallics to alkenones and alkenals,

585-586 Conjugated polyenes (see Polyenes) Conrotation, definition and occurrence of,

1006-1009, 1013-1014 Constitutional isomers, 45 Contraceptive steroids, 1479 Coolite, 1396 Coordination polymerization, of alkenes, 396-397,

1446, 1511 Cope, A. C., and sigmatropic rearrangement, 1006 Cope rearrangement, 1089 Copolymers, from 1,3-alkadienes, 506-508

definition of, 505 of ethene and propene, 1432, 1435 properties and types of (table), 1432-1433 ratios of incorporation in, 1452- 1453 types of, 1452-1453

Copper catalysis, of arenediazonium salt reactions, 1134-1 136

Copper phthalocyanine, 14 14 Coprostane, 1475 Coprostanol, 1477 Coral rubber, 1433 Corey, E. J., and prostaglandin syntheses,

1502- 1503 and synthesis of juvenile hormone, 1470

Corey, R. B., and alpha helix, 1251 Corey-Pauling-Kolton models (see CPK models)

Corn syrup, 935 Cornforth, J. W., and steroid synthesis, 1477-1478 Corrin rings, 1490 Cortisone, structure and occurrence, 1473

synthesis of, 1478-1479, 1495-1497 Cotton, 933 Cotton effect and optical rotatory dispersion,

890-893 Coumarin, 1328 Couper, A., 5 Coupling constants (see Nmr spectra) Covalent bonds, 18-2 1 CPK models, 37-39 Crafts, J. M., and acylation of arenes, 105 1-1053

and arene alkylation, 1047- 1050 Cresols (see also Methylbenzenols), from coal

tar, 1081 Crick, F., and DNA structure, 1249, 1275 Cross-linking (see Polymers) Crossed Cannizzaro reaction, 754 Crotonaldehyde (see 2-Butenal) Crotyl alcohol (see 2-Buten-1-01) Crown ethers, 666 Crystal violet, 1404 Cubane, physical properties and strain energy

of (table), 482-483 Cumene (see I-Methylethylbenzene) Cumulated double bonds, stereochemistry of,

508-5 1 1 Curtius degradation, amines from, 1150, 1 153, 1156 Cyan dye, 1410-1414 Cyanide ion, in benzoin condensation, 1324- 1325 Cyanides (see Nitriles) Cyanine dyes, 1412 Cyanoacetic acid, 793, 81 1 Cyanoacetic esters, acidity of, 826 Cyanobenzenamines, base strengths of, 1 1 16 Cyanoborohydride, 1 154 Cyanocobalamin (see Vitamin B, ,) Cyanoethanoate esters, acidity of, 826 Cyanoethanoic acid, 793, 8 1 1 Cyanogen bromide, addition to alkenes, 379 Cyanohydrin formation, 689-690 Cyanohydrins, in Kiliani-Fischer synthesis, 91 1 Cyclic conjugated polyenes, annulenes, properties

and reactions of, 1087-1088 azulene, properties and reactions of, 1084-1085 cyclobutadiene as, 178, 989-99 1 cyclooctatetraene, properties and reactions of,

1085-1086 fluxional compounds, electrocyclic equilibration

of, 1089- 1090 pentalene, attempts to synthesize, 1086-1087

Cyclic ions, and Hiickel rules, 996-999 Cyclic polyethers (see also Ethers), metal com-

plexes of, 665-666 Cycloadditions, of cyclopropanone, 78 1

of cyclopropenone, 78 1 of diazomethane, 1200 general types of, 492-493 in planning of syntheses, 526-527

[2 + 11 type, with carbenes, 565 [2 +2] type, of DNA and RNA, 1393-1394

of ethene, 502 of ethenylbenzene and chlorotrifluoro-

ethene, 1313 with fluoroalkenes, 569, 1014-1017, 13 13 and Hiickel rule, 999-1002, 1010-1014 ketene dimerizations as, 503 with ketene, 1002 ketenes and 1,3-cyclopentadiene, 503 mechanism of, 503-504 photochemically induced, 503, 1013- 1014,

1389, 1392-1393 polar mechanism for, 1023- 1024 possible concerted examples of, 1002 1,2-propadiene dimerization, 502 with 1,2-propadiene, 1002 radical mechanism for, 1014-1017 stepwise mechanism for, 10 14- 1017 stereospecificity of, 1014- 1017 tetrafluoroethene and 1,3-butadiene, 502 tetrafluoroethene dimerization, 502, 568 thermodynamics of, 502-503

[4+ 11 type, sulfur dioxide and 1,3-butadiene, 500-501

[4 + 21 type (Diels-Alder), addends for (table), 492-498

of arenes, 1077 1,3-butadiene and 1,4-benzenedione, 13 12 concerted nature of, 498-499, 999 exo-endo preferences in, 496-498 and Hiickel rule, 999- 1000, 1004-1005, 1010 kinetic vs. equilibrium control in, 497 mechanism of, 498-499 of naphthalene, 1077 photochemical, 1388 polymerization by, 1420 pressure effects on, 1077 of quinones, 13 12 of singlet oxygen, 1391-1392 stereospecificity of, 494-499 substituent effects on, 493-498 synthetic uses of, 526-527

l,2-Cycloalkadienes, from gem-dichlorides, 704-705 Cycloalkanes, cis-trans isomers of, 112- 1 13

conformations of, 448-463, 480-48 1 for larger rings, 469-474

conformational representations of, 126-127, 449-453, 462, 470-474, 480-48 1

electronic spectra of, 29 1-292 Haworth projections of, 127 heat of combustion and strain energy of

(table), 464 infrared stretching frequencies for, 276, 278-280 larger-ring members of, synthesis of, 469-470 ring-opening reactions of, 466-467 strain energies and bond energies of, 465

Cycloalkanones, from dicarboxylic acids, 846-847 from dicarboxylic esters, 85 1-852

Cycloalkenes, chemical properties of, 474-475 chiral forms of trans isomers of, 475-476

heats of hydrogenation of (table), 475 nomenclature for, 60 physical properties of (table), 474-475 strain energies of, 474-475 transition-metal complexes of, 15 10

trans-Cycloalkenes, chiral forms of, 5 10 Cycloalkyl halides, physical and chemical prop-

erties of, 550-55 1 Cycloalkylidenes, chiral forms of, 5 10 Cycloalkynes, from gem-dichlorides, 704-705 Cyclobutadiene, angle strain in, 99 1

cycloaddition reactions of, 1507 dirnerization of, 990, 1507 electronic configuration of, 992-994 generation of, 1507 iron compounds of, 1507 molecular orbital treatment of, 989-994 quinones of, 13 13 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 photodisso- ciations, 138 1

Cyclobutanone, from cyclopentanone photodisso- ciations, 138 1

photochemistry of, 138 1 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, 13 13 Cyclobutenediones, angle strain in, 991 Cyclobutenes, electrocyclic reactions of,

1005-1014 1,5-Cyclodecadiene, 1524 Cyclodecane, conformations of, 473-474

heat of combustion and strain energy of (table), 464

1,4,7-Cyclodecatrienes, 1524 Cyclodecyne, physical properties and strain of, 475 Cyclodextrins, 935-936 1,5,9-Cyclododecatriene, 1523 Cycloheptane, conformations of, 47 1-472

physical properties of (table), 446 1,3,5-Cycloheptatriene, radical from, esr spectrum

of, 1369 synthesis of, 13 14 tropolone from, 13 14 tropylium ion from, 1315

Cycloheptatrienyl radical, esr spectrum of, 1369 Cycloheptene, physical properties and strain

of, 475 1,3-Cyclohexadienes, electrocyclic reactions of,

1005-1012 1,4-Cyclohexadienes, from Birch reduction,

1074- 1075 1,4-Cyclohexadienone (see 1,4-Benzenedione) Cyclohexanamine, base strength of, 11 14

from benzenamine reduction, 1073 infrared spectrum of, 1104 physical properties of, 1 10 1

Cyclohexane, from benzene reduction, 1072- 1073 boat conformation of, extreme form of, 449-451

"flagpole" hydrogens in, 450 preparation of, 450 stability of, 450 twist-boat form, 450-45 1

carbon-13 nmr spectra of derivatives of, 460 chair conformation of, axial positions in,

452-46 1 equatorial positions in, 452-46 1 equilibria and, 453-461 ring inversion of, 454-461 stability of, 450

chemical properties of, 466-467 cis-trans isomerism of derivatives of, 458-460 conformational representations of, 126-127,

449-445 conformations and conformational analysis of,

448-46 1 cyclohexanone from, 1441 E2 reactions and conformations, 468 heat of combustion and strain energy of (table),

79-80, 464 hexanedioic acid from, 144 1 models of, 45 1-453 nomenclature for, 57-58 from petroleum, 108 1 physical properties of (table), 239, 446 planar conformation of, strain in, 448-449

Cyclohexanol, from benzenol reduction, 1073 dehydration of, 251 physical properties of, 129 1

Cyclohexanols, from alkyl-substituted phenols, 1300

Cyclohexanone, from cyclohexane, 144 1 enamine from, 702 hexanedioic acid from, 144 1 oxime of, formation of, 1 180

rearrangement of, 1 18 1 physical properties of, 679

Cyclohexene, bromine addition to, 362, 365, 367 bromine substitution of, with tert-butyl

hypobromite, 106 charge-transfer complex with iodine, 367 from ethene and 1,3-butadiene, 492 hydrogen fluoride addition to, 368 oxidation of, with nitric acid, 1043 physical properties and strain of, 475 Raman spectrum of, 285-286

Cyclohexylamylose, 935-936 Cyclonite, 701 Cyclononane, conformations of, 473

heat of combustion and strain energy of (table), 464

physical properties of (table), 446 cis-Cyclononene, physical properties and strain

of, 475 trans-Cyclononene, physical properties and strain

of, 475 Cyclonoyne, physical properties and strain of, 475 1,5-Cyclooctadiene, from 1,3-butadiene, 1523-1524

nickel complex of, 1510 Cyclooctane, conformations of, 472

heat of combustion and strain energy of (table), 464

infrared spectrum of, 280 physical properties of (table), 446

Cyclooctatetraene, dianion of, 1085 dication of, 1085 electrocyclic equilibrium of, 1085- 1086 electronic configuration of, 992-994 geometry of, 990 halogen addition to, 1086 iron tricarbonyl complex of, Mossbauer

spectrum of, 1360 molecular-orbital theory of, 989-994 physical properties of, 1085 planar form of, 994, 1085 preparation of, 990, 1085 reactions of, 1086 resonance and, 989 uranium derivative of, 1508

cis-Cyclooctene, physical properties and strain of, 475

trans-Cyclooctene, chiral forms of, 475-476 physical properties and strain of, 475

Cyclooctyne, physical properties and strain of, 475 Cyclopentadecane, heat of combustion and strain

energy of (table), 464 1,3-Cyclopentadiene, cycloaddition with

ethyne, 1314 [4 + 21 cycloadducts of, 526-527 dimerization of, 1420 electrocyclic reactions of, 1007- 1008, 10 13- 1014 organometallics from, 574 pi (n-) metal derivatives of, 1504-1508,

1512-1514 polymerization of, 1420 sandwich compounds of, 1504-1508, 15 12-15 15 transition-metal compounds, 1504- 1508,

1512-1514 Cyclopentadienyl anion, Huckel rule and, 996-998 Cyclopentadienyl cation, and Huckel rule,

997-998 Cyclopentane, chemical properties of, 466-467

conformations of, 462 heat of combustion and strain energy of

(table), 464 physical properties of (table), 446

Cyclopentanone, hydrogenation of, 710

photochemistry of, 138 1 physical properties of, 679

Cyclopentanophenanthrene, as parent steroid structure, 1471

Cyclopentene, hydroxylation of, 434-436 physical properties and strain of, 475

Cyclophosphoramide, as carcinogen, 1 164 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, 113 1 proton nmr shifts of, 448 rearrangement of, 42 ring-opening reactions of, 466-467 substituted, cis-trans isomers of, 113-1 14

Cyclopropanecarboxaldehyde, preparation of, 7 19 Cyclopropanes, from carbene additions to

alkenes, 565 from carbenes and alkenes, 575 from 1,3-dihalides with metals, 575

Cyclopropanone, hemiketal from, 677-678 preparation and reactions of, 780-78 1 reactivity of, 677-678

Cyclopropanones, addition reactions of, 786-787 in Favorskii rearrangements, 749 ring-openings of, 780-78 1 stability of, 780-78 1 synthesis of, 780

Cyclopropene, physical and chemical properties of, 474-475

Cyclopropenone, carbonyl double bond in, 78 1 synthesis and reactions of, 781

Cyclopropenyl cation and anion, 997-998 Cyclopropyl halides, S, 1 and S,2 reactivity of, 55 1 Cyclopropylmethyl halides, SN 1 and SN2 reactivity

of, 551 Cyclotetradecane, conformation of, 470-47 1 Cysteine, disulfide linkages from, and protein

structures, 1253-1254 in penicillins and cephalosporins, 1492 properties of, 1209

Cystine, properties, 1209 and protein structures, 1253- 1254 in wool, 1457-1458

Cytochrome c, properties, 1250 Cytochromes, in biological oxidations, 1309 Cytosine, as DNA component, 1272-1277

lactam-lactim isomerism of, 1273 in RNA, 1278

2,4-D, 561 Dacron, polyester fiber, 673, 1433, 1438

Dale, J., and conformations of large ring cycloalkanes, 470-474

Dansyl chloride, in peptide sequence determinations, 1230

DDT, 536, 561 Decalin, cis-trans isomers of, conformations of,

480-48 1 Decamethylzirconocene and nitrogen

complex, 1508 Decarbonylation, of diphenylpropanetrione, 779

of 2-oxoalkanoate esters, 832 Decarboxylation, 8 1 1-8 14

of amino acids, 1223-1224 enzymatic of 2-oxobutanoic acid, 1285 ketones from, 732 of 3-oxobutanoic acids, 834 of propanedioic acids, 834

Degenerate orbitals, of cyclic polyenes, 992 and Hund's rule, 153-155

Delocalization energy (see Resonance) Delphinidin, 1403 Delrin, 696, 1433 Denaturation, of proteins, 1259, 1270 Deoxyadenosylcobalamine, 1525 Deoxyribonucleic acids (see also DNA): electron

microscopy and, 262-263 photochemistry of, 1393- 1394

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

furanoside structure of, 1274 phosphates of, 1272- 1274

Desoxycholic acid, 1475- 1476 Detergents, action of, 803-804

biodegradation of, 1057 sodium alkylbenzenesulfonates as, 1056- 1057

Deuteration of arenes (see also Electrophilic aromatic substitution), of arenes, 1057

Dewar benzene, 175, 973-974 Dextrin, 935 Dextrorotatory, definition of, 119, 863 Diacetone alcohol, 752-753, 756-757 2,2-Diaminoazaethene, base strength of, 11 18 Diaminobenzenes (see Benzenediarnines) 2,4-Diaminobenzenol, 13 1 1 4,4'-Diaminobiphenyl, as carcinogen, 1 162 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, 1 1 18 1,5-Diazacyclohexane- 1,4-dione, 1222 1,3-Diazacyclopentadiene, base strength of, 11 18 Diazacyclopropanes, 1202 1,2-Diazacyclopropene, properties of, 120 1- 1202 Diazanes, azides from, 1202

preparation and reactions of, 1 194, 1 197 Diazirenes (see Diazacyclopropenes) Diazirines, 120 1 - 1202 Diazo compounds, preparation of, 1199

reactions of, 1 199- 1200

Diazo coupling reactions, azo compounds from, 1137

mechanism, 1 137 pH dependence of, 1137

Diazoic acids, in alkanamine-nitrous acid reactions, 1 130

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, 1 199 Arndt-Eistert reaction of, 1200 with benzenol, 1294 carbene from, 566, 1200 carboxylic esters from, 856, 1199 as carcinogen, 1 164 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, 1 129- 1 13 1 from amino acids, 1223

Diazonium salts, from arylamines, reactions of (table), 1 133-1 139

from arylamines, formation of, 1133 Diazotate salts, from diazonium salts, 1130, 1139 Dibenzenechromium, 1506- 1507 Dibenzocarbazole, as carcinogen, 1 162 Dibenzocyclopentadiene, acid strength of, 1322 4,5,4',5'-Dibenzothioindigo, 1407 Diborane (see also Hydroboration), ether and

sulfide complexes of, 42 1 formation of, 421 hydroboration with, 420-424 reduction of carboxylic acids with, 810

1,2-Dibromobenzene, possible isomers of, 10 Dibromocarbene, formation and addition to

cyclohexene, 575 from tetrabromomethane and alkyllithiums, 566 from tribromomethane and base, 566

3,3-Dibromo-2,2-dimethylbutane, nmr spectrum of, 1347

1, 1-Dibromoethane, proof of structure by the substitution method, 8-9

1,2-Dibromoethane, nmr spectrum of, 303-304 proof of structure by substitution method, 8-9 and rotational isomerism, 7-8

Di-tert-butyl peroxide, initiation of polymerization with, 1447

Dibutyl phthalate, 1435 1,2-Di-tert-butylethylene, heats of hydrogenation

of cis-trans isomers of, 415-416 Dicarboxylic acids, acidities of (table), 846-849

acyloin reaction of, 852-853 anhydrides from, 847 decarboxylation of, 847 Dieckmann condensation of, 85 1-852 hydroxyketones from, 852-853 imides from, 850 ketones from, 732, 847 physical properties of (table), 846-849 thermal behavior of, 846-847 uses of, 848-849

1,2-Dichlorobenzene, 1,2-benzenediol from, 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, 1 13 Dichloromethane, hydrolysis of, 563

uses of, 562 Dichloromethylbenzene, benzenecarbaldehyde

from, 1318 from methylbenzene, 13 17

Dichromate (see also Chromic acid), benzenamine oxidation with, 1145

N,Nf-Dicyclohexylcarbodiimide, peptide syntheses with, 1240- 1241, 1246

in chemiluminescence reactions, 1399 Dicyclopentadiene, copolymers of, 1435

from 1,3-cyclopentadiene, 1420 Dicyclopentadienyliron, 1504-1506 Dicyclopropylmethane, from di-n-propenylnickel,

1522 Dieckmann condensation, synthesis of

alkoxycarbonylcycloalkanones with, 85 1-852 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, 13 1 1

Diethylene glycol, 662 N,N-Diethylethanamine, base strength of, 1 1 18

physical properties of, 1 101 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, 13 18 Difluoromethylbenzenes, from aldehydes, 13 18 Digitalis steroids, 1473 Digitogenin, structure and occurrence, 1473 Digitoxigenin, structure and occurrence, 1473 Diglyme, 656 Dihydropyran, 653 1,3-Dihydroxy-9,10-anthracenedione, 1407 Dihydroxybenzenes (see Benzenediols) 2,3-Dihydroxybutandioic acid (see Tartaric acid) Dihydroxymethane (see Methanal) 1,3-Dihydroxy-2-propanone, phosphate esters of,

biological aldol addition of, 760-761 in glycolysis, 948 in photosynthesis, 942-943

properties and occurrence of, 907 Diimide, formation of, 4 18-4 19

mechanism of hydrogenation with, 419 self-destruction of, 4 19 stereochemistry of hydrogenations with, 419 thermochemistry of, 4 18

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

2,4-Diisocyano- 1-methylbenzene, 1454- 1455 Diketene, reactions of, 773

structure of, 773 Diketopiperazines, from amino acids, 1222 Dimethyl sulfate, with benzenolate anion, 1294

preparation of, 629 Dimethyl sulfoxide (see Methylsulfinylmethane) Dimethylacetylene (see 2-Butyne) 4-N,N-Dimethylaminoazobenzene, as carcinogen,

1162 N,N-Dimethylaniline, coupling with

benzenediazonium salts, 1137 N,N-Dimethylbenzenamine, coupling with

benzenediazonium salts, 1 137 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, 1 197 Dimethyldiazene, decomposition of, 1 198 1, 1-Dimethylethanamine, physical properties

of, 1101 N,N-Dimethylformamide (see

N,N-Dimethylmethanamide) 1,1-Dimethylhydrazine 3,4-Dimethylidenecyclobutene, angle strain in, 991

Dimethylmercury, bond angles of, 159 N,N-Dimethylmethanamide, aldehydes from, with

Grignard reagents, 729 physical properties of, 239 solvent properties of, 1168

N,N-Dimethylmethanamine, electronic spectrum of, 289

2,2-Dimethylpropyl halides, solvolysis of, 250 Dimethylzinc, bond angles of, 159 Dinitramine, 1195 2,4-Dinitroaniline, 1128 2,4-Dinitrobenzenamine, preparation of, 1 128 1,4-Dinitrobenzene, synthesis of, 1187- 1 189 2,4-Dinitrobenzenol, 1-chloro-2,4-dinitrobenzene

from, 1295 2,4-Dinitrofluorobenzene, in peptide sequencing,

1229- 1230 2,4-Dinitrophenylhydrazones, 698 Dinucleotides, examples of, 926-927 1,2-Diols, from alkene hydroxylations, 434-437

from oxacyclopropane hydrolysis, 435-437 Diosgenin, 1478 1,2-Dioxa-3,4-cyclobutanedione, chemiluminescence

from, 1396-1398 1,2-Dioxacyclobutanes, chemiluminescence from,

1395-1396 1,2-Dioxa-3-cyclobutanones, chemiluminescence

from, 1398-1399 1,4-Dioxacyclohexane, formation of, 662

physical properties of, 239, 654 1,4-Dioxane (see 1,4-Dioxacyclohexane) Dipeptides (see Peptides) Diphenyl ether, 1295 1,2-Diphenyldiazane, from nitrobenzene, 1 194 Diphenyldiazene, decomposition of, 1 198

as dye component, 1407 from nitrobenzene, 1 194 reduction of, 1194

1,2-Diphenyldiazene oxide, from nitrobenzene, 1 194

reduction of, 1 194 Diphenylethanedione, rearrangement of, 775 1,2-Diphenylethene, cis-trans, photochemical

isomerization of, 1384- 1386 electronic absorptions of, 103 1, 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, 130 1 Disrotation, definition and occurrence of,

1006-1009, 1013-1014 Dissymmetric molecules, 1 16 Diterpenes, acid of, 1469

alcohols of, 1468 definition of, 1463

DMF (see N,N-Dirnethylmethanamide) DMSO (see Methylsulfinylmethane) DNA (see also Deoxyribonucleic acid), bases in,

1271-1275 as genetic material, 1271, 1274- 1275 helical structure of, 1273-1275 molecular weights of, 127 1-1272 replication of, 1276- 1277 role of, 1271, 1274-1275 structure of, 1271-1275

Dodecanethiol, as chain transfer agent, 1449 Donor-acceptor complexes (see Charge-transfer

complexes) Doppler effect in Mijssbauer spectroscopy,

1359-1360 Double bonds, formulation of, 165-167

rotation about, 167, 1384- 1386 Double-bond character, and bond lengths, 987-988 Dreiding, A., molecular models of, 451-453 Dubois, R., and bioluminescence, 1397-1399 Durene (see 1,2,4,5-Tetramethylbenzene) Dyes, examples of, 1405- 1408

important properties of, 1408 photosensitizing, 1392, 1411-1412

Dylan, 1432 Dynamite, 648

E,Z convention, for cis-trans isomers, 885-887 and oxime isomers, 887 priority order for, 886-887

El reaction (see 1,2-Elimination reactions, El mechanism)

E2 reaction (see 1,2-Elimination reactions, E2 mechanism)

Ecdysone, role of, 1469 structure and occurrence, 1473

Einstein, A., unit of radiative energy named for, 269

Elastase, serine function in, 1265-1266 Elastin, function of, 1249 Elastomers (see also Polymers, elastomeric), from

1,3-alkadienes, 505-508 Electrical effects, on acid ionizations, 796-800

on aldehyde and ketone reactivity, 678 definition of, 23, 796-800

Electrocyclic rearrangements, conrotation in, 1006-1009, 1014

cyclobutene-butadiene interconversions, 1005-1014

cyclohexadiene-hexatriene interconversions, 1005- 1009

definition of, 1005 disrotation in, 1006- 1009, 1014 energy charge of, 1005 equilibration by, in fluxional molecules,

1089- 1090 of ergosterol, 1394 ,

Huckel rule, 1005-1012 photochemical, 1013-1014, 1387-1388 stereospecificity of, 1006-1009

Electrocyclic rearrangements, equilibration by, in cyclooctatetraene, 1085-1086

Electrode potentials of quinones, 1306-1307 Electrolysis, of carboxylic acid salts, 8 13 Electromagnetic radiation, energy of, 269

wavelengths of, 265-268 Electromagnetic spectrum, frequency units for,

266, 268 spectroscopic uses of, 265-267

Electron contours, 180- 182, 440, 983 Electron delocalization (see also Resonance), and

bonding in hydrogen, 963-964 Electron diffraction, 265 Electron microscopy, for determination of

structures, 262 Electron-pair bonds, theoretical treatment of,

961-964 Electron paramagnetic resonance spectroscopy

(see Esr spectroscopy) Electron spectroscopy for chemical analysis

(ESCA), 1358 Electron-spin resonance spectroscopy (see Esr

spectroscopy) Electronegativity, and acid ionizations, 798-799

and alkene additions, 377, 380-381 and bond angles, 171-172 and carbon-13 shifts, 337 and proton nmr chemical shifts, 307-3 14

Electronegativity scale, definition of, 377 table, 378

Electronic configurations, of atoms, 152-153, in valence states, 158-160, 163, 168

of hydrogen, 962

Electronic excitation energy transfer, 1376-1377 Electronic repulsions, between bonding electrons,

and bond angles, 157-164, 169-172 theoretical calculations and, 982

Electronic spectra, of alcohols, 605 of alkenals and alkenones, 767-768 of alkenes, 353 of alkynes, 356 of anthracene, 1033 applications of, 293 of arenes, 1030- 1034 auxochromes and, 1030- 103 1 Beer-Lambert law in, 291, 293 benzene chromophore and, 1030- 1034 of benzene derivatives, 1032- 1033 benzenoid band in, 1032- 1034 of carboxylic acids (table), 793, 795 /3-carotene, 1401 of charge-transfer complexes, 1 192- 1 193 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, 1 187 of pentacene, 1033- 1034 of phenanthrene, 1034 of phenols, 1288 n to n'x transitions in, 288-293 of polyenes, 29 1-292 of polynuclear aromatic hydrocarbons,

1033-1034 prediction of band positions, 293 of pyrene, 1034 reference works for, 348 and resonance stabilization, 140 1- 1404 rotational energy levels and, 287 transition energies of (table), 287-293 vibrational energy changes and, 287

Electronic spectrum, of amines, 1105 of amino acids, 1216 of benzene, 1032 2-butanone, 292 3-buten-2-one, 292 and color, 1399-1408 molecular-orbital treatment of, 980-98 1 of 2-propanone, 288

Electrophilic aromatic substitution, acylation, of arenes, 105 1-1053

of azulene, 1084 aldehyde syntheses by, 1053- 1055 alkene additions and, 1037- 1040 alkylation, limitations of, 1049- 1050

mechanism of, 1047- 1050 procedures for, 1047-1048

rearrangements in, 1049- 1050 of anthracene, 1069, 1072 of arenamines, 1 128- 1 129 in arene alkylations, 1047- 1050 of azulene, 1084 of benzene (table), 1037-1040 catalysts for, 1041 chlorination by, cyclodextrin effect on, 935-936 chloromethylation, 1054, mechanism of, 13 19 chlorosulfonylation, of benzene, 1056 Friedel-Crafts alkylation, 1047- 1050 Gattermann reaction and, 1054- 1055 Gattermann-Koch reaction and, 1053 halogenation, orientation in, 1070- 1072

procedures for, 1044- 1045 hydrogen exchange by, 1057 intermediates in, 1037- 1040 @so substitution in, 1066-1068 kinetic vs. equilibrium control in, 1066 - metalation, by mercuric salts, 1058 of naphthalene, 1069- 107 1 nitration, mechanism of, 1041

orientation in, 1058-1072 procedures for, 1041- 1043

nitro compounds from, 1 187-1 190 nitrosation, with arylamines and nitrous

acid, 1136 orientation in, electronic substituent effects

in, 1059-1068 meta-directing groups (tables), 1060-1062 ortho-para directing groups (tables),

1060- 1064 patterns of (table), 1059-1060 steric effects of substituents in, 1064 structure proofs for, 1058-1059 transition state and, 1060- 1064, 1066- 1072

of phenanthrene, 1069, 107 1 of phenols, 1296-1300 of polynuclear arenes, 1069-1072 scope and mechanism, 1037-1040 sulfonation, procedures for, 1055- 1057

reversal of, 1055 Electrophilic catalysis, of S, mechanisms, 232-234 Electrophilic reagents, definition of, 207-21 1 Electrophoresis, 1248 Electrostatic effects, and carboxylic acid

ionizations, 799-780 Elimination, definition of, 42 Elimination-addition mechanism (see Nucleophilic

aromatic substitution) Elimination reactions, general characteristics of,

240-25 1 1,l-Elimination reactions, carbenes from, 563-566 1,2-Elimination reactions, characteristics of,

240-252 conformational preferences in, 466-468 El mechanism, acid catalyzed, 25 1

with alcohols, 63 1-632 amines with nitrous acid, 1 130- 1 13 1, 1 133 carbocations in, 249-25 1, 63 1-633

in competition with SN1, 248-249 leaving groups for, 249-25 1 orientations in, 249-250 reactivity order in, 249 rearrangements in, 250-25 1, 632-633 scope of, 248-251

E2 mechanism, acid catalyzed, 251 with alcohols, 630 alkene mixtures from, 245 alkoxides for, 615 of alkyl compounds, 241-248 antarafacial character of, 245-248 antarafacial route, 245-247 basic reagents and, 241-244 competition with S,2, 241 as concerted reaction, 241 concerted vs. stepwise, 247 of ethenyl halides, 243 kinetics of, 241 leaving groups for, 242 orbital model of, 247 orientation effects in, 245 with phosphate esters, 634 reactivity orders for, 242-244 reagents for, 241-245 solvent effects on, 242 stereochemistry of, 245-248 stereospecificity of, 247-248 steric effects and, 242-243 structural effects on, 242-244 suprafacial route, 246-248 temperature effects on, 244 of tetraalkylammonium salts, 242, 1126 in Williamson ether synthesis, 6 15

references for, 252 1,3-Elimination reactions, in amines with nitrous

acid, 1131 cyclopropanes from, 564

Embalming compound, 775 Emulsion, 930 Enamines, alkylation of, 764-765

from amines, 1122 in biological aldol, 760-76 1 formation of, 702 Michael additions of, 845 rearrangement of, 703

Enantiomers, asymmetric synthesis of, 893-894 of 2-butanol, 119 definition of, 115 and diastereomers, 135-139 mechanisms for interconversion of, 895-897 and meso compounds, properties of, 137-138 physical properties of, 1 19- 120 racemization of (see Racemization) resolution of, 866-872 rotation of polarized light by, 119-120 sawhorse drawings of, 127 separation of (see Resolution)

Enantiotopic groups, definition of, 888 Enantiomeric purity, definition of, 870-87 1

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

Endo-exo isomerism, 496-497 Endothermicity, definition of, 76 Ene reaction, of singlet oxygen, 1392 Energy transfer, in chemiluminescence, 1395-1396

definition of, 1374 diphenylmethanone to naphthalene, 1376-1377 ketones to alkenes, 1385-1386 in visual process, 1417

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

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

enols from, 738-739 formation of, 736-738 in halogenations, 742-747 nucleophilic displacements with, 761-763,

833-834 resonance stabilization of, 650

Enols, acidities of (table), 736-738 acidity of, 649-65 1 from enolate ions, 738-739 from hydration of alkynes, 383-384 resonance stabilization of, 650 stabilities of, 648-65 1, 740-741

Enthalpy, definition of changes in, 76 of organic compounds, reference works for,

105-106 Entropy, and carboxylic acid ionizations, 801-802

concept of, 85-87 definition of, 85 effect in methane-steam gas reaction, 410 of gases, 86 and heat of reaction, 84-85 and molecular disorder, 85-86 of organic compounds, reference works for,

105-106 of ring formation, 87 of solids, 86

Enzymes, cell-wall hydrolysis with, 1254 cellulose hydrolysis with, 1270 cleansing uses of, 1270 for decarboxylation, 1285 denaturation of, 1270 disaccharide configurations with, 930 in hydration of trans-butenedioic acid, 371-372 immobilization of, 1270 induced fit in, 1261-1262 inhibition of activity of, 1269-1270 lock-and-key fit, 1261 mechanisms of operation of, of

carboxypeptidase, 1263- 1265 intermediates in, 1262- 1266 serine in, 1265-1266 substrate complexes, 1260- 1262

nomenclature of, 1260 peptide hydrolysis with, 123 1- 1234 properties of, 1260- 1266 proteolytic, 1260, 1263-1266 regulation of activity of, 1269 ynthetases and, 1270-127 1 technology of, 1270- 127 1 x-ray structure determinations of, 126 1- 1262

Eosin, 1392 Epichlorohydrin, in epoxy resins, 1444- 1445

preparation of, 541-542 Epinephrine, 1099 Epoxidation of alkenes, 435-437, 662 Epoxides (see Oxacyclopropanes) Epoxy resins, chemistry of, 1444-1445

epichlorohydrin for, 542 Equatorial positions (see Cyclohexane) Equilenin, structure and occurrence of, 1472 Equilibrium constants, and reactivity, 8 1-88 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), 13 5 8 Esr spectroscopy, of biological reactions, 1368

elements of, 267, 1366- 1367 exchange effects on, 1367-1368 of radicals and radical ions, 1366-1367

Essential oils, 1462 Ester interchange, 82 1 Esterification, acid catalysis of, 6 15-6 18

equilibrium of, 618 mechanism of, 6 16-6 18 thermodynamics of, 6 16

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, 12 1-123 electronic spectrum of, 289 energies of conformations of, 121-122 from ethene reduction, 41 1-412

Ethane, fluorination of, 97 from photolysis of 2-propanone, 1379 reaction with bromine, 14 rotational barrier of, 121-123

saturated character of, 14-15 single bond in, 3 1 space-filling model of, 38

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

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

esters of, chemiluminescence in perhydrolysis of, 1396

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

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

Ethanedioyl dichloride, acyl halides from, 857 Ethanenitrile, bonding in, 3 1-32

physical properties of, 239 in Ritter reactions, 1 178- 1 179 synthesis of, 1185

Ethanoic acid, acidity of (table), 736-738 in alkaloid biosynthesis, 1489 ammonia addition to, 700 in aromatic ring biosynthesis, 1481-1482 bonding in, 3 1-32 in cholesterol biosynthesis, 1486-1488 from ethanol oxidation, 639 in fatty acid biosynthesis, 1480-148 1 infrared spectrum of, 794 ketene from, 772 physical properties of, 239, 792 in terpene biosynthesis, 1483-1485 in vinegar, 49

Ethanoic anhydride, with 1,4-benzenedione, 13 11-13 12

with glycine, 1222 Ethanol, acidic properties of, 6 12-6 13

alkoxide from, 612-613 azeotrope with water, 607 dehydration of, ethene from, 630-63 1

ethoxyethane from, 630-63 1 drying of, 607 formation of, 12 from hydration of ethene, 361 with hydrogen bromide, 13 infrared spectra, hydrogen bonding and,

602-604 nrnr spectrum of, characteristics of, 295-296

exchange effects on, 3 11-3 13 oxidation of, ethanal from, 639

ethanoic acide from, 639 physical properties of, 60 1 space-filling model of, 38 from starch, 935

Ethanoyl coenzyme A, acyl transfer with, 837-840 in carbohydrate metabolism, 944, 949-953 and fatty acid biosynthesis, 1480- 148 1

Ethanoyl nitrate, 1043 N-Ethanoylaminoethanoic acid, 1222 Ethanoylbenzenamines, base strengths of, 11 16 2-Ethanoyloxybenzenecarboxylic acid

(aspirin), 1328

Ethene, ab initio calculations of, 180-182 acidity of, 439-440 addition to 1,3-butadiene, 493 atomic-orbital model of, 165- 167 ball-and-stick models of, 35 bond angles of, 35-36 bond distances in, 37 bromine addition to, 14-16, 359 carbon monoxide copolymer of, 1453 copolymer with propene, 396 as "cycloethane," 463, 467 1,3-cyclopentadiene adduct of, 526-527 dimerization of, 502 double bond in, 3 1 electronic spectrum of, 289-290 from ethanol dehydration, 630-63 1 ethanol from, by hydration, 607 heat of hydrogenation of, 415 hydration of, 361 hydroboration of, 420 hydrogenation of, 4 1 1-4 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, 145 1-1452

block polymer from, 1452 chlorotrifluoroethene adduct of, 13 13 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, 1 199 by Williamson synthesis, 6 14-615, 655

from alkenes, 655

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

autoxidation of, 658-659 block polymers of, 1454 boron trifluoride complexes of, 656 chloro, formation and reactivity of, 704 classification of, 654-656 complexes with Grignard reagents, 577 cyclic, Hantzch-Widman nomenclature for,

659-660 IUPAC rules fo nomenclature of, 659-661 metal complexes of, 665-666

electronic spectra of, 605 infrared stretching frequencies for, 276 IUPAC rules of nomenclature for, 192, 654-656 mass spectra of, 607 oxonium salts from, 656-657 peroxides from, 658-659 phenylmethyl, as protecting group for OH,

65 1-652 physical properties of, 654-656 preparation of (table), 655 reactivity of, 600, acids and, 656-657

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

as solvents for organometallic reactions, 571-572, 577

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

65 1-652 unsaturated, protecting group formation with,

529-530 Williamson synthesis for, 6 14-6 15, 655

Ethoxyethane, boron fluoride complex of, 656 3om ethanol dehydration, 630-63 1, 650-65 1 physical properties of, 239, 654 triethyloxonium salts from, 657

Ethyl acetate (see Ethyl ethanoate) Ethyl acetoacetate (see 3-Oxopropanoate esters) Ethyl alcohol (see Ethanol) Ethyl aminoethanoate, diketopiperazine from, 1222

ethyl diazoethanoate from, 1223 with nitrous acid, 1223

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

Ethyl bromide (see Bromoethane) Ethyl chloride (see Chloroethane) Ethyl cyanoacetate, acidity of, 826 Ethyl diazoethanoate, preparation of, 1223 Ethyl ether (see Ethoxyethane) Ethyl hydrogen sulfate, in dehydration of ethanol,

630-63 1 Ethyl iodide (see Iodoethane) Ethyl malonate (see Propanedioate esters) Ethyl nitroacetate (see Ethyl nitroethanoate) Ethyl nitroethanoate, acidity of, 826

synthesis of, 1191 Ethyl orthoformate (see 1, 1, 1-Triethoxyethane) Ethyl oxalate (see Ethanedioate esters) Ethyl 3-phenylpropenoate (ethyl cinnamate),

Michael additions of, 844

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

industrial perparation of, 647 properties of, 647 uses of, 647-648

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

atomic-orbital model for, 167-168 ball-and-stick models of, 35 bond angles of, 35 bond distances in, 37 bromine addition to, 359 cycloaddition with 1,3-cyclopentadiene, 13 14 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, 1 191- 1 192 Eye chemistry, 1416-1417

FAD (see Flavin adenine dinucleotide) Faraday, M., 10 Farnesene, 1464, 1468 Farnesol, as insect hormone, 1468

pyrophosphate of, 1485, 1488 squalene from, 1485, 1488 as terpene alcohol, 1468

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

Fatty acids, biosynthesis of, 1480- 148 1 characteristics of, 789-79 1 metabolism of, 837-840

Favorskii rearrangement, 748-749 Fehling's solution, 9 13 Fenchone, 1467-1468 Fermentation, in glycolysis, 949

of starch, 935 Ferric bromide, catalysis of arene bromination

with, 1044- 1046 Ferric chloride, with phenols (color test),

1294-1295 Ferricinium ion, 1506 Ferrocene, discovery of, 1504- 1505

electronic configuration of, 1505- 1506 physical properties of, 1504- 1506 reactions of, 1504-1506 structure and conformations of, 1505- 1506

Fiberglass, 1440 Field effect, and carboxylic acid ionizations,

799-780 Fireflies, 1397-1399 Fischer projection formulas, 128-159 '

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

Fischer, E. 0 . H., 418 Fischer, H., and heme synthesis, 1257-1258 Fischer, O., and mauveine structure, 1406 Fischer-Tropsch process, 723 Flavin adenine dinucleotide, as biological oxidizing

agent, 646 in carbohydrate metabolism, 946

Flavin mononucleotide, in biological oxidations, 1308- 1309

Flavone, structure as prototype, 146 1- 1462 Flavonoids, 146 1- 1462 Flax, 933 Flower pigments, 1403 Fluoranthrene, from coal tar, 1080 Fluorene, acid strength of, 1322

from coal tar, 1080 Fluorescamine, with aminoacids, 12 17 Fluorescein, 1392 Fluorescence, of benzene, 1375

definition of, 1374 Fluorination, of alkanes, 99

difluoromethylbenzenes from, 13 18 trifluoromethylbenzenes from, 13 18

Fluoroacetic acid, 792 Fluoroarenes, from arenediazonium salts,

1134-1135 Fluorocarbons, as blood replacements, 569

definition of, 568 development of, 568 physical and chemical properties of, 569 physiological properties of, 569

Fluorochloromethanes, 567 1-Fluoro-2,4-dinitrobenzene, in peptide

sequencing, 1229-1230 Fluoroethanoic acid, 792 2-Fluoroethanol, toxicity of, 569 Fluoroethene, polymer of, 39 1, 1430- 1432

Fluoromethane, 18 ion-cyclotron resonance studies of, 1365

Fluxional molecules, 1089- 1090 Folic acid, structure and biochemical formation,

1 123-1 124 sulfanilamide effect on, 1 123- 1124

Formal bonds, in resonance treatment, 973 Formaldehyde (see Methanal) Formic acid (see Methanoic acid) Formose, and prebiotic evolution, 1283 Formulas, molecular, determination of, 3-4 N-Formylaminomalonic ester synthesis of amino

acids, 1226 Four-center reactions, hydroboration as, 424 Franck-Condon principle, definition of, 1372

in singlet excitation, 1372- 1374 Free energy, definition of, 84

of organic compounds, reference works for, 105-106

standard, 84-85 values for, 85, 87

Free radicals (see Radicals) Free rotation, concept of, 7-8, 121-123 Friedel, C., and acylation of arenes, 105 1-1053

and arene alkylation, 1047- 1050 Friedel-Crafts alkylation of arenes, 1047-1050 Friedel-Crafts ketone synthesis, 105 1- 1053 Friedman, L. J., and cantharidin synthesis,

1497-1498 Front-side approach, 219-223 D-Fructose, 1,6-diphosphate, from biological

aldol reaction, 760-76 1 in glycolysis, 947-948 in photosynthesis, 943

hemiacetal form of, 62 1 osazone from, 924 6-phosphate, conversion to mannose

6-phosphate, 9 19 in glycolysis, 947-948

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

Fructoside, definition of, 925 Functional derivatives, of carboxylic acids (table),

8 17-820 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, 1 148

imides in, 1176 D-Galactose, properties and occurrence of, 907

structure and configuration, 905 Galactoside, definition of, 925

L-Galacturonic acid, 937 Gallic acid, 1304 Gammexane, 1076 Gasoline, composition of, 74 Gates, M., and morphine synthesis, 1499 Gattermann aldehyde synthesis, 1053-1055 Gattermann-Koch aldehyde synthesis, 1053 Gauche conformation, definition of, 124 Gel filtration, 1248 Gel polymers (see Polymers, gel) gem, definition of, 647 Generalized theory of acids and bases, 208-211 Genetic code, 1271, 1276- 1277 Genetic control, DNA in, 1271, 1274-1275 Gentiobiose, amygdalin and, 1327 Geon, 1432 Geranial, 1465- 1466 Geraniol, 1 14- 1 15 Geranyl pyrophosphate, 1484-1485 Gibbs free energy (see Free energy) Ginger, oil of, 1464 D-Glucaric acid, 9 13 Gluconeogenesis, 955-956 D-Glucose, absolute configuration of, 876-877

aldehyde derivatives of, 913-914 aldehyde form of, equilibrium with, 917 aldehyde reactions of, 9 13-9 14 a and ,B forms of, 914-918 amine derivatives of, 936-937 with amines, 923 amygdalin and, 1327 anomers of, 914-9 18 carbon- 13 nmr spectrum of, 9 17-9 18 configuration of, 908-909 conformation of, 9 15-9 16 D-glucaric acid from, 913 glucosylamines from, 923 in glucovanillin, 925-926 hemiacetal form of, 621 metabolism of, 944-950, 955-956 methanol reaction of, 914 methylation of, 92 1-922 mutarotation of anomers of, 917-9 18 occurrence of, 908 osazone from, 924 periodate oxidation of, 921-923 with phenylhydrazine, 924 (;-phosphate, in gluconeogenesis, 955-956

in glycolysis, 947-948 properties and occurrence of, 907 pyranose ring in, 920-922 reanangement to fructose and mannose,

918-919 as reducing sugar, 913 ring-size determination of, 92 1-923 sodium periodate oxidation of, 92 1-922 sorbitol from, 913 structure and configuration, 905 tetramethyl derivative of, 92 1-922

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

Glucovanillin, 925-926 Glutamic acid, in carboxypeptidase, 1263-1264

properties, 1209 synthesis of, 1226

Glutamine, hydrolysis of, 1229 properties, 1209

Glutaric acid (see Pentanedioic acid) Glutathione, 1242- 1243 Glyceraldehyde, chiral forms of, 132-133 D-Glyceraldehyde, absolute configuration of,

875-876 in gluconeogenesis, 955 in glycolysis, 947-948 3-phosphate, biological aldol reaction of,

760-76 1 in photosynthesis, 942-943

properties and occurrence of, 907 structure and configuration, 904

D-Glyceric acid, phosphates of, in photo- synthesis, 942

phosphates of, in glycolysis, 949 Glycerides, hydrolysis of, 790 Glycerol (see 1,2,3-Propanetriol) Glycin, 13 1 1 Glycine, in carboxypeptidase, 1263- 1264

from chloroethanoic acid, 1225 in collagen, 1458 diketopiperazine from, 1222 with ethanoic anhydride, 1222 ethyl ester of, diketopiperazine from, 1222

ethyl diazoethanoate from, 1223 with nitrous acid, 1223

forms of, 1212-1213 ionizations of, 1212-1213 isoelectric point of, 1212 properties of, 1208

Glycols (see appropriate diols) Glycolysis, mechanism of, 946-950 Glycosides, structures of, 925-937 Glymes, 656 Glyoxal, 774-775, 1078 Glyptal resins, 1439- 1440 Goddard, W. A., 111, and GVB orbital theory,

180-182 and ozone structure, 433

Gomberg, M., and triphenylmethyl radical, 1323 Gout, 1316 Graft polymers, 1454- 1455 Grape flavor, 1328 Graphite, properties and structure of, 17-18 Greek letters, and substitution positions, 225 Grignard, V., and organomagnesium

compounds, 576 Grignard reagents (see

Organomagnesium compounds) Griseofulvin, 536 Guanidine, base strength of, 11 18 Guanine, as DNA component, 1272-1277

in RNA, 1278 Guanosine diphosphate, in citric acid cycle,

95 1-954 structure of, 953

D-Gulose, structure and configuration, 905 L-Guluronic acid, 937 Gutta-percha, 507, biosynthesis of, 1485, 1488 GVB method, for benzene, 983-984

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

Gyromagnetic ratio, 297

Hair curling, 1458 Haller-Bauer cleavage of ketones, 747 Hallucinogens, 1098 Haloalkanes, physical properties of (table),

537-538 Haloalkynes (see Alkynyl halides) Haloarenes (see also Aryl halides), from arene-

diazonium 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 organo- metallic compounds by, 573-574

Halogenation, selectivity in, of alkanes, 98-102 Halogenation of arenes (see also Electrophilic

aromatic substitution), 1044- 1045, 1070- 1072

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

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

and alkynes, 389 Hammett, L. P., and reactivity correlations,

1329-1337 Hammett equation, formulation of, 1330-133 1

limitations of, 1336-1337 scope of, 1335

Hammett rho (p ) constant (table), 1330-1337 Hammett sigma (o) constants (table), 1330-1337 Hashish, 1305 Hassel, O., and conformational analysis, 124, 450 Haworth, W. N., and oligosaccharide structures,

928-929 Haworth projections, 9 15 Heart poison, 1473 Heat of reaction, calculation of, 76-80

definition of, 76 reference works for, 105-106

Heat of solution, of ions, 212-2 13 Heats of formation, of alkanes, 86-87 Heats of hydrogenation, of alkenes (table)

415-416 Heavy-metal salts, electrophilic catalysis of halide

S, reactions, 234

Index 4 565

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

Heme, structure of, 1257 Hemiacetals (see also Memiketals), from alcohols

and carbonyl compounds, 621-624 D-glucose as, 9 13-9 18 mechanism of formation of, 622-624

Hemicelluloses, 937-938 Hemiketals (see also Hemiacetals), from alcohols

and carbonyl compounds, 62 1-624 from cyclopropanones, 780-78 1 mechanism of formation of, 622-624

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

Hemp, 933 Henderson-Hasselbalch pH equation, 209 Heparin, 936-937 Heptanedioic acid, properties and uses of, 849 Heptoses, properties and occurrences of, 907 Herbicides, nitro compounds as, 1 195 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 cyclo-

additions, 493 Hexachloroethane, bond distances in, 37 Hexachlorophene, 56 1 1,4-Hexadiene, copolymers of, 1432, 1435 1,5-Hexadiene, from di-T-propenylnickel, 1522 Hexafluoroacetone hydrate, 647 Hexafluoropropene, copolymers of, 568, 1432

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

nitration of, 701 structure of, 700

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

Hexanedioic acid, from cyclohexane and cyclohexanone, 144 1

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

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

with bromine, 968, 971 electrocyclic reactions of, 1005- 10 12 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

Hindered rotation (see Restricted rotation) Hinokitiol, 13 14 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 determina-

tions, 1249 Hoffmann, R., and orbital symmetry rules, 1005 Hofmann degradation, amines from, 1 150,

1153, 1155 Hofmann elimination, 1126 Holding groups, and E2 reactions, 468

stabilization of conformations with, 458-460 Homo, definition of, 12 1 1 HOMO orbitals, 98 1 Homocysteine, 12 1 1 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, 12 1 1 Huckel, E., aromaticity rule, and cyclic ions,

996-998 and cyclic polyenes, 989-995

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

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

999-1005, 1010-1014 and electrocyclic reactions, 1005- 1014 and sigmatropic rearrangements, 1006, 10 10- 1012 and tropylium cation, 1315

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

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

Hunsdiecker reaction, 8 13 Hybrid orbitals (see Atomic orbitals) Hybridization, of atomic orbitals, 159- 16 1

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, 1 194, 1 197 reactions of, 1 194- 1 197 uses of, 1197

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

Index

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

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

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

of 1,5-cyclooctadiene, 423 mechanism of, 425 orientation in additions to alkenes, 42 1-424 stereochemistry of, with alkenes, 422-424

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

appropriate) Hydro forming, 1079- 1083 Hydroformylation, aldehydes from, with

alkenes, 729 of alkenes, 722-723, 15 18-15 19 industrial alcohol syntheses by, 759 mechanism of, 1518-1519

Hydrogen, calculations of bond energy of, 982-983

Hydrogen bonding, in alcohols, concentration effects on, 3 11-3 12

infrared spectra and, 602-604 of alcohols, 600-605 and alpha helix, 1152-1 153 of amides, 1168 of amines, 1 103- 1 105 of carboxylic acids, 791 in DNA structure, 1275-1277 of enols, 740, 776 in enzyme reactions, 1262- 1263, 1266 ethanol, infrared spectra and, 602-604 and hydrogen fluoride, 20 infrared stretching frequencies for, 277 intramolecular hydrogen bonding, of

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

in phenols, 1288 and pleated sheet, 1252-1253 in proteins, 1251-1253, 1259 and proton nmr spectra, 311-313, 741-742,

1291-1292 in tRNA structure, 1279-1282

Hydrogen bromide, addition to alkenes, 379 radical-chain addition to alkenes, 386-389

Hydrogen chloride, addition to alkenes, 379 Hydrogen cyanide, addition to alkenals and

alkenones, 768 addition to aldehydes and ketones, 689-690 physical properties of, 239 in prebiotic evolution, 1282-1284

Hydrogen fluoride, addition to ethyne, 382 additions to alkenes, 368, 379 physical properties of, 19-20, 239

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

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

- Hydrogen peroxide, addition to alkenes, 434-437

in nitrile hydrolysis, 1178 oxidation of amines with, 1 143- 1 144

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, 6 1 1 catalysts for, 411-414, 417-418, 1517-1518 homogeneous, mechanism for rhodium catalyst,

1517-1518 homogeneous catalysts for, 417-418

Hydrogen-deuterium exchange, of arenes, 1057 Hydroperoxides, from alkenes, with hydrogen

peroxide, 72 1 from Grignard reagents and oxygen, 587 ketones from, by rearrangement, 721-722, 732 rearrangements of, to carbonyl compounds,

721-722, 732 Hydroquinone (see 1,4-Benzenediol) Hydroxamic acids, from esters, 858

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

835-836 from Reformatsky reaction, 836 from unsaturated acids, 841-842 unsaturated acids from, 843

4-Hydroxyalkanoic acids, lactones from, 843 2-Hydroxybenzenecarbaldehyde, from

benzenol, 1299 hydrogen bonding in, 1288 physical properties of, 1290

4-Hydroxybenzenecarbaldehyde, physical properties of, 1288, 1290

2-Hydroxybenzenecarboxylic acid, from benzenol, 1298- 1299

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

methyl ester of, 1327-1328 4-Hydroxybenzenecarboxylic acid, from benzenol,

1298-1299 3-Hydroxybutanal (aldol), dehydration of, 755-756

preparation of, 749-75 1 2-Hydroxybutanedioic (malic) acid, from biological

hydration of trans-butenedioic acid, 371-372 as intermediate in citric acid cycle,

95 1-954 2-Hydroxybutanoic acid, oxidation of, NAD+

and, 645 Hydroxycyclobutenediones, 13 13 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, 148 1- 1482 2-Hydroxymethyl-2-methyl- 1,3-propanediol,

polyesters from, 1440 3-Hydroxypentanoic acid, from 2-oxobutanoic

acid, 840 N-(4-Hydroxyphenyl)aminoethanoic acid, 13 1 1 4-Hydroxphenylmethanol, from benzenol, 1300 1 1-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 ~ a n o i c acid, in gluconeogenesis, 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, 146 1- 1462

structure as prototype, 1461-1462 Inductive effects, amine basicities and, 11 14-1 116

in aromatic substitution, 1060- 1064 and carboxylic acid ionization, 798-800

Infrared spectra, of alcohols, hydrogen bonding effects on, 604

of alkanediols, hydrogen bonding effects on, 604 of alkenes, 351-352 of alkynes, 356 of amides, 1170-1171 of amines, 1104

of amino acids, 1215 of arenes, 1027-1030 bending vibrations in, 272-282 of carbonyl compounds (table), 680-681 of carboxylic acids, 281-282, 793-794 conjugation effects on, 292 of diatomic molecules, 272 elements of, 267 of ethanol, 602-604 of ethers, 656 fingerprint region of, 278 hydrogen bonding effects on, 277, 281, 602-604,

793, 1104, 1171 of nitriles, 1 184 of nitro compounds, 1187 overtones in, 352-353 practice of, 273-274 reference works for, 347-348 stretching vibrations in, and atomic masses,

274-275 and bond types, 275 energy changes in, 277 force constants for, 274-275 general considerations, 272-284 and rotational transitions, 275-277 table of, 276-277

structure determination with, 28 1-282, 3 13-3 14 Infrared spectrum, of 3-bromopropene, 324

of 2-butanone, 273 of I-butene, 351-353 of cyclohexanamine, 1104 of cyclooctane, 280 of cyclopropanecarboxylic acid, 28 1-282 of dimethylbenzenes, 1029 of N,N-dimethylmetl~anamide, 117 1 ethanal in tetrachlorometlzane, 794 ethanoic acid in tetrachloromethane, 794 ethanol in tetrachloromethane, 794 of ethynylbenzene, 356 N-methylbenzenamine, 1 104 of methylbenzenes, 1028 of methylcyclohexane, 280 of octane, 279 of N-phenylethanarnide, 1 17 1 of propanamide, 1 17 1 of 2-propanone, 273 of 2,2,4-trimethylpentane, 279 of tropylium ion, 13 15

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

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

Insect pheromones, isomerism and activity of, 141 Insecticides, aryl halides for, 56 1

examples of, 1328 Insulin, function of, 1249

properties, 1250 Interelectronic repulsions, theoretical calculations

and, 982 International Union of Pure and Applied

Chemistry nomenclature (see IUPAC rules)

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

Inversion, of amines, 1 109- 1 1 10 in S, reactions (see Nucleophilic displacement

reactions) Invertase, 930 Iodination, of arenes, 1044- 1046 Iodine chloride, addition to alkenes, 379 Iodine, addition to alkenes, 379

addition to cyclohexene, 367 charge-transfer complex with cyclohexene, 367

Iodobenzene, electronic absorptions of, 1032-1033 preparation of, 1046- 1047

N-Iodobutanimide and hydrogen fluoride, in additions to alkenes, 380

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

Iodoethane, nrnr spectrum of, 3 16-3 18 Iodoform, 746 Iodomethane, amines from, 1125

electronic spectrum of, 289 1-Iodopropane, microwave spectrum of, 27 1 Iodopsin, 1416-1417 Ion-cyclotron resonance, elements of, 267,

1364- 1365 gas-phase acidities from, of alcohols, 1364

of alkynes and water, 437 of carboxylic acids, 802

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

Ion-exchange chromatography, for amino acids, 12 19- 1220

for protein separations, 1248 synthesis of resins for, 1221

Ionization equilibria, of amino acids, 12 12- 12 15 Ionizing power, of solvents, 237-239 Ions, solvation of, 237-238 Ipso substitution of arenes, 1066-1068 Iron compounds, ferrocene as, 1369, 1504- 1506

Mijssbauer spectroscopy of, 1359 Iron tricarbonyl, 1,3-butadiene complex of, 152'

cyclobutadiene complex of, 1359, 1507 cyclooctatetraene complex of, 1359 norbornadiene complex of, 15 10

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, 1 155-1 156

in Curtius degradation, 1 156 in Hofmann degradation, 1 155-1 156

Isoeugenol, 1327 Isoleucine, properties of, 1208 Isomerism, cis-trans, 1 1 1- 1 14, 475-476, 5 1 1,

885-887 and sense of taste and smell, 140-141

configurational, 114 conformationd, examples of, 12 1-125, 448-463,

469-474, 480-48 1, 1345- 1347 diastereomers, 133- 139

geometric, 1 1 1 optical, of 2-butanol, 1 19-120

configurations of, 119, 874-877 conventions for, 119, 879-884 D,L convention for, 13 1- 139 Fischer projections for, 128-159 isomer numbers, 134- 139 representations for, 119, 127, 128-139 resolution and determination of purity of,

866-873 and rotation of polarized light, 118-1 19,

862-866 and taste and odor, 140-141 of threonine, 133-135

types of, 44-45 Isomers, constitutional, 45

position, 44-46 structural, 45

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

unit, 1463, 1483-1485 Isophthalic acid, polyesters from, 1440 Isoprene (see 2-Methyl- 1,3-butadiene) Isoprene rule, basis of, 1462- 1463, 1483- 1488

definition of, 68 3-methyl-3-butenyl pyrophosphate and, 1463,

1483-1485 Isoprenoid compounds, of animal origin, 1469

biosynthesis of, 1483- 1488 structures and types of, 1462-1469

Isopropyl (see 1-Methylethyl) Isopropyl alcohol (see 2-Propanol) Isopropylbenzene [see (1-methylethy1)benzene)l 4-Isopropyltropolone, 13 14 Isotactic polymers, 1430-1435 Isotope effect (see Kinetic isotope effect) IUPAC rules of nomenclature, for acyl halides, 198

for acids, 195 for alcohols, 191 for aldehydes, 192- 193 for alkanecarbonyl groups, 196 for alkanes, 5 1-57 for alkanoyl groups, 193 for alkenes, 59-61 for alkoxy groups, 192 for alkoxycarbonyl groups, 197- 198 for alkyl halides, 56 for alkyl radicals, 52-56 for alkynes, 61-62 for amides, 199, 1169 of amine salts, 1102 for amines, 200-201, 1 100-1102 for amino groups, 201 for anhydrides, 198 of arenes, 62-64, 1024-1025 for benzene and its derivatives, 61-63,

1024- 1025 for benzenols, 191 for carboxamides, 199 for carboxylate groups, 195

Index

for carboxylic acids, 195 for carboxylic anhydrides, 198 for carboxylic esters, 196-198 for cycloalkanes, 57-58 for cycloalkenes, 60 for ethers, 192 functional groups, precedence order of, 186- 187,

188-189 table of, 188-189

for ketones, 194 names to structures, 187-189 for nitriles, 192 for nitroalkanes, 56 numbering of chains in, 52-56, 186-189 for 0x0 derivatives, 194 parentheses in, 54-56 for phenols, 191 of polycycloalkanes, 476-479 for polyenes, 60-61 primary groups, 54 reference books for, 62, 141-142, 204 secondary groups, 54 single- or multiple-word names in, 203-204 of spiranes, 478 for stereoisomers, reference works for, 141-142 structures to names, 186-187 substituents, precedence of, 56 for substituted alkanes, 56 tertiary groups, 54

Jensen, F. R., and cyclohexane conformational equilibria, 456-457

Johnson, W. S., and biomimetic steroid syntheses, 1488-1489

and estrone synthesis, 1496- 1497 Jute, 933 Juvenile hormone, isolation and action of, 1469

as isoprenoid compound, 1469 synthesis of, 1470

KekulC, A., and cyclobutadiene, 989 and molecular formulas, 5 and structure of benzene, 10 structures for benzene, 173-176, 972-975

Kel-F, 568, 1432 Kendrew, J., and x-ray diffraction structure

determinations, 1249 Keratin, 1259 Kerosine, 74 Ketals, from alcohols and carbonyl compounds,

62 1-624 as ethers, 667

hydrolysis of, 624 mechanism of formation of, 622-624 as protecting groups for carbonyl functions,

715-716 Ketene, acylating reactions of, 772

anhydrides from, 857 from cyclobutanone photodissociation, 138 1 cyclopropanone from, with diazomethane, 780 dimerization of, 772 from photolysis of %-propanone, 1379 properties of, 772

Ketenes, carbenes from, 566 cycloadditions with, 773 dimerization of, 503 preparation of, 77 1

Keto-en01 equilibria, 736-741, 776-778, 827-828 Ketoketenes, 77 1 Ketones, acidities of (table), 736-738

from acyl halides, and alkyltetracarbonylferrates, 1516

and alkylzirconocenes, 15 14- 15 15 with cadmium alkyls, 731

additions to, of alcohols, 694 carbon nucleophiles, 689-793 general characteristics of (table), 685-689 of hydrogen cyanide, 689-690 of hydrogen sulfite, 695 of nitrogen nucleophiles (table), 697-703 of organometallics, 577-582 table of examples, 688-689 of thiols, 694 ylides, 69 1-692

from alcohol oxidations, with azabenzene-chromic oxide, 642

biochemical with NAD+, 644-646 with chromic acid, 640-641, 730 Oppenauer method, 730 with permanganate, 643

alcohols from, with Grignard reagents, 609 by Meerwein-Ponndorf-Verley reduction, 6 1 1 by reduction, 6 10-61 1

aldol additions of, 752-754, 756-758, 760-761 from 1,2-alkanediols, by oxidation, 7 17, 730

by rearrangement, 720, 73 1 from alkenes, by hydroboration and

carbonylation, 732 and ozone, 730

alkyl aryl reactivities, Hammet correlation of, 1334

alkylation of, carbon vs. oxygen, 762-763 enamines as alternatives, 764-765 thermodynamics .of, 762

from alkylboranes, by carbonylation, 725-726 from alkylcadmiums with acyl halides, 584 from alkylcoppers, 584 aluminum complexes of, 1052 amides from, by Haller-Bauer cleavage, 747 amines from, 1148, 1154 from arene acylations, 105 1- 1053 azines from, 698 borane reduction of, 707-708 borohydride reduction of, 705-708

from cadmium alkyls and acyl halides, 584 carboxylic acids from, 855 chiral, optical rotatory dispersion of, 890-893

racemization mechanisms of, 895-896 CIDNP in photochemical reactions of,

1353-1356 Claisen condensations with, 832 from copper alkyls and acyl halides, 584 from decarboxylation of dicarboxylic acids, 847 diazo derivatives of, 693 diazomethane reactions with, 692-693 from dicarboxylic acids, by decarboxylation, 732 gem-dichlorides from, 704 electronic excitation of, 1375-1376 electronic spectra of, 681 enamines from, 702 en01 and enolate reactions of, 735-763 en01 content of (table), 740 enolization of, acid induced, 739

base induced, 736-738 equilibrium for, 736-738, 740-741 by Grignard reagents, 582 in haloform reaction, 746-747 in halogenation, 742-745 in nucleophilic reactions, 749-754, 76 1-763

excited states of, 1375-1376 fluorescence and phosphorescence of, 1375-1376 general characteristics of, 671-678 from Grignard reagents (table), 579, 583-584 Haller-Bauer cleavage of, carboxamide from, 747 a-halo, reactivity of, 225, 748-749 haloform reactions of, 746-747

arenecarboxylic acids from, 13 17 a-halogenated, Favorskii rearrangement

of, 748-749 reduction of, 748 SN1 and S,2 reactivity of, 748

halogenation of, base and acid catalyzed, 742-745

mechanism of, 742-745 hemiketal formation from, 62 2 -624 hydration of, 647, 673-674 hydrazones from, 698 from hydroperoxides by rearrangement,

721-722, 732 3-hydroxyalkanoic acids from, 835-836 imines from, 697-699 infrared frequencies, 276, 680-68 1 IUPAC rules of nomenclature for, 194 ketal formation from, 62 1-624 from lithium reagents and carboxylates, 583 mass spectra of, 684 Meerwein-Ponndorf-Verley reduction of,

709-7 10 nitriles from, 1 185 from nitriles, with Grignard reagents, 73 1 nmr spectra of, 684 from Oppenauer oxidation, 730 from organoboranes, 428-429 oxidation of, Baeyer-Villiger, 7 13-7 14 oximes from, 698 from 3-oxoalkanoic esters, by hydrolysis, 73 1

from 3-oxobutanoic acids, 834 from ozonization of alkenes, 43 1-433 with phosphorus pentachloride, 704 photocl~emical cycloadditions of, with alkenes,

1389-1390 photochemistry of, CIDNP effects on, 1353-1356 photoreduction of, 1382- 1383 as photosensitizers, 1385- 1386 physical properties of (table), 678-679 preparative methods for (table), 7 17-729 protecting groups for, 7 15-7 16 reactivity of, and angle strain, 677-678

and bond polarity, 674-678 and electronegative substituents, 678

reduction of, with aluminum alkoxides, 709-710 Clemmenson, 7 1 1 by Grignard reagents, 582 with hydrides (table), 705-708 by hydrogenation, 7 10 photochemical, 1382- 1383 by Wolff-Kishner, 71 1-712

semicarbazones from, 698 with sulfur tetrafluoride, 705 unsaturated (see also Alkenones)

1,baddition of organometallics to, 585-586 addition reactions of, 768-770 electronic spectra of, 767 photochemical cycloadditions of, 503 spectral properties of, 767-768

Ketoses, structures and occurrence of, 903-908 Kharasch, M. S., radical mechanism for hydrogen

bromide additions to alkenes, 386 Kinetic control, of additions to alkenes, 374-376

in carbocation rearrangements, 633 Kinetic isotope effect, in chromic acid oxi-

dation, 641 Kolbe electrolysis, 8 13 Kolbe-Schmitt reaction, 1298-1299 Krebs, H. A., and citric acid cycle, 944, 951-954 Krebs cycle, 944, 951-954

aldol addition in, 839-840 Kuhn, R., and cis-trans isomers of cumulated

trienes, 5 1 1

P-Lactamases, 1492 Lactams, as functional derivatives of carboxylic

acids, 8 19 P-Lactams, in penicillins and cephalosporins, 1492 Lactic acid (see 2-Hydroxypropanoic acid) Lactic acid dehydrogenase, 645 Lactide formation, 843 Lactones, as functional derivatives of carboxylic

acids, 8 19 from hydroxy acids, 843 from unsaturated acids, 842-843

Lactose, properties and occurrence of, 907 structure and configuration of, 929

Ladder polymers, 1456- 1457 Ladenburg, A., structure for benzene, 12 Ladenburg benzene, prismane and, 482 LAH (see Lithium aluminum hydride reduction) Lanosterol, structure and biosynthesis of,

1486-1487 Lanthanide shift reagents, 872-873 Le Bel, J. A., 6

and asymmetric carbon, 116 and tetrahedral carbon, 118

Least structural change, principle of, 13 Leather, 1459 Leaving groups (see also Nucleophilic displace-

ment reactions), for amide formation, 1177-1 178

Lemon, oil of, 1464, 1466 Leucine, isomers of, and taste, 140

properties of, 1208 Levorotatory, definition of, 119, 863 Lewis, G. N., and acid-base theory, 208-209

and theory of valence, 19 Lewis acids definition of, 208-209 Lewis bases, definition of, 208-209 Lewis structures, and electron-pair bonds, 19 Librium, 1098 Lichen pigment, 1304 Light (see Photochemistry, Electronic spectra, etc.) Light absorption (see Electronic spectra or

Photochemistry) Lily-of-the-valley, 1468 Limonene, 1464 Linalool, 1465-1466 Lindane, 536-537, 1076 Lindlar catalyst, for selective reduction of

alkynes, 414 Line spectra, 268-269 Line widths in nmr spectra, 1343-1344 Linoleic acid, 789-790 Lipids, 790, 805 Lithium aluminum hydride reduction, alcohols

from, with carbonyl compounds, 610, 809-810, 824

with oxacyclopropanes, 6 10 aldehydes from, acids and acyl derivatives,

728, 8 10-81 1, 824-825 amide and nitrile reductions, 719, 728,

824-825 amines from, 824-825, 1146- 1148, 1 154 of carboxylic acids to alcohols and aldehydes,

810-811 of nitriles to aldehydes, 719, 824 procedures for, 705-706

Lithium bis(trimethylsilyl)amide, enolate anion formation with, 836

Lithium hydride, bonding and physical properties of, 19-21

reactions of, 20-21 "Living" polymerizations, 145 1- 1452 London, F., dispersion forces and, 455 London forces, 455 Lowry, T. M., and acid-base theory, 208 LSD, 1097

Lubricating oils, 74 Lucas, H. J., and alcohol-type test, 626 Luciferin and lucerifase, 1397- 1399 Lucite, 1433 LUMO orbitals, 98 1 Lustron, 1433 Lycopene, biosynthesis of, 1485, 1488

electronic absorptions of, 1401 as isoprenoid hydrocarbon, 1464 structure of, 1401

Lynen, F., and fatty acid biosynthesis, 1480 Lysergic acid, 1097 Lysine, codon for, 1282

genetic code for, 1277 ionization equilibria of, 1214- 12 15 properties, 1209

Lysozyme, carbon-13 spectrum of, 1286 disulfide bridges in, 1254- 1255 function of, 1254 properties, 1250 structure of, 1254-1255

D-Lyxose, structure and configuration, 904

Magenta dye, 1410-1414 Maleic acid (see cis-Butenedioic acid) Maleic anhydride (see cis-Butenedioic anhydride) Malonic ester acid synthesis, 833-834 Malonic esters (see Propanedioate esters) Maltose, properties and occurrence of, 907

from starch, 934 structure and configuration of, 929

D-Mannose, osazone from, 924 6-phosphate, conversion to fructose

6-phosphate, 919 properties and occurrence of, 907 structure and configuration, 905

D-Mannuronic acid, 937 Markownikoff's rule, definition of, 376

uses of, 377-381 violation of, electron-attracting groups and,

380-381 by radical addition reactions, 386-388

Mass spectra, of alcohols, 607 of aldehydes, 340-341, 684 of alkynes, 357 of amines, 1 106- 1 108 of amino acids, 1216 apparatus for, 340, 136 1-1363 characteristics of, 340-345 chemical ionization procedure for,

1361-1363 elemental compositions from, 341-343 of ethers, 607, 656 field ionization procedure for, 1361 fragmentations in, 344-345, 1360- 1365 hydrocarbons, chemical ionization of, 1362 isotopes and, 342-343

of ketones, 340-341, 684, 1362 methane, chemical ionization of, 136 1- 1362 molecular formulas from, 341-343 molecular weights from, 341 parent peak in, 341-345, 1361-1363 rearrangements in, 345 reference works for, 342, 349, 1370 sample volatilization in, 1363

Mass spectrum, of 2-butanone, 340-341 of I-(3,4-dimethoxyphenyl)ethanone, 1362 of 2,2-dimethylbutane, 344 of ethyl butanoate, 344 of methylbenzene, 345 of octadecane, 1363 of 2-pentanone, 346 of propanal, 34e341 of 2-propanone, 340-341

Mauveine, 1406 Mayer, V., 27-28 Mayo, F. R., radical mechanism for hydrogen

bromide additions to alkenes, 386 Meerwein reaction, 1 135-1 136 Meerwein-Ponndorf-Verley reduction, 6 1 1,

709-7 10 Meisenheimer, J., and aryl addition complexes, 555 Melmac (melamine) resins, 1444 Melvalonic acid, in cholesterol biosynthesis,

1486- 1488 in terpene biosynthesis, 1483-1485, 1488

Membrane lipids, 790, 805 Menadione, 13 10 Menthol, 1466- 1467 Menthone, 1466- 1467 Mercaptobenzothiazole, 1429 Mercaptoethanoic acid, with wool, 1458 Mercuration of arenes, 1058 Mercuric salts, addition to alkynes, 383-384

additions to alkenes, 380 Merrifield, R. B., and solid-phase peptide

syntheses, 1242- 1247 Mescaline, 1097 Mesityl oxide, 756 Mesitylene (see 1,3,5-Trimethylbenzene) Meso compounds (see also Chirality and Iso-

merism), 135-139 Mess,enger RNA, 1279-1282 Mestranol, 1479 meta, definition of, 63 Meta-directing groups (tables) 1060-1062 Metabolism (see Biosynthesis, Glycolysis, etc.) Metal carbonyls (see Transition-metal complexes) Metal chelates, of 2,4-pentanedione, 777 Metal-halogen exchange, preparation of organo-

metallic compounds by, 573-574 Metaldehyde, 696 Metalloporphyrins, 1256-1259 Metaphosphoric acid, esters of, formation and

reactions of, 634-637 Metathesis of alkenes, 1520- 152 1 Methanal, alcohols from, with Grignard reagents,

577, 579, 608 in aldol additions, 753-754

ammonia addition to, 700 Bakelite resins from, 1442- 1443 ball-and-stick model of, 35 with benzenol, 1442- 1443 bond angles of, 35 bonding in, 31-32, 674-675 Cannizzaro reaction of, 707-709 in chloromethylation of arenes, 1054, 1319 electronic excitation of, 1375-1376 excited states of, 1375-1376 fluorescence and phosphorescence of,

1375-1376 geometries of excited states of, 1376 hexamethylenetetramine from, 700 molecular energy levels of, 1375-1376 physical properties of, 679 polymerization of, 696 in prebiotic evolution, 1282-1284 resins from, 1442-1444 with urea to give resin, 1443-1444

Methanamide, physical properties of, 239 Methanamine, physical properties of, 110 1 Methane, bonds and geometry of, 169

in chemical ionization mass spectrum of, 1361-1362

chlorination of, 8 1-85, 88-96 combustion of, 76 electronic spectrum of, 289 heat of combustion of, 76 ionization of, 1361 mass spectral use of, 1361-1362 from photolysis of 2-propanone, 1379 physical properties of, 19-2 1 polychlorination of, 100 in prebiotic evolution, 1282 space-filling model of, 38 steam-gas reaction of, 410

Methanediol, 646-647 Methanenitrile, bonding in, 3 1-32 Methanoic acid, physical properties of, 239, 792 Methanol, acidic properties of, 613

atomic-orbital model of, 164-165 with carbon monoxide, ethanoic acid from, 1520 electronic spectrum of, 289 ethanoic acid from, 1520 hydrogen bromide salt of, 613-614 industrial preparation of, 6 12 physical properties of, 239, 601

Methide anion, geometry of, 169 Methionine, properties, 1209 Methodology of organic synthesis, 5 13-5 15 Methoxybenzene, benzenol from, 1295

from benzenol, 1294 chlorination of, cyclodextrin effect on,

935-936 cleavage with hydrogen bromide, 1295

Methoxychloromethane, as carcinogen, 1 164 Methoxyethene, physical properties of, 654

preparation of, 649 Methoxymethane, electronic spectrum of, 289

with hydrogen bromide, 13 trimethyloxonium salts from, 657

Methyl anthranilate, 1328 Methyl bromide (see Bromomethane) Methyl Carbitol, 662 Methyl carbocation, geometry of, 169 Methyl Cellosolve, 656 Methyl chloride (see Chloromethane) Methyl chloromethyl ether, as carcinogen, 1 164 Methyl ethyl ketone (see 2-Butanone) Methyl fluoride (see Fluoromethane) Methyl D-glucosides, 9 15 Methyl 2-hydroxybenzenecarboxylate, 1327- 1328 Methyl iodide (see also Iodomethane)

amines from, 1 125 nucleophilic reaction with rhodium, 1520

Methyl methacrylate (see Methyl 2-methyl- propenoate)

Methyl 2-methylpropenoate, block polymer from, 1452

copolymerization of, 1452 polymers of, 391, 1433, 1451

Methyl parathion, 1328 Methyl phenyl ether (see Methoxybenzene) Methyl phenyl ketone (see Phenylethanone) Methyl radical, geometry of, 169- 170 Methyl salicylate, 1327- 1328 Methyl vinyl ketone (see 3-Buten-2-one) Methylacetylene (see Propyne) Methylamine (see Methanamine) 4-N-Methylaminobenzenol, 13 1 1 N-Methylaniline (see N-Methylbenzenamine) 4-Methylbenzenamine, base strength of, 11 15 N-Methylbenzenamine, infrared spectrum of, 1104 Methylbenzene, benzenecarboxylic acid from, 13 17

benzenol from, 1292-1293 bromination of, with bromotrichloromethane,

103-104 chlorination of, with tert-butyl hypochlorite,

103-104 halogenation of, ring, 1046 industrial syntheses based on, 1083 iodination of, 1046 mass spectrum of, 345 nitration of, 1042-1043, 1189

. from petroleum, 1079- 1083 physical properties of, 1027 side-chain halogenation of, 97, 104, 546-547,

1046, 1317-1318 stabilization energy of, 985

Methylbenzenes, infrared spectra of, 1027-1029 4-Methylbenzenol, physical properties of, 1289 Methylbenzenols, from coal tar, 1291 2-Methyl-1,3-butadiene, anionic polymerization

of, 1451 copolymer with 2-methylpropene, 506, 508 copolymerization of, 1453 polymers and copolymers of, 1432-1433

cis-trans isomers of, 507-508 elastic properties of, 507-508

purification through sulfur dioxide adduct, 500-501

stabilization energy of, 986 sulfur dioxide adduct, 500-501

2-Methylbutane, bromination of, 10 1- 102 chlorination of, 100- 102

2-Methyl-2-butanol, nmr spectrum of, 305 2-Methyl-2-butene, heat of hydrogenation of, 415 3-Methyl-3-butenyl pyrophosphate, as biological

isoprene unit, 1463, 1483-1485 Methylcyclohexane, carbon- 13 nmr spectrum

of, 460 conformational equilibria of, 453-454, 457, 460 infrared spectrum of, 280 from petroleum, 108 1

Methylene (see Carbene) Methylene blue, 1392 Methylene glycol, 646-647 (I-Methylethenyl)benzene, nmr spectrum of,

325-327 (I-Methylethy1)benzene (isopropyl benzene),

acid strength of, 1322 autoxidation of, 721 benzenol from, 72 1-722, 1293 physical properties of, 1027 2-propanone from, 721-722, 1293

3-Methyl-3- hydroxypentanedioic acid (mevalonic acid), 1483- 1488

Methyllithium, 18 Methylmalonyl coenzyme A, conversion to

succinyl coenzyme A, 1526 N-Methylmethanamide, nitrogen-15 nmr spectrum

of, 1175 2-Methyl-l,4-naphthalenedione, vitamin K activity

of, 1310 N-Methyl-N-nitrobenzenamine, as carcinogen, 1 164 1-Methyl-3-nitrobenzene, synthesis of, 1 190 N-Methyl-N-nitrosourea, as carcinogen, 1 164 N-Methyl-N-nitro-2,4,6-trinitrobenzenamine, 1 192 Methylphenols (see Methylbenzenols) 2-Methylpropane, in alkylation of 2-methyl-

propene, 397-398 heat of combustion of, 79 yield calculations for bromination of, 5 15-5 16

Methylpropanedioyl coenzyme A, conversion to butanedioyl coenzyme A, 1526

Methylpropanoic acid, conversion to butanedioic acid, vitamin B,, and, 1526

2-Methyl-2-propanol, acidic properties of, 613 dehydration of, 63 1-632 industrial preparation of, 607

2 - ~ e t h ~ l ~ r o ~ e i e , alkylation by 2-methylpropane: 397-398

cationic polymerization of, 393-395 copolymer with 1,3-butadiene, 506, 508 from dehydration of 2-methyl-2-propanol,

63 1-632 diisobutylene from, 394-395 hydration of, 369 hydrogen bromide addition to, kinetic vs.

equilibrium control in, 374-376 polymers and copolymers of, 391, 1432 radical-chain polymerization of, 396 in Ritter reaction, 1178-1 179

2-Methylpropenenitrile, 689 N-Methylpyrrolidine, solvent properties of, 1168

Methylstyrene [see (I-Methyletheny1)benzenel Methylsulfinylmethane, in Gabriel m i n e

synthesis, 1127 oxidation of alcohols and halides with, 718 physical properties of, 239 as solvent, 238

1-Methyl-2,4,6-trinitrobenzene (TNT), from methylbenzene, 1189

oxidation of, 1 189 1,3,5-trinitrobenzene from, 1189

Metol, 1311 Micelles, formation of, 803-804

reactions in, 804-805 Michael addition, of alkenones, 770

amino acids from, 1226 in annelation reactions, 1478 in color photography, 1413-1415 of enamines, 845 in methanal-benzenol reaction, 1442 of nitro compounds, 1196 in steroid syntheses, 1478 of unsaturated esters, 844-845

Microwave spectroscopy, elements of, 267 of 1 -iodopropane, 27 1 reference works for, 347 uses of, 270-27 1

Migration aptitudes of groups, 714 Miller, S., and prebiotic evolution, 1283 Mint, 1462 Mirror image isomers (see Chirality) Mobius, A. F., strip of, 1001 Mobius orbital systems, and cycloadditions,

1000-1004, 1010-1014 and electrocyclic reactions, 1005-1014 energy levels of, 1000-1003 and sigmatropic rearrangements, 1006,

1010-1012 Models, ball-and-stick, 3 Mohr, E., strainless cyclohexane theory of,

464, 480 Molecular disorder, and entropy, 85-87 Molecular energy levels, electronic component of,

270, 287-293 rotational component of, 270-271, 275 vibrational component of, 270-286

Molecular formulas, conventions for, 3 1-34 determination of, 2, 3 three-dimensional representations of, 125- 130

Molecular geometry (see Bond angles, Bond lengths, and specific compounds)

Molecular-orbital treatment, ab initio method and, 98 1-984

a parameter of, 964-965, 970-971 of benzene, 969-971 of benzene with bromine, 971 p parameter of, 964-965, 970-971 of 1,3-butadiene, 975-977 calculation of energy levels, 992-994, 1002 of cyclic ions, 996-998 of cyclic polyenes, 989-995 of 1,3,5-cyclohexatriene, 969-9 of electrocyclic rearrangements, 1005-1014

of electron-pair bonds, 96 1-963 and electronic spectra, 980-98 1 of ethene, 964-965 GVB method and, 983-984 of 1,3,5-hexatriene with bromine, 97 1 of hydrogen, 96 1-964 of pericyclic reactions, 999-10 17 of propenal, 977 of 2-propenyl cation, 979-980 of sigmatropic rearrangements, 1006,

1010-1012 stabilization energies (table), 985-986

Molozonides, as intermediates in ozonization reactions, 433

Molybdenum hexafluoride, aryl side-chain fluorides from, 13 18

Monosaccharides, definition of, 902-903 Morphine, 1097

synthesis of, 1499- 1500 Mossbauer spectroscopy, elements of, 267

organoiron compounds and, 1359-1360 principles and uses of, 1359-1360

Moth hormones, 1469, 1473 Mutarotation, of L-glucose anomers, 9 17-9 18 Mylar, polyester film, 1433 Myleran, as carcinogen, 1164 Myoglobin, function, 1249- 1250, 1254- 1259

as oxygen carrier, 1254-1259 properties, 1250 structure of, 1254-1259

Myrcene, 1462-1464

NADH (see Nicotinamide adenine dinucleotide, reduced form)

NADPH (see Nicotinamide adenine nucleotide phosphate)

Name reactions, 1053 1-Naphthalenamine, from 1-naphthalenol,

1295-1296 2-Naphthalenamine, as carcinogen, 1 162

from 2-naphthalenol, 1295-1296 Naphthalene, acylation of, 1070

from azulene, 1084 1,s-bis(bromomethy1)-, crystal structure of,

264-265 bromination of, 1070 from coal tar, 1080 cycloadditions to, 1077 1,s-dibromo-, space-filling model of, 37-38 electronic spectra of, 1033 energy transfer to, from

diphenylmethanone, 1377 hydrogenation of, 1073 inhibition of diphenylmethanone

photoreduction, 1383 negative radical ion of, esr spectra of, 1367 nitration of, 1043, 1070

phosphorescence of, 1377 physical properties of, 1027 quinones of, 1305-13 10 sodium in ethanol reduction of, 1073 stabilization energy of, 985 substitution reactions of (table), 1069- 107 1 sulfonation, 1070 triplet state of, 1377

1,2-Naphthalenedione, as quinone, 1305 1,4-Naphthalenedione, blood coagulants from, 13 10

as quinone, 1305 vitamin K activity of, 1310

2,6-Naphthalenedione, as quinone, 1306 I-Naphthalenol, with aryldiazonium salts, 1300

I-naphthalenamine from, 1295-1296 physical properties of, 1290

2-Naphthalenol, 2-naphthalenamine from, 1295-1296

physical properties of, 1290 Naphthalenols, from coal tar, 1081 Naphthols (see Naphthalenols) Naphthylamines (see Naphthalenamines) Natta, G., and polymer stereochemistry, 1430- 1435 Natural products, approaches to study of,

1461-1462 biosynthetic pathways for, 1461-1462 definition and classification of, 1460- 146 1 structure determination of, 1461 and synthetic chemistry, 146 1

Natural rubber, 507-508 biosynthesis of, 1485, 1488 vulcanization of, 1429- 1430

NBS (see N-Bromobutanimide) Neopentane (see 2,2-Dimethylpropane) Neopentyl derivatives, rearrangement of, in

solvolysis reactions, 250 solvolysis of, 250 steric hindrance in SN reactions of, 224-225

Neopentyl iodide, synthesis, 587 Neoprene, 506, 1433 Neral, 1465-1466 Nerol, 1465-1466 Neryl pyrophosphate, 1484- 1485 Neutron diffraction, 265 Newman projections, 125-126 Niacin, 1099 Nickel, 1,3-butadiene trimerization with, 1523

1,5-cyclooctadiene complex of, 15 10 T-propenyl complexes of, preparation of, 1522

reactions of, 1522- 1524 structures of, 1522-1523

Nicotinamide adenine dinucleotide (oxidized form, NADC), alcohol oxidation with, 644-647

Nicotinamide adenine dinucleotide (reduced form, NADH), in carbohydrate metabolism, 945-952

Nicotinamide adenine dinucleotide phosphate (oxidized form, NADPf), in photosynthesis, 940-941

Nicotinamide adenine dinucleotide phosphate (reduced form, NADPH), in fatty acid biosynthesis, 148 1

in terpene biosynthesis, 1485 Nicotinic acid, 1099 Ninhydrin, 779

with amino acids, 1216-1218, 1221 Nitrate ion, and resonance, 176- 177 Nitration, of alkanes, 105

of arenes (see also Electrophilic aromatic substitution), acyl nitrates in, 1043

alkyl substituted, 1042- 1043 ips0 mechanism for, 1066- 1068 mechanism of, 1041 nitric and sulfuric acids in, 1041-1042 nitronium salts in, 1041, 1044 orientation in, 104 1- 1042, 1058- 1072

Nitrenes, in Curtius degradation, 1156 in Hofmann degradation, 1 155- 1 156

Nitric acid (see also Nitration) cyclohexene oxidation with, 1043 in iodination of arenes, 1045-1046 in nitration of arenes, 1041-1043 oxidations of alkylarenes and alkyl aryl ketones

with, 1317 Nitriles, acidities of (table), 736-738

from aldehydes and ketones, 1185 aldehydes from, by hydride reduction, 7 19,

728, 824 alkylation of, 1 185 amides from, 858, 1177-1178 from amides, 1185 amines from, by hydride reduction, 824-825 from arenediazonium salts, 1 134, 1 185 as carboxylic acid derivatives, 202, 819 carboxylic acids from, 854, 1185 dipole moments of, 1 185 from halides, 1 184- 1 185 infrared spectra of, 1184 infrared stretching frequencies for, 276 IUPAC rules of nomenclature for, 202 ketones from, with Grignard reagents, 73 1 from oximes, 1185 preparation of, 1 184- 1 185 reactions of, 1185 reduction to aldehydes, 719, 728, 824 reduction to amines, 1 146- 1 147 Ritter reaction and, 1149, 1 178-1 179 solvent properties of, 1184 unsaturated, in [4 + 21 cycloadditions (table),

493-494 Nitrilium ions, in Ritter reaction, 1178--1179 Nitro compounds, aci forms of, 1195-1 196

acidity of, 1 195- 1 196 aldol additions of, 1196 from aldol and Michael additions, 758, 1196 from alkanes, 1 187 from alkyl halides, 1 190- 1 19 1 from arene nitration, 1039- 1044, 1058- 1072,

1187-1188 from arenes, 1 187- 1 190 charge-transfer complexes of, 1 192-1 193 diazene oxides from, 1194 dipole moments of, 1186 electronic spectra of, 1187

as explosives, 1 19 1- 1 192 as herbicides, 1195 infrared spectra of, 1 187 Michael additions of, 1196 as polymerization inhibitors, 1449 reduction of, amines from, 1146- 1 147,

1151, 1193 azanols from, 1194 nitroso compounds from, 1 193- 1 194

resonance and, 1186 by Sandmeyer reaction, 1191 thermochemistry of, 119 1 unsaturated, in [4 + 21 cycloadditions (table),

493-494 volatility of, 1 186-1 187 water solubility of, 1187

Nitroalkanes, acidities of (table), 736-738 aldol additions of, 758 preparation of, 105, 1187

Nitroanilines (see Nitrobenzenamines) Nitroarenes, from arenediazonium salts, 1134

by nitration, 1041- 1044, 1059- 1060, 1065- 107 1 2-Nitrobenzenamine, from

N-nitrobenzenamine, 1 140 4-Nitrobenzenamine, base strength of, 11 15 N-Nitrobenzenamine, rearrangement of, 1 140 Nitrobenzenamines, base strengths of, 11 15-1 116 Nitrobenzene, from benzene, 1041

electronic absorptions of, 1402- 1403 nmr spectrum of, 1036-1037 reduction of, azanols from, 1193-1 194

azo compounds from, 1194 azoxy compounds from, 1194 benzenamine from, 1193- 1 194 diazanes from, 1194 hydrazines from, 1 194 reagents for, 1 193- 1 194

as solvent, in arene acylations, 1052, 1070 Nitrobenzenecarboxylic acids, and Hammett

equation, 1329- 1330 4-Nitro- l,2-benzenedicarboxylic acid, 13 17 4-Nitrobenzenol, acidity of, 1294

and anion, electronic absorptions of, 1402 electronic absorptions of, 1402- 1403 physical properties of, 1289

Nitrobenzenols, hydrogen bonding in, 129 1 - 1292 nmr spectra of, 1291-1292

4-Nitrobiphenyl, as carcinogen, 1 162 Nitroethane, 11 87

from alkane nitrations, 105 Nitroethanoate esters, acidity of, 826 Nitrogen (see also Amines, Amides, Nitriles, etc.),

fixation of, by decamethylzirconocene, 1508 by titanocene, 1508

oxidation states of, 1141-1 142 Nitrogen bases, drugs from, 1098-1099

naturally occurring examples, 1097-1099 Nitrogen mustard, as carcinogen, 1164 Nitrogen ylides, 692-693 Nitromethane, aci form of, 1195

acidity of, 1195 aldol addition of, 1196

from alkane nitrations, 105, 1187 from nitroethanoic acid, 1 19 1 physical properties of, 239 thermochemistry of, 1 19 1

Nitronium ion, in arene nitration, 1041-1044 formation of, 1041

Nitronium salts, 1044 2-Nitropropane, aldol and Michael addition

reactions of, 1196 Nitropropanes, 1187 N-Nitrosamines, from alkanamines, 1129- 1 13 1 Nitrosamines, rearrangement of, 1139 Nitrosation, of alkan- and benzenamines,

1129-1130, 1136 N-Nitrosazacyclohexane, as carcinogen, 1 164 Nitroso compounds, azo compounds from, 1194 N-Nitrosoamides, diazomethane from, 1 199 Nitrosobenzene, from

N-phenylhydroxylamine, 1 194 N-Nitroso-N-methylbenzenamine, rearrangement

of, 1139 Nitrosyl chloride, additions to alkenes, 380 Nitrous acid, with alkanamines, 1129-1 13 1

amine reactions of, alcohols from, 1096 with amino acid esters, 1223 with amino acids, 1223 azides from, 1202 with diazanes, 1202 tertiary m i n e complexes with, 1130

Nitrous oxide, and resonance, 176- 177 Nitryl chloride, additions to alkenes, 380 Nmr spectra, of alcohols, 605

of aldehydes, 684 of alkenals and alkenones, 768 of alkenes, 353 of alkynes, 356-357 of amides, broad lines in, 1 172- 1 173

cis-trans isomerism and, 1 172- 1 173 nitrogen-15 in, 1175 proton exchange and, 1172

of amines, chemical shifts in, 1105 hydrogen exchange in, 1105-1 106 inversion effects on, 1 1 10- 11 11

of arenes, ring current effects on, 1034-1035 spin-spin splittings in, 1036- 1037

of carbon-13, characteristics of, 335-339 chemical shifts of, 335-336 and cyclohexane derivatives, 460 decoupling of protons and, 336-337 of D-glucose, 9 17-9 18 of lysozyme, 1286 sensitivity of detection of, 335 structural analysis with, 336-337 of warfarin, 336-337

of carbon-13 satellites in, 338 of [18]annulene, ring-current effect on, 1035 of carboxylic acids, 793-795 and chemical exchange, chemical-shift effects

from, 311-313 spin-spin splitting effects from, 321-322

chemical shift in, averaging by chemical exchange, 3 1 1-3 13

averaging by conformational equilibration, 303-304, 456, 460-46 1, 1345-1347

and carbon bond types, 3 10-3 1 1 and chemical exchange of protons, 3 11-3 13 and chirality, 302-304 conventions for, 304-306 of cyclopropane protons, 448 diamagnetic effects in, 300-301 electronegativity effects on, 307-310 equivalence of atoms in, 300-304 exchange averaging of, 1345- 1346 general characteristics of, 300-3 15 and hydrogen bonding, 3 11 and infrared for structure determination,

3 13-3 14 magnetic field strength and, 304-306 pprn scale for, 306 proton values for (table), 306-3 1 1 reference standard for, 304 shielding parameters of, 300-301 Shoolery7s rule for, 3 10 standard for, 304 stereochemistry and, 301-304 structure correlations for, 306-3 15 tetramethylsilane as reference, 304 units for, 304-306

chemically induced dynamic polarization and, 1353-1356

chiral-shift reagents and, 872-873 chiral solvents and, 871-872 CIDNP and, 1353-1356 conformational equilibration and, 303-304, 456,

460-461, 1345-1347 of cycloalkanes, 447-448 and decoupling, 322 diastereotopic atoms in, 303 of I, 1-difl9orocyclohexane, fluorine-19, 460 elements of, 267 enantiomeric purity and, 87 1-872 enantiotopic atoms in, 303 energies of transitions in, 299 of ethers, 656 exchange effects on, 1345-1346 field sweep in, 298-299 field-frequency relations for, 297-298 fluorine- 19 of cyclohexane derivatives, 46 1 fluorine- 19 splittings in, 539 forbidden transitions in, 1352 frequency sweep in, 298-299 of Grignard reagent, 1524 and hydrogen bonding, 605, 793-795, 1291-1293 hydrogen bonding effects on, with carboxylic

acids, 793-795 instrumentation for, 295-296 integrals of peaks, 300, 322 of ketones, 684 lanthanide shift reagents and, 872-873 lifetime of states and, 1343-1346 line widths in, 1343-1344 magnetic energy levels in, 295, 297-299,

1349-1352 magnetic field effects on, 304-306

of methylcyclohexane, carbon- 13, 460 of nitrobenzenols, 1291-1292 nitrogen- 15, of N-methylmethanamide, 1 175 nuclear spin and, 297 nuclei for, 295-296 paramagnetic ion effects on, 1344 peak areas in, 300 principles of, 295-299 proton chemical shifts of, 310 reference works for, 348, 1369 relaxation effects on, 1344 resonance frequencies, 297 ring-current effect on, 1034- 1035

in annulenes, 1035, 1088 ringing in, 298-299 and rotation about single bonds, 303-304,

1345- 1347 shift averaging in, 1345- 1346 shift reagents and, 872-873 spin quantum numbers for, 297-298 spin-spin splitting in, alkenes, 320, 325-326

of benzene protons, 1036- 1037 binomial coefficients and, 3 19 calculation of, 1348-1353 characteristics of, 3 16-322 chemical-shift effects on, 305, 317, 332-333 and conformations, 32 1-32 1 coupling constants for, 317, 319-321, 325-326 and decoupling, 322, 336 equivalent nuclei and, 3 16, 3 19, 332 ethyl groups, 3 16-3 18 first-order, 3 16 intensities of lines with, 3 18-3 19, 325-326 iodoethane, 3 16-3 18 line multiplicities in, 316-318, 325-326 long-range, 320 n + 1 rule for, 3 17-3 19 patterns of, 3 16-3 19, 325-327 proton structural variations of, 3 19-32 1,

325-327 saturated systems, 3 19-32 1 second-order, 3 16-3 17, 333 and structural analysis, 322-327 theory of, 1348- 1353 three-bond, 3 19-32 1 two-bond, 3 19-320

in structural analysis, 322-327 7 scale for, 306 and uncertainty principle, 1343- 1346

Nmr spectrum, of Zbromobutane, 328 of 3-bromopropene, 324 of I -buten-3-yne-4-D, 1353 carbon- 13, of D-glucose, 9 18

of lysozyme, 1286 of methylcyclohexane, 460 of polypropene, 1434 of warfarin and its sodium salts, 336-337

of cyclooctane, 447 of 3,3-dibromo-2,2-dimethylbutane, temperature

effects on, 1347 of 1, I-dimethoxyethane, 3 19 of (2,2-dimethoxyethyl)benzene, 328

of ethanol, 295-296, 3 11-3 12 of ethyl 3-oxobutanoate, 827 of N-ethylethanamine, 1105 of ethynylbenzene, 357 of D-glucose, carbon-13, 9 17-9 18 iodoethane, 3 16 of methyl methoxyethanoate, 3 13-3 14 of 2-methyl-2-butanol, 305 of methylcyclohexane, carbon- 13, 447 of I-methylethyl ethanoate, 328 of 1-methylethenyl ethanoate, 328 of 1-(methylethenyl)benzene, 325-327 methylketene dimer, 774 of nitrobenzene, 1036 of nitrobenzenols, 129 1- 1292 nitrogen- 15, of N-methylmethanamide, 1 175 of octane, 334 of 2,4-pentanedione, 742 of 1-phenylethanamine, 873 of phenylethanoic acid, 795 of phenylnlethanol, 795 of propanal, 323 of propanamide, 1173 of 2-propenylmagnesium bromide, 1524 of 2,2,3,3-tetrachlorobutane, temperature effects

on, 1345-1346 of 1,1,2-trime thylazacyclopropane, 1 1 1 1 of 2,2,4-trimethylpentane, 334 of warfarin and its sodium salt (carbon-13),

336-337 Nomenclature (see also IUPAC rules)

philosphy of, 49-5 1 single- or multiple-word names in, 203-204

Nonane, heat of formation of, 86 Nonbonded interactions (see also Steric hindrance)

in methane chlorination, 89-90 between neon atoms, 89 potential energy of, 89

Nonpolar substances, definition of, 20 Norbornadiene, 1,3,5-cycloheptatriene from, 13 14

iron tricarbonyl complex of, 15 10 quadricyclene from, 503 synthesis of, 1314 thermal rearrangement of, 13 14

Norbornene, 999 Nordel, 1432 Norrish, R. G. W., and type I and I1

photodissociations of ketones, 1379- 1380 Novocaine, 1098 Nuclear magnetic resonance spectra (see Nmr

spectra) Nucleic acids (see also Deoxyribonucleic acids

and Ribonucleic acids), definition of, 927 Nucleophiles (see Nucleophilic reagents) Nucleophilic displacement reactions, acid

catalysis of, 232-234 of alkenyl halides, 549-550 of alkyl halides, 539-541 of alkynyl halides, 549-550 of allylic halides, 544-546 of aril halides, activating substituents for,

552-555

by addition-elimination mechanisms, 552-555 benzenamines from, 552-553, 557-558, 1120 benzenols from, 554-555, 557-559 benzyne intermediates in, 558-559, 1120 elimination-addition path for, 557-559, 1 120 mechanism of, 553-555, 1 120 Meisenheimer complexes and, 555 rearrangements in, 558-559 by S,I and S,2 mechanisms, 552

crown ethers and, 666 of cycloalkyl halides, 550-55 1 of cyclopropyl halides, 55 1 of cyclopropylmethyl halides, 55 1 electrophilic catalysis of, 233-234 general characteristics of, 2 13-2 14 kinetics of, 215-2 17 leaving group reactivity and acid strengths,

232-233 leaving group selection for, 230-233 leaving groups, and reactivity in, 230-233 mechanisms of, 2 14-2 17 nucleophilicity, and base strength, 236

and solvation, 236 and structure, 235-237

of phenylmethyl halides, 546 on polyhaloalkanes, 563-564 radical mechanisms for, 572-573 reagents for, 207-2 1 1 references for, 252 reversibility of, 236-237 S, reactions, characteristics of, 215-218 S,I mechanism, amines with nitrous acid,

1130-1131, 1133 of haloalkanoic acids, 8 17 ion pairs in, 223 kinetics of, 2 15-2 17 leaving group structures and rates of,

230-233 in micelles, 804-805 of oxacyclopropane ring openings, 663-665 phenyl reactivity enhancement of, 228-229 racemization with, 897 reactivity of organic halides in, 226-230 rearrangements in, 250-25 1 silver-ion enhancement of, 234 solvent effects on, 237-238 s tereochemistry of, 222-223 steric acceleration of, 229 steric hindrance effects on, 229 transition states for, 226-227

S,2 mechanism, and alkyl group structure, 224-225

amines and alkyl halides, 1125-1126 in competition with E2 elimination, 241 crown ether catalysis of, 666 electrophilic catalysis of, 232-234 with enamines, 764-765 of enolate anions, 761-763, 833-834 in Gabriel synthesis, 1127 of haloalkanoic acids, 8 15-8 16 kinetics of, 215-217 nitriles from, 1 184- 1 185

of oxacyclopropane ring openings, 663-665 and racemization, 896 reactivity of nucleophiles (table), 235-237 reactivity of organic halides in, 224-225 with solvent, 218 solvent effects on, 238 stereochemistry of, 219-221 and steric hindrance, 224-225 in sulfonamide syntheses of mines, 1127 with sulfur-stabilized carbanions, 765-766 transition metals and, 1516, 1520, 1526

solvent effects on, 236-239 solvent participation, kinetics of, 218 solvolysis, mechanisms for, 2 18 structural effects on, 224-234 thermochemistry of, 2 12-2 13

Nucleophilic reagents, definition of, 207-2 1 1 Nucleophilicity, and base strength, 210-2 1 1

and structure, 235-237 Nucleosides, structure of, 1274 Nucleotides, base-pairing of, 1274- 1275

definition of, 926-927 in DNA chains, 1274-1275 sequences of, in genetic code, 1276-1277 structure of, 1274

Nylon 6, 673, 1181, 1433, 1441 Nylon 66, 1181, 1433, 1441

hydrogen bonding in, 1426- 1427 properties of, 1433

0-alkylation, of enolate anions, 762-763 of phenols, solvent effect on, 1297-1298

Ocimene, 1464 Ocimum basilicum, oil of, 1464 . T-Octadienylnickel, from 1,3-butadiene, 1523

cycloaddition reactions of, 1523- 1524 Octafluorocyclobutane, from dimerization of

tetrafiuoroethene, 502, 568 physical properties of, 569

Octane, heat of combustion of, 79 infrared spectrum of, 279 nrnr spectrum of, 334

cis-2-Octene, synthesis of, 5 18-522 Odors and stereoisomerism, 140- 14 1 Oil of wintergreen, 1327-1328 Olefins (see Alkenes) Oleic acid, 789-790 Oligosaccharides, definition of, 927

properties and occurrences of, 907 Oppanol, 1432 Oppenauer oxidation, aldehydes from, with

alcohols, 727 ketones from, with alcohols, 730

Opsin, 1416-1417 optical activity (see also Chirality), discovery

of, 118 origin of, 862-864

and polarized light, 1 18- 120 rotation of polarized light in, 118-120 wavelength variation of rotations, 890-893

Optical antipodes (see Enantiomers) Optical isomerism (see Chirality, Isomerism, and

Optical activity) Optical rotation (see also Optical activity),

conventions for, 865-866 molecular, 866 specific, 865-866 wavelength variation of, 890-893

Optical rotatory dispersion, absolute configurations from, 892-893

Cotton effect and, 890-893 definition of, 890-89 1

Oral contraceptives, 1479 Orange, oil of, 1464 Orbital hybridization, 159- 16 1 Orbital phase, 156 Orbitals (see Atomic orbitals or Molecular orbitals) Organic chemistry, definition of 2 1-22

scope of, 21-22 uses of, 22

Organic photochemistry (see Photochemistry) Organic syntheses, principles in planning of,

5 13-530 Organoboranes (see also Hydroboration), acid

cleavage of, 427, 429 alcohols from, 427-428 from alkenes and diborane, 420-424 alkyl- and dialkyl-, addition to alkenes and

alkynes, 422-424 preparation of, 420-423 stability of, 423

from alkynes and diborane, 422-423 h i n e s from, 427 azanyl hydrogen sulfate and, 427 hydrocarbons from, 427 isomerization of, 424-426, 523-524 oxidation of, alcohols from, 427-430

aldehydes from, 428-429 ketones from, 428-429 mechanism of, 429-430 stereospecificity of, 427-428

properties of, 420-421 rearrangements in reactions of, 430 in syntheses, 426-429, 521, 523-525

Organohalogen compounds, definition of, 535 general characteristics of, 535 insecticides of, 536-537 naturally occurring, 535-536 physical properties of (table), 538 spectroscopic properties of, 539

Organolithium compounds, 1,4-addition to alkenones and alkenals, 585-586

alcohols from, 58 1-582 alkylcoppers from, 584 ketones from, with carboxylates, 583 with ketones, 581-582 thermochemistry of additions of, 578

Organomagnesium compounds, 1,4-addition to alkenones and alkenals, 585-586

alcohols from (table), 577-581 with acyl halides and

anhydrides, 609 with aldehydes, 609 with esters, 609 with ketones, 609 with methanal, 577, 579, 608 with oxacyclopropanes, 609

aldehydes from, with N,N- dimethylmethanamide, 729

with triethoxymethane, 729 with aldehydes, 577-580

table, 577-579 alkylcadmiums from, 584 with alkynes, 578 with arnides (table), 579 with carbon dioxide (table), 579, 583 carboxylic acids from (table), 579, 583 dialkylmagnesium compounds, 576 enolizations with, 582 ether complexes of, 577 ferric chloride coupling with, 1505 with halogens, 586-587 hydrolysis of products of, 580 ketones from, with nitriles, 731 with oxacyclopropanes, 578 with oxygen, 586-587 preparation of, with aryl halides, 576

coupling in, 572 from 1,6dihalides, 575 with ethenyl halides, 572 Grignard procedure, 576 with 3-halopropenes, 572 solvents for, 571-572

reduction of carbonyls with, 582 side reactions in additions of, 582 structure and equilibria of, 577 with sulfur, 586-587

Organometallic compounds, 1,4-addition to alkenones and alkenals, 585-586

carbenes from (table), 566, 575-576 general characteristics of, 570 ionic character of C-M bonds of, 571-572 preparation of, from acidic hydrocarbons, 574

by halogen-metal exchange, 573-574 by metal exchange, 574 metals with halides, 57 1-573 from polyhalogen compounds, 575 procedures for (table), 590 radical mechanisms in, 572-573 solvents for, 571-572

reactivity of, 570-57 1 thermochemistry of additions of, 578 of transition metals, alkene complexes,

1509-1510, 1521-1524 with alkyl-metal bonds, 15 10- 15 16, 1520,

1525-1526 carbene complexes, 15 12, 152 1 sandwich type, 1505-1508 vitamin B,, as, 1525-1527

Organonilrogen compounds, types of (summary), 1 184

Organopotassium compounds, reactivity of, 570-57 1

Organosodium compounds, reactivity of, 570-57 1

Orientation in aromatic substitution, 1059-1072, 1187-1 190

Orlon, 1427, 1433 Orsellinic acid, 1480 ortho, definition of, 63 Ortho-para directing groups (tables), 1060- 1064 Osmium tetroxide, alkene additions of, 434 Osmium tetroxide-sodium periodate, ketones

from, with alkenes, 730 Overlap, of atomic orbitals, 155- 16 1 Oxacycloalkanes, nomenclature systems for,

659-66 1 Oxacyclobutane (trimethylene oxide, oxetane),

reactions of, 661 Oxacyclobutanes, from photochemical

cycloadditions, 1389- 1390 Oxa-2-cyclobutanone, as carcinogen, 1 164 Oxa-2-cyclohexene, protecting group for OH

with, 653 Oxacyclopentane (tetrahydrofuran, THF, oxolane),

physical properties of, 654 as solvent, 661

for organometallic preparations, 572 Oxacyclopropane (ethylene oxide, oxirane), from

ethene oxidation, 42, 437 hydrolysis to 1,2-ethanediol, 437 industrial uses of, 66 1-662 physical properties of, 654 polymerization of, 1423 reactions of, 66 1-662

Oxacyclopropanes, alcohols from, with Grignard reagents, 609

by hydride reduction, 6 10 from alkene oxidations, 435-437 with Grignard reagents, 578 hydrolysis of, 435-437 preparation of, 662-663 ring-opening reactions of, 663-665 from ylide reactions of ketones, 692-693

Oxalic acid (see Ethanedioic acid) Oxaloacetic acid (see 2-Oxobutanoic acid) Oxalyl chloride (see Ethanedioyl dichloride) Oxalyl derivatives (see Ethanedioyl derivatives) 3-Oxa- 1,5-pentanediol, 662 Oxazacyclopropanes, inversion rates of, 11 10 Oxazine dyes, 1406 Oxidation (see also individual oxidizing agents, as

Ozone, etc.), of arenes, with oxygen, 1077- 1078

of arenes, with ozone, 1078-1079 balancing equations of, 406-409 definition of, 42-43, 405-409

Oxidation states, of carbon (table), 405-409 of nitrogen, 1141-1 142

Oxidative phosphorylation, in alcohol oxidations, 646

Oximes, from aldehydes and ketones, 698 amides from, 1 180- 1 18 1

Beckmann rearrangement of, 1149, 1153, 1180-1181

E,Z convention for, 887, 1181 nitriles from, 1 185 reduction to amines, 1146, 1148 stereoisomerism of, 1 13 1 sulfonate esters of, 11 80 syn and anti isomers of, 1 18 1

Oxiranes (see also Oxacyclopropanes), 660 0x0 reactions (see also Hydroformylation),

722-723 2-Oxoalkanoate esters, decarbonylation of, 832 3-Oxoalkanoate esters, acidities of (table), 736-738

from 2,4-dioxoalkanoate esters, 832 ketones from, by hydrolytic cleavage, 730

3-Oxoalkanoic acids, in alkanoic acid metabolism, 837-840

2-Oxobutanedioic acid (oxaloacetic acid), in citric acid cycle, 951-954

from 2-hydroxybutanedioic acid, NAD+ and, 645

in terpene biosynthesis, 1482- 1488 3-Oxobutanedioyl coenzyme A, in terpene

biosynthesis, 1482, 1488 3-Oxobutanoate esters, acidity of, 826

acylation of, 835 alkylation of, 833-834 carboxylic acids from, 834 from diketene, 773 from 2,4-dioxoalkanoate esters, 832 enol-keto interconversion of, 827-828 enolization of, 826-828 ketones from, 834 Michael addition of, 844 nmr spectrum of, 827 separation of forms of, 828

2-Oxobutanoic acid, citric acid from, 840 enzymatic decarboxylation of, 1285

3-Oxobutanoic acid, decarboxylation of, 812, 834 Oxonium salts, of alcohols and ethers, 613-614,

656-657 2-Oxopentanedioic acid, in citric acid cycle,

95 1-954 2-Oxopropanoic acid, decarboxylation of, thiamine

pyrophosphate and, 1267-1269 en01 phosphate of, as phosphorylating agent, 649 in gluconeogenesis, 955-956 in glycolysis, 946, 949-950 from 2-hydroxypropanoic acid, with NAD+, 645

Oxygen, with alcohols, 639 copolymer with ethenylbenzene, 1453 coupling into metabolic processes, 1308-1309 as diradical, 1391 electronic configuration of, 139 1 with Grignard reagents, 586-587 as radical-chain inhibitor, 95 role in carbohydrate metabolism, 944-945 singlet state of, with biological systems, 1393

chemical generation of, 1392- 1393 chemistry of, 139 1-1393 electronic configuration of, 139 1 photochemical generation of, 139 1-1392

with triphenylmethyl radicals, 1323 Oxygen carriers, hemoglobin as, 1258-1259

myoglobin as, 1255-1259 synthetic, 1258

Oxytocin, structure and synthesis, 1242-1244 Ozone, alkene reactions of, 43 1-433

destruction in atmosphere by chlorofluorocarbons, 537

electronic structure of, 433 with triethyl phosphite, 1393

Ozonides, formation of, 43 1-433 methanol reaction of, 432 reduction of, 43 1-432

Ozonization, aldehydes from, 727 of arenes, 1078- 1079 ketones from, with alkenes, 730 mechanism of, 432-433 procedures for, 43 1-432

Palmitic acid, 789-790 Pantothenic acid, structure, 12 1 1 Paper chromatography, for amino acids, 12 18- 12 19 para, definition of, 63 Para Red, 1407 Paradigm of transition-metal compound

stabilities, 1504 Paradigms, of organic chemistry, 3 Paraffin hydrocarbons (see Alkanes) Paraformaldehyde, 696 Paraldehyde, 696 Partial rate factors (see Electrophilic aromatic

substitution) Pasteur, L., and resolution of tartaric acid, 118 Paterno, E., 3, 8 Pauli, W., and exclusion principle, 153- 155 Pauli principle, bonding in hydrogen and, 961 Pauling, L., and alpha helix, 125 1

electronegativity chart, 377 and x-ray diffraction structure

determinations, 1249 Pectins, 937 Pederson, C. J., and metal complexes of cyclic

polyethers, 666 Penicillins, biochemical action of, 1490

biosynthesis of, 1492 enzymatic degradation of, 1490 structure and function of, 1491 synthesis of, 1492

1,3-Pentadiene, heat of hydrogenation of, 4 15 stabilization energy of, 986

1,4-Pentadiene, heat of hydrogenation of, 41 5 Pentaerythritol, 754

polyesters from, 1440 Pentalene, 1086- 1087

bis-nickel derivative of, 1508 Pentanedioic acid, properties and uses of, 847 2,4-Pentanedione, acidities of (table), 736-738

alkylation of, 763 beryllium salt of, 777 copper salt of, 777 with diazomethane, 1199 enolization of, 740-742, 776-777 physical properties of, 679 salts with metals, 777

2-Pentanone, photochemistry of, cyclobutanols from, 1381

dissociation in, 1380 cis-2-Pentene, heat of hydrogenation of, 415 trans-2-Pentene, heat of hydrogenation of, 415 Pentoses, structures and configurations of,

904-907 Pentyl alcohol (see 1-Pentanol) Peppermint, oil of, 1466 Pepsin, precursor of, 1269 Peptides, abbreviations for, 1228-1229

alpha helix of, 1251-1252 a i d e groups in, 1227-1228 amino-acid backbone, 1227-1229 amino-acid compositions of, 1229 amino-acid sequences, determination of,

1229-1234 C-terminus of, 1228 carboxypeptidase hydrolysis of, 123 1 chymotrypsin hydrolysis of, 1233 conventions for, 1228 with dansyl chloride, 1230 denaturation and, 1228 Edman degradation of, 1230- 123 1 formation of, in prebiotic evolution, 1284 helical structures of, 125 1-1252 hydration of, 1228 hydrolysis of, 1229 N-terminus of, 1228 peptide bond of, 1227 primary and secondary structure of, 1228 separation from proteins, 1248 structure of, 1227-1229 synthesis of, coupling reagents for, 1240-1247

Merrifield procedure for, 1242-1247 procedures for (table), 1236-1247 protecting groups in (table), 1236-1247 racemization problems in, 1238- 1240 solid-phase supports for, 1242-1247 yield problems in, 1236, 1238-1240

tertiary structure of, 1228 thiohydantoins from, 1230-123 1 trypsin hydrolysis of, 1232-1233

Perfluorocarbons, preparation of, 99 Performic acid (see Peroxymethanoic acid) Perfume ingredients, 1328 Pericyclic reactions, Claisen ally1 ether

rearrangement and, 1298 cycloadditions and, 999-1005, 1010- 1017 definition of, 419, 498 electrocyclic type, 1005- 10 14 and Hiickel rule, 999-1017 rules for prediction of, 1010- 1012 sigmatropic type, 1006, 1010

of singlet oxygen, 139 1-1392 Periodate, oxidation of 1,2-alkanediols with, 717 Perkin, W. H., and founding of dye industry,

1405-1406 Perlon, 1433 Permanganate, aldehyde oxidation, 7 12

1,2-alkanediols from, with alkenes, 643 1,3,5-cycloheptatriene to tropolone, 1314 hydroxylation of alkenes, 434 mechanism of oxidation with, 643 methylbenzene to benzenecarboxylic acid, 13 17 for nitro compounds from amines, 1144 oxidation of alcohols with, 643

Peroxidation of alkenes, diols from, 434-436 mechanism of, 436

Peroxide effect, in hydrogen bromide addition to alkenes, 386-389

Peroxides, from arenoxy radical dimerizations, 1302 ascaridole as, 1466 and chemiluminescence, 1395- 1399 chlorination induced by, 102- 103 decomposition of, 102- 103 from ethers, 658-659 polymeric from ethenylbenzene, 1453 in prostaglandin biosynthesis, 1494 from semiquinone dimerization, 1307

Peroxybenzenecarboxylic acid, 713 with alkenes, 435-436

Peroxycarboxylic acids, in additions to alkenes, 380 alkene additions of, 435-436 oxidation of amines with, 1143-1144

Peroxymethanoic acid, with alkenes, 435-436 Peroxytrifluoroethanoic acid, with alkenes, 436 Perutz, M., and x-ray diffraction structure

determinations, 1249 Pesticides, aryl halides for, 561 PETN, 754 Petroleum, arenes from, 1079-1083

chemicals from, 1079-1083 composition of, 74 gases from, 74 refining of, 74 source and uses of, 74-75

pH, definition and equations for, 209 Phenacetin, 1328 Phenanthrene, bromination of, 107 1- 1072

from coal tar, 1080 nitration of, 1071 oxidation of, with ozone, 1079 from photolysis of 1,2-diphenylethene, 1387 physical properties of, 1027 reduction of, 1074 stabilization energy of, 985 sulfonation of, 1071

Phenobarbital, 1098 Phenol (see Benzenol and Phenols) Phenolphthalein, 1405 Phenols, acidities of (table), 736-738, 1289-1290,

1293-1294, 1334 aldehydes from, 1299 aldol-type reactions of, 1300

arenamines from, 1295- 1296 from arenamines, 1293 from aryl halides, 557-559 with aryldiazonium salts, 1300 bromination of, 1296- 1297 Bucherer reaction and, 1295-1296 C-alkylation of, 1297-1298 from coal tar, 129 1 with dichlorocarbene, 1299 electronic spectra of (table), 1288-1290 as enols, 65 1, 1288 esters from, 1294 ethers of, cleavage of, 1295

preparation, 1294, 1297-1298 ferric chloride complexes of, 1294- 1295 haloarenes from, 1295 Hammett reactivity and acidity correlations

with, 1334 hydrogenation of, 1300 infrared stretching frequencies for, 277 IUPAC rules of nomenclature for, 191 Kolbe-Schmitt reaction of, 1298-1299 0-alkylation of, 1297-1298 oxidative coupling of, 1301-1302 physical properties of (table), 1288- 129 1 radicals in oxidation of, 1301-1302 resonance in, 1288 salts of, with alkyl halides, 1294

C-alkylation of, 1297- 1300 0-alkylation of, 1297-1300 with 2-propenyl halides, 1297-1298

with trichloromethane, 1299 Phenyl cations, from benzenediazonium salts, 1133,

1135-1 136 Phenyl esters, amides from, 1177-1178 Phenyl isothiocyanate, in Edman degradation of

peptides, 1230- 123 1 Phenylacetic acid (see Phenylethanoic acid) Phenylalanine, anticodon of, 1282

properties of, 1210 synthesis of, 1226

Phenylamine (see Benzenanline) N-Phenylazanol, azo compounds from, 1194

from nitrobenzene, 1 194 rear-rangelnent of, 1140

1-Phenylbutanone, photochemistry of, 1381 Phenylcyclobute~ledione, synthesis and

derivatives of, 13 13 Phenyldiazane, synthesis and reactions of, 924,

1138, 1140 Phenylethanenitrile, from chloromethylben-

zene, 1318 Phenylethanoic acid, nmr spectrum of, 795 Phenylethanoic acids, Hammett acidity correlations

with, 1334 Phenylethanone, from acyclation of benzene, 1052

physical properties of, 679 9-Phenylfluorene, acid strength of, 1322 Phenylglycine, synthesis of, 1225 Phenylhydrazine, with u-glucose, 924

synthesis and rearrangement of, 1 138, 1 140

N-Phenylhydroxylamine, from nitrobenzene, 1 194 reactions of, 1140, 1194

Phenylmagnesium bromide, ferric chloride coupling of, 1505

Phenylmercuric ethanoate, from mercuration of benzene, 1058

Phenylmethanol, from chloromethylbenzene, 13 18 nmr spectrum of, 795

Phenylmethoxycarbonyl protecting groups, in peptide syntheses, 1237-1247

Phenylmethyl cations, ease of formation of, 1320 Phenylmethyl chloride (see Chloromethylbenzene) Phenylmethyl halides, preparation of (table),

546-547, 587-588, 1046, 1054 reactions of, 546 reactivity in SN2 reactions, 225 reactivity of (table), 589 S,I reactivity of, 228-229

Pheromones, insect, isomerism and activity of, 141 reference works for, 142

Phillips catalyst for alkene polymerization, 396 Phloroglucinol (see 1,3,5-Benzenetriol) Phosphate esters, adenosine and, 635-637

biochemical derivatives of, 635-637, 1483-1485 DNA and, 1273 formation of, 634-635, 940-956 hydrolysis of, 635-637 nucleotides as, 926-927

Phosphine, bond angles of, 172 Phosphines, radical-chain addition to alkenes

and alkynes, 389 Phosphoenolpyruvate, in glycolysis, 949 Phosphoglycerides, 790, 805 Phospholipids, 790, 805 Phosphorescence, of benzene, 1375

definition of, 1375 of naphthalene, 1377

Phosphoric acid, esters of, formation and reactions of, 634-637, 940-956, 1483-1485

Phosphorus halides, alkyl halides from alcohols and, 626-627

Phosphorus pentachloride, in acyl chloride formation, 809

with ketones, 704 Phosphorus trichloride, in acyl chloride

formation, 809 Photochemical initiation of polymerization, 1447 Photochemistry, alkene isomerizations by,

1384-1386 of biological systems, 1371, 1393-1394 chemiexcitation, 1395-1399 chlorination of alkanes, 91-95 of chlorofluorocarbons in atmosphere, 537 CIDNP effects in, 1353-1356 of color photographic processes, 1410-1415 cyclizations in, of dienes, 1387

of 1,2-diphenylethene, 1387 cycloadditions in, alkenes with ketones,

1389-1390 of DNA and RNA, 1394 electrocyclic reactions of, 1013- 1014

1,3-dienes to cyclobutenes, 1387 1,2-diphenylethene to phenanthrene, 1387 stereochemistry of, 1387- 1388

energy transfer in, characteristics of, 1374, 1376-1377

diphenylmethanone to naphthalene, 1376-1377 of ethene-carbon monoxide polymers, 1453 excitation of carbonyl group, 1375-1376 Franck-Condon principle and, 1372 of ketones, CIDNP effects in, 1353-1356

Norrish type I, 1379-1381 Norrish type 11, 1380-1381

of methanal, excited states of, 1375-1376 and nmr CIDNP effects, 1353-1356 photodissociation in, mechanism of, 1373-1374

of 2-propanone, 1379-1380 quantum yields in, 95

photodissociation processes, 1379 reduction by, benzopinacol from, 1382- 1383

of diphenylmethanone, 1382- 1383 mechanism of, 1382-1383

singlet states in, of benzene, 1375 energy transfer from, 1374 Franck-Condon principle in formation of,

1372-1374 intersystem crossing and, 1374-1375 lifetimes of, 1374-1375 of methanal, 1375-1376 potential-energy curves for, 1373 as primary product of electronic excitation,

1372-1373 triplet states from, 1374-1375 vibrational relaxation of, 1374

triplet states in, of benzene, 1375 electronic configuration of, 1373-1374 Hund's rule and stability of, 1373 lifetimes of, 1375 of methanal, 1375-1376 phosphorescence from, 1375 potential-energy curves for, 1373 from singlet states by intersystem crossing,

1373-1375 uses of, 1371 vision and, 1416-1417

Photodissociation, of ketones, 1379-138 1 mechanism of, 1374 Norrish types I and 11, 1379-1381

Photoelectron spectroscopy, elements of, 267 of hydrocarbons, 1357- 1358 principles and uses of, 1356-1357

Photoelectron spectrum, of benzene, 1357 of ethene, 1357 of ethyne, 1357

Photographic developers, chemistry of, black and white, 13 10-131 1

chemistry of, color, 141 1-1414 Photosensitization, "and energy transfer, 1377

ketones for, 1385-1386 in photographic films, 141 1-1412 singlet oxygen from, 1392

Photostationary states, 1386

Photosynthesis, Calvin cycle, 94 1-943 carbohydrates from, 939-943 character of, 939-943 chlorophyll in, 939-94 1 esr spectra during, 1368 path of carbon in, 941-943 phosphorylation in, 94 1-943

Phthalic acid (see 1,2-Benzenedicarboxylic acid) Phthalic acids (see respective benzenedicarboxylic

acids) Phthalic anhydride (see 1,2-Benzenedicarboxylic

anhydride) Phthalimide (see 1,2-Benzenedicarboximide) Phthdimidomalonic ester synthesis of amino

acids, 1226 Phthalocyanines, 1408 Phytol, as diterpene, 1468- 1469

occurrence of, 1468- I469 Pi (7~) bonds, of ethene, molecular-orbital

treatment of, 964-965 valence-bond treatment of, 965-966

formulation of, 165- 167 Pi (7~) complexes (see also Charge-transfer

complexes), from alkenes and halogens, 367 in arene halogenation, 1044- 1045 of nitro compounds, 1 192- 1 193 of transition metals with alkenes, 1509-1510,

1517-1519, 1523 Pi (n) electron rules (see Hiickel rules) Picolines, from coal tar, 1080 Picrates, 1192 Picric acid, 1 192

physical properties of, 1289 Pigments, copper phthalocyanine as, 1408

uses of, 1408 Pinacol (see 2,3-Dimethyl-2,3-butanediol) Pinacol-pinacolone rearrangement, 720 Pinacolone (see 3,3-Dimethyl-2-butanone) Pinene, 1464 Piperidine (see Azacyclohexane) Piperonal, 1328 Planck's constant, definition of, 269

and uncertainty principle, 1343 Plant gums, 937 Plasticizers, for polychloroethene, 1435 Plastoquinone, 1309 Platinum, alkene complexes of, 1509- 15 10

cyclohexyne complex of, 15 10 Pleated sheets, protein conformations as,

1252-1253 Plexiglas, 1433 Poison ivy, 1304 Polarized light, circularly, 864

origin of optical activity and, 862-864 plane, 862-864

Polaroid color-print process, 1414- 1415 Polycarbonate resins, 1439 Polychloroethene, physical properties and uses of,

391, 1430, 1432, 1435 Polycycloalkanes, IUPAC rules of nomenclature

of, 476479

physical and chemical properties of (table), 482-484 propellane types of, 483-484

Polyenes, nomenclature for, 60-6 1 as visual pigments, 1416-1417

Polyesters, synthesis of, 1438-1440 Polyethene, characteristics of, 1425-1426, 1430,

1432, 1434-1435 formation and uses of, 395-397

Polyethenylbenzene, physical properties of, 1430, 1433

Polyethers (see also Ethers), cyclic, metal complexes of, 665-666

Polyfluoroethene, physical properties of, 568, 1430, 1432

Polyfunctionality, characteristics of, 488, 788 Polyhaloalkanes, reactions with metals, 575

uses of, 562-563 Polyhydric alcohols (see Alkanediols,

Alkanepolyols) Polyisobutylene, formation and uses of, 393-395 Polyketides, 148 1- 1482 Polymerization (see also Copolymers and

Polymers), addition, of 1,3-cyclopentadiene, 1420

of 1,3-alkadienes, by 1,2 addition vs. 1,4 addition, 504

atactic vs. isotactic polymers from, 505 commercial products from, 504-508 monomers for (table), 504-508

alkene monomers for (table), 391 of alkenes, 390-397 anionic mechanism for, 392-393 cationic mechanism for, 393-395 chain transfer in, 1449 condensation, Bakelites from, 1442- 1443

epoxy resins from, 1444-1445' of 1,2-ethanediol, 1423 melamine resins from, 1443-1444 polyamides from, 144 1 polyesters by, 1438-1440 reactions for, 1438 urea-methanal resins from, 1443-1444

copolymers of ethene and propene, 396, 1435 degree of, 1420 fiberglass by, 1440 growing chain in, 1420 inhibitors, 1449 initiators, 1447 "living" mechanism, 145 1- 1452 of methanal, 696 radical mechanism of, catalysts for, 395, 1447

chain transfer in, 1449 direction of addition in, 1447- 1448 inhibitors for, 1449 initiation of, 395, 1447- 1448 termination of, 396, 1447- 1449

Polymers (see also Copolymers, and individual polymers), addition, of alkenes, 1446- 1453

atactic, 504-505, 1430-1435 by anionic mechanism, 392-393, 1452-1453 by cationic mechanism, 393-395, 145 1

copolymers from, 1452- 1453 by radical mechanism, 375-376, 1446-1449 by Ziegler mechanism, 396-397, 1446

from 1,3-alkadienes, uses of, 505-508 vulcanization of, 505

amorphous, properties of, 1427- 1435 backbone of, 1420 bifunctional, 1452 block, ester-ether type, 1454

polyurethanes as, 1454-1455 by Szwarc procedure, 1452

from chloroethene, 548-549 cold drawing of, 1428, 1435 cross-links in, effects of, 1422-1423, 1428-1430,

1435, 1439-1440, 1443-1445, 1457 crystallites in, 1425-1435 decomposition temperatures of, 1427, 1456- 1457 definition of, 1419 of 1,l-difluoroethene and hexafluoropropene

(Viton), 568 elastomeric, characteristics of, 1422, 1428-1429

cross-links in, 1428-1430, 1435 of ethene and propene, 1435 plastic flow in, 1428-1429 vulcanization of, 505, 1429- 1430, 1435

emulsion, 1447 end groups on, 1420, 1448-1449, 1452 fiber formation, 1427-1428, 1435 fiberglass, 1440 flexibility of chains in, 1427- 1429, 1435, 1456 gel, 1422 glass temperatures of (table), 1427-1435 graft, preparation of, 1455 high-temperature, 1456-1457 hydrogen bonding in, 1426- 1427 importance of, 1419 isotactic; 504-505, 1430- 1435 ladder, arenecarboxarnides as, 1457

polyimides as, 1456 quinoxalines as, 1456

melting points of (table), 1427-1435 of methanal, 696 molecular weights, number average, 1420- 142 1

weight average, 142 1 oriented and unoriented, 1428, 1435 photodegradable, 1453 photoinitiation of, 1447 hhysical properties of (table), 1422- 1423,

1425- 1435 plastic flow in, 1422 polyaldehyde type, 696 polyethene, crystallites in, 1425-1426

properties of, 396, 1425-1426, 1430, 1432, 1434-1432, 1434-1435

polypropene, 396, 1430-1435 preparation of (see Polymerization) PVC plastics, 549, 1430, 1432, 1435 solvent swelling by, 1422 stereoisomerism of, 504-505, 1430- 1435 structural elements of, 1419-1420 syndiotactic, 1430-1435

of tetrafluoroethene (Teflon), 568, 1430-1432 thermoplastic, characteristics of, 1422,

1425-1429 thermosetting, characteristics of, 1422- 1423 types of, 1421-1423 uses of (table), 1432-1433 van der Waals forces and, 1422, 1426-1429

Polymethanal, properties of, 696, 1430, 1433 Polynuclear arenes, oxidation of, 1078- 1079 Polynuclear aromatic hydrocarbons (see also

Polynuclear arenes) angular and linear, 1025 IUPAC rules of nomenclature for, 1025--1026 reduction of, 1073-1074 ring index for (reference), 1026

Polynucleotides, definition of, 927 Polyols, urethane foams from, 1455 Polyoxymethylene, 696 Polypropene, atactic, 1430- 1435

carbon-13 nmr spectrum of, 1434 isotactic, 1430- 1435 physical properties, 396, 1430-1435 stereoisonlers of, 1430-1435 syndiotactic, 143 1, 1434

Polypropenenitrile, properties of, 1427, 1433 spinning of, 1427

Polypropylene (see Polypropene) Polysaccharides (see also Cellulose, Starch, etc.)

definition of, 927 properties and occurrence of, 908

Polystyrene, 1430, 1434 Polytetrafluoroethene, physical properties of,

568, 1430-1432 Polyurethane foams, 1454- 1455 Polyvinyl alcohol, polymers of, 1433 Polyvinyl chloride (see Polychloroethene) Polyvinyl derivatives (see Polyethenyl derivatives) Polyvinyl fluoride, physical properties of,

1430, 1432 Polyvinylbutyral, safety-glass laminates of, 1433 Porphin, 1257 Porphyrins, vitamin B,, and, 1490 Porter, G., and photochemistry, 1380 Position isomers, 44-46 Potassium tert-butoxide, elimination reactions

with, 615 Potassium permanganate (see Permanganate) Potassium phthalimide (see Gabriel synthesis) Potential-energy curve, for hydrogen molecule,

960-96 1 Prebiotic evolution, 1282- 1284 Primaquine, 1098 Primary structures, of peptides, 1228 Principle of least structural change, 13 Prismane, physical and chemical properties of, 482 Procarboxypeptidase, 1269 Prochiral center, 889 Prochirality, in biochemical transformations,

888-889 definition of, 888

Progesterone, structure and occurrence of, 1472 microbial oxidation of, 1478

Projection formulas (see Chirality) Proline, and alpha helix, 1252

in collagen, 1458 with ninhydrin, 12 17 properties of, 12 10

Proof of structure (see Structure determination) 1,2-Propadiene (allene), atomic-orbital mode1

of, 408-509 ,1 [2 + 21 cycloadditions, 1002, 1017 dimerization of, 502 heat of hydrogenation of, 415 hydration of, 512 isomerization of, 5 12-5 13

Propanal, mass spectrum of, 340-341 nmr spectrum of, 323 physical properties of, 679

Propane, from di-v-propenylnickel, 1522 nitration of, 105, 1187

Propanedioate esters, acidity of, 826 acylation of, 835 alkylation of, 833-834 amino acids from, 1225-1226 1,2-benzenedicarboximido derivative of,

amino-acid syntheses and, 1224 carboxylic acids from, 834 N-formamido derivative of, amino-acid

syntheses and, 1224 methanamido derivative of, amino-acid

syntheses and, 1224 Michael additions of, 844 from 2-oxobutanedioate esters, 832 phthalimido derivative, amino-acid syntheses

and, 1224 Propanedioic acid, decarboxylation of, 847

properties and uses of, 847 1,2-Propanediol, in fiberglass, 1440

polyesters from, 1440 Propanedioyl ACP, 148 1 Propanenitrile, synthesis of, 1185 1,2,3-Propanetriol (glycerol), from fats, 790

manufacture of, 542 physical properties of, 239 polyesters from, 1439- 1440 properties of, 648 uses of, 648

1,2,3-Propanetriyl trinitrate, as explosive, 648 Propanoic acid, physical properties of, 792 1-Propanol, physical properties of, 601 2-Propanol, acidic properties of, 613

chromic acid oxidation of, 640-641 from hydration of propene, 361 industrial preparation of, 607 in photoreduction of diphenylmethanone,

1382-1383 2-Propanone, acidities of (table), 736-738

aldol additions of, 752-753 to benzenecarbaldehyde, 756 to methanal, 753

aldol product of, dehydration of, 756-757 preparation of, 752-753

from chromic acid oxidation of 2-propanol, 640-64 1

from 1,2-dioxacyclobutane, triplet state of, 1395-1397

electronic absorption, 287-289, 795 from ethanoic acid, 49-50 halogenation of, base and acid catalyzed, 742-745 from hydration of propyne, 383-384 from hydroperoxide rearrangement, 72 1-722 infrared spectrum of, 273 from isopropylbenzene, 1293 ketene from, 77 1-772 keto-en01 equilibrium of, 736-740 mass spectrum of, 340-341 oxime of, rearrangement of, 1 180 photochemistry of, 1379-1380 from photoreduction of

diphenylmethanone, 1383 physical properties of, 679 from 1,2-propadiene, 5 12 as solvent, 238

Propellanes, physical and chemical properties of (table), 482-484

Propenal, molecular-orbital treatment of, 978 physical properties of, 679 valence-bond treatment of, 974-975

Propene, alkene metathesis of, 1520- 152 1 allylic bromination of, with N-bromobutanimide,

542-543 allylic chlorination of, 543 bond-dissociation energies of, and resonance,

177-178 bromine substitution of, with

N-bromobutanimide, 104, 542-543 chlorine substitution on, 178, 543 copolymer with ethene, 396, 1435 electronic absorptions of, 289 ethene and butene from, 1520-1521 heat of hydrogenation of, 415 hydration of, 361, 383-384 polymerization of, 390-391, 396, 1446 polymers and copolymers of (see also

Polypropene), properties of, 39 1, 396, 1432, 1435

radical-chain addition of HBr to, 385-389 radical-chain polymerization of, 396

Propenenitrile, anionic polymerization of, 145 1 copolymer with 1,3-butadiene, 506 coupling with arenediazonium salts, 1136 in glutamic acid synthesis, 1226 Michael addition to, 1226 polymers from, 391

2-Propenyl cation, molecular-orbital treatment of, 979-980

valence-bond treatment of, 978-979 2-Propenyl halides, with benzenolate anions,

1297-1298 preparation of (table), 541-544, 587-588 reactions of, 544-546 reactivity in SN2 reactions, 225 reactivity of (table), 589 SN1 reactivity of, 228-229

2 - ~ r o ~ e n ~ l m a ~ n e s i u m bromide, nmr spectrum of, 1524

Propenylnickel complexes, chemistry of, 1525- 1524 as (T) complexes, 1521-1524

2-Propenyloxybenzene, preparation and rearrangement of, 1298

Propiolactone, as carcinogen, 1164 Propionaldehyde (see Propanal) Propionic acid (see Propanoic acid) Propylbenzene, from acylation and reduction of

benzene, 1053 physical properties of, 1027

Propylene (see Propene) Propylene oxide (see Methyloxacyclopropane) Propyne, heat of hydrogenation of, 415

radical-chain addition of HBr to, 390 Prostaglandins, biosynthesis of, 1493- 1494

structure and function of, 1492-1493 synthesis of, 1493-1494, 1502-1503

Prostanoic acid, 1492 Prosthetic groups, of myglobin, 1256-1257 Protecting groups, for mine functions, 1 157- 1 16 1

for carbonyl functions, 7 15-716 general characteristics of, 529 for hydroxyl function, 529-530, 65 1-653 illustration of use of, 529-530 in peptide syntheses, 1236- 1239, 1244- 1246

Proteins, biosynthesis of, DNA and, 1271, 1277 coiling of, 1249- 1252 collagen as, 1458-1459 cystine linkages in, 1253- 1254 denaturation of, 1259, 1270 fibrous, 1259 formation of, in prebiotic evolution, 1284 functions of (table), 1249-1250 industrial uses of, 1270- 127 1 properties of (table), 1250 quaternary structures of, 1259 RNA in, 1277-1280 separations of, affinity chromatography, 1248

electrophoresis, 1248 gel filtration, 1248 ion-exchange chromatography, 1248 ultracentrifugation, 1248

stereoisomers of, 894 structures of, three-dimensional, 1249-1259 synthesis of, RNA and mechanism of, 1277-1282 wool a ~ , 1457-1458

Protic solvents, 238 Protoporphyrin IX, 1257 Pseudomauveine, 1406 Pseudopelletierene, 990 D-Psicose, structure and configuration of, 906 Puffer fish toxin, 599 Purine, derivatives of, in DNA, 1273 Purity of organic compounds, tests for, 258-262 Pyranose rings, 920-922 Pyranthrone, 1407 Pyrazolines, cyclopropanes from, 1200

from diazomethane, 1200 Pyrene, from coal tar, 1080

quinone of, 1306 1,8-Pyrenedione, as quinone, 1306 Pyridine (see Azabenzene)

Pyridoxal phosphate, with amino acids, 1224- 1225

Pyridoxamine, 1099 Pyrimidine, derivatives of, in DNA, 1273

lactam-lactim isomerism of, 1273 Pyrogallol (see 1,2,3-Benzenetriol) Pyromellitic anhydride, polyesters from, 1440 Pyrophosphoric acid, esters of, formation and

reactions of, 634-637 Pyruvic acid (see 2-Oxobutanoic acid)

Quadricyclene, from norbornadiene, 503 ring opening of, 1013

Quantum theory, advanced, of simple molecules, 179-182, 981-984

and organic chemistry, 23 Quantum yields, definition and use of, 95,

1379, 1383 Quaternary structures, and hemoglobin, 1259

keratin and, 1259 of proteins, 1259

Quercetin, 1305 Quinhydrone, 1307 Quinine, 867, 1097 Quinoline, 1080, 1 1 18 Quinoneimines, in photographic development, 13 1 1

Wurster's Blue as, 1307 Quinones (see also Benzenediones,

Naphthalenediones, etc.), addition reactions, 131 1-1313

of benzene, 1301, 1303, 1305-1307, 1309-1312 biologically important examples, 1308- 13 10 of biphenyl, 1306 of 1,3-cyclobutadiene, 13 13 electrochemistry of, 1306- 1307 of naphthalene, 1305-1306, 13 10 as photographic developers, 13 10-13 1 1 as polymerization inhibitor, 1449 preparation of, 1145, 1301-1303 of pyrene, 1306 reduction of, 1306-1307 reduction potentials of, 1306- 1307 semiquinones from, 1307 types of, 1305-1306

Quinoxalines, 1326 as ladder polymers, 1456

R,S convention for configurations, priority order of groups in, 879-884

uses of, 133, 879-884 Racemic acid (see Tartaric acid) Racemization, definition of, 1 17-1 18

mechanisms for, 895-897 in peptide syntheses, 1238- 1240 in SN1 reactions, 222-223

Radical anions, from aryl halides and metals, 573 in Birch reduction, 1075 from naphthalene, esr spectra of, 1367-1369

Radical-chain addition, of hydrogen bromide, to alkenes, 386-388

Radical-chain polymerization, of alkenes, 395-397, 1446-1449

Radical-chain reactions, inhibition of, 95, 1449 initiation of, 91-94, 102-103, 391, 1447 polymerization as, 1446-1449, 1452-1453 steps of, 93-95, 395-397, 543-544, 1446-1449 termination of, 94-95, 392, 1448-1449

Radicals, in addition copolymerizations, 1452- 1453 in addition polymerization, 395-396, 1444-1449 alkyl, relative stabilities of, 388 from azo compounds, 1198 bonding and geometry of, 169-170 in cycloadditions, 1014- 1017 in phenol oxidations, 1301-1302 in photochemical reactions, 1353-1356, 1379- 138 1

Raffinose, properties and occurrence of, 907 Raman spectra, of alkenes, 284-286

of alkynes, 356 reference works for, 348 of tropylium ion, 1315

Raman spectroscopy, elements of, 267 and infrared spectra, 284-286 principles of, 284-286

Raman spectrum, of cyclohexene, 286 of tetrachloroethene, 285

Raney nickel, preparation and use of, 413 Rate-determining step, 90 Rayon, 933 Reaction constants, of Hammett equation,

1330-1337 Reaction kinetics, 2 15-2 17 Reaction mechanisms, concerted vs. stepwise, 98,

498-499, 1014-1017 concerted, 89-90, 98 elementary ideas of, 15-16 formulation of, 98 radical chain, 93-96 rate-determining step in, 90 stepwise, 89-90, 98, 1014-1017

Reaction order, 2 15-2 17 Reaction rates, problems of predicting, 96-97 Reaction types, classifications of, 42-43 Reactions, heat of, 76-80 Reactivity, elementary ideas of, 14 Rearrangements, 1,2-alkanediols to carbonyl

compounds, 720 1,2-alkyl shifts in carbocations, 250 of alkylbenzenes, 1050 in alkylborane carbonylations, 725-726 of alkylzirconocenes, 15 13-15 14 in arene alkylations, 1049- 1050 Beckmann, of oximes, 1 180- 1 18 1 benzilic acid, 1326 carbocation, in alcohol dehydrations, 632-633

in mines with nitrous acid, 1131 in SN1 and El reactions, 250-25 1

in Curtius degradation, 1156 eugenol to isoeugenol, 1327 Favorskii, with halo ketones, 748-749 in Hofmann degradation, 1155-1 156

1,2-hydrogen shifts in carbocations, 250 ketones from, of 1,2-alkanediols, 73 1 migration aptitudes in, 714 of N-substituted benzenamines, 1139-1 140 of unsaturated alkanoic acids, 841

Redox reactions, balancing equations of, 406-409 of carbon, 405-409

Reducing and nonreducing disaccharides, 928 Reducing sugar, D-glucose as, 913 Reduction (see also Aldehydes, reduction of, etc.),

balancing equations of, 406-409 definition of, 42-43, 405-409 of halides, with tin hydrides, 109 with hydrides, of carbonyl compounds (table),

705-708 Reductive alkylation of aldehydes and ketones,

amines from, 1149, 1154 Reductive amination, 1154 Reflection symmetry, 1 16 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, 1 17- 1 18 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, 1 1 13- 11 15 and annulenes with large rings, 1090 and azulene, 1084 and benzene, 1 1, 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, 1 192- 1 193 and Cold War politics, 11 and color, 1401-1404 concepts of, 172- 179, 96 1-964, 972-975,

981-984 cyclobutadiene and, 178, 989 cyclooctatetraene and, 989 and delocalization energy, 173-176, 963-964, 967 Dewar benzene and, 973-974

and diphenylmethyl cation, 1320 of electron-pair bonds, 96 1-963 and electronic spectra, 290-293 and en01 acidities, 649-65 1 in ethene, 965-966 formal bonds in, 973 and guanidine base strength, 11 18 GVB method and, 983-984 and Hammett correlation, 133 1-1332, 1337 and hyperconjugation, 228 and infrared spectra, 292 and nitro compound conjugate bases, 1195 and orientation in aromatic substitution,

1060- 1072 in phenols, 1288 of 2-propenyl cation,. 978-979 and reactivity, 177-178 representations for, 175- 178 rules for, 175-177 stabilization energies (table), 985-986 stabilization of carbocations by, 228-229 and tropolone, 13 14- 13 15 in tropylium ion, 1315

Resorcinol (see 1,3-Benzenediol) Retina, structure and pigments, 1416-1417 Retinal, 1416-1417 . Reversed micelles, 804 Rhizopus nigricans, progesterone oxidation

with, 1478 Rho (p ) constants (table), 1330-1337 Rhodium, catalysts of, hydroformylation,

1518-1519 hydrogenation, 4 17-4 18, 15 17- 15 18 in methanol carbonylation, 1520

mechanism for homogeneous hydrogenation with, 1517

Rhodopsin, 1416-1417 Riboflavin, 1099 Ribonuclease, properties, 1250 Ribonucleic acids (see RNA) Ribonucleosides, definition of, 926 D-Ribose, in nucleosides, 926

phosphate esters of, in gluconeogenesis, 955 in prebiotic evolution, 1283 properties and occurrence of, 907 structure and configuration, 904

Ribosomal RNA, 1278 Ribosomes, 1278, 1282 D-Ribulose, phosphate esters of, in

gluconeogenesis, 955 in photosynthesis, 94 1-942

structure and configuration of, 906 Ritter, J., and discovery of ultraviolet

radiation, 287 Ritter reaction, amides and amines from, 1149,

1178-1179 RNA, composition of, 1277-1278

in protein synthesis, 1277-1280 mRNA, 1279-1282 rRNA, 1278 tRNA, anticodon loop of, 1280-1281

function of, 1280-1282

in protein synthesis, 1280- 1282 structure of, 1279-1280

Roberts, J. D., and benzyne mechanism, 560 Robinson, R., and steroid synthesis, 1477-1478 Rodinal, 131 1 Rose bengal, 1392 Rosenmund reduction, aldehydes from, with acyl

halides, 719, 728 Roses, oil of, 1466 Rotational barrier, of biphenyls, 5 1 1

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, 1 138 Sandwich compounds, 1505-1506 Saponification, 82 1 Saponins, digitogenin as, 1473 Saturated hydrocarbons (see also Alkanes), ethane

as example of, 14-15 Savin, oil of, 1464 Sawhorse projections, 125-126 Schiemann reaction, 1135 Schiff bases, 1122

retinal pigment as, 1416-1417 Schmidt degradation, mines from, 1150,

1153, 1156 Schwartz, J., and zirconocene chlorohydride,

1512-1515 Sea pansy, 1398 Secobarbital, 1098 Secondary structures, of peptides, 1228 Sedoheptulose, properties and occurrence of, 907 Selinene, 1464 Semicarbazones, from aldehydes and ketones, 698 Semiempirical quantum calculations, 179- 182 Semiquinones, 1307 Sensitizers, photochemical 1376-1377, 1385-1387,

1392- 1393 photographic, 1310, 141 1-1412

Separation techniques, 257-258, 259-262, 1248 Sequence determination of peptides, 1299-1234 Serine, at enzyme active sites, 1265- 1266

genetic code for, 1277 properties of, 1208

Serotonin, 1099 Serturner, F. W. A., and alkaloid isolation, 1097 Sesquiterpenes, alcohols of, 1468

definition of, 1463 hydrocarbon, of, 1468

Sevin, 1328 Sex attractants, of insects, 141 Sex hormones, 1472-1473, 1479 Shark liver, oil of, 1464 Sheehan, J. C., and penicillin synthesis, 1492 Sigma (a) constants (table), 1330-1337 Sigma (a) orbital, definition of, 156 Sigmatropic rearrangements, Claisen ally1 ether

rearrangement and, 1298 Cope rearrangement and, 1006 definition of, 1006 and Hiickel rule, 1006, 1010-1012 inversion in, 1012 Mobius transition states for, 1006, 1010- 10 12 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, 13 10-13 11 Silver ion, catalysis of S, reactions of halides, 234 Silver nitrite, with alkyl halides, 1 19 1 Silver oxide and aldehydes, 712 Simmons, H. E., and carbene generation, 566 Simmons-Smith generation of carbenoid

species, 566 Single bonds, formulation of, 155- 164, 168- 172 Singlet states (see also Photochemistry, singlet

states in), 1372-1375 Sitosterol, 1474 Skew conformation, definition of, 124 S,l reactions (see Nucleophilic displacement

reactions, S, 1 mechanism) S,2 reactions (see Nucleophilic displacement

reactions, SN2 mechanism) Snarol, 696 Soaps (see also Detergents), detergent action

of, 803 from fats, 790 preparation of, 803

Sodium alkylbenzenesulfonates, as detergents, 803-804, 1056-1057

preparation of, 1056- 1057 Sodium amide, carbanion formation with, 1322 Sodium benzenolate, 1032, 1293-1294, 1298-1299 Sodium bisulfite (see Sodium hydrogen sulfite) Sodium borohydride, reduction of aldehydes and

ketones with (table), 705-708 Sodium cyanoborohydride, 1 154

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, 145 1

Sodium nitrite, with alkyl halides, 1190-1 191 as preservative for meat, 1163

Sodium pento thal, 1098 Sodium periodate, 1,2-alkanediol oxidation

with, 727 oxidation of sugars with, 92 1-922

Sodium phenaxide, 1032, 1293-1294, 1298-1299 Sodium tetracarbonylferrate, 15 16 Sodium trifiuoroethanoate, toxicity of, 569 Solid-phase peptide synthesis, general procedure,

1242-1247 supports for, 1244- 1245

Solvation effects, and carboxylic acid ionizations, 801-802

nucleophilicity and, 236 on phenol alkylations, 1297-1298

Solvation energies, of ions, 438-439 Solvents, ionizing power of, 237-239

properties of (table), 237-239 Solvolysis (see Nucleophilic displacement

reactions) D-Sorbose, structure and configuration of, 906 Soybean sterol, 1472 Space-filling models, 37-39, 451-455

and predictions of reactivity, 89-90, 93 Specific rotation, 865-866 Spectroscopic techniques for structure analysis

(table), 267 Spectroscopy, reference works for, 347-349,

1369-1370 wavelength conventions for, 265-268

Spin-orbit coupling, 1397 Spin-spin splitting (see Nmr spectra, spin-spin

splitting in) Spiranes, chiral forms of, 510

IUPAC rules of nomenclature of, 478 Spiro[2.2]pentane, physical properties and strain

energy of (table), 482-483 Squalene, biosynthesis of, 1485, 1488

from farnesol, 1485, 1485 as isoprenoid hydrocarbon, 1464 lanosterol from, 1486--1488 oxide of, 1486-1487

Squaric acid, 13 13 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 1 10 of diimide reductions, 419 of E2 eliminations, 245-248 of electrocyclic reactions, 1006- 1012 of halogen additions to alkenes, 362, 365-366 of homogenous hydrogenation, 4 17 of hydroboration, 422-424 hydrogenation of alkenes with, 41 8-4 19 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), 147 1 - 1474 numbering system for, 1474 synthesis, 1477- 1479

Sterols (see Steroids) Stigmasterol, structure and occurrence of, 1472 Stilbene (see also 1,2-Diphenylethene), cis-trans,

photochemical isomerization of, 1384-1386 Stimulants, 1098 Stork, G., and cantharidin synthesis, 1497-1498

and cedrene synthesis, 1498 Strain energies, of cycloalkanes, 464-465 Strecker synthesis of amino acids, 1225 Structural formulas, development of, 4- 16 Structural isomers, 45 Structure determinations, 3

by physical methods, electron diffraction and, 265

electron microscopy and, 262-263 neutron diffraction and, 265 x-ray diffraction and, 262-265

by reaction product studies, 12-16 Strychnine, 867 Styron, 1433

Substituent constants, of Hammett equation, 1330-1337

Substitution, definition of, 42 Substitution method for proof of structure, 8-9, 14 Substitution reactions (see Nucleophilic

displacement, Electrophilic aromatic substitution, etc.)

Substrate-enzyme complexes, 1260- 1262 Subtilisin, histidine function in, 1266

serine function in, 1265-1266 Subtraction colors, 1399-1400, 1409-1415 Succinic acid (see Butanedioic acid) Succinimide (see Butanimide) Sucrose, properties and occurrence of, 907

reactions of, 930-93 1 structure and configuration of, 929-93 1 structure determination of, 93 1-932 synthesis of, 93 1

Sulfanilamide, 1 123- 1124 Sulfate esters, from additions to alcohols, 369-371

from alcohols, 628-629 Sulfenyl chlorides, additions to alkenes, 380 Sulfolane (sulfur dioxide and 1,3-butadiene

adduct), 500-501 ,

Sulfonamide synthesis of amines, 1127 Sulfonamides, acidity of, 1123

as amine protecting groups, 1161 amines from, 1127 as antibacterial agents, 1123-1 124 in Hinsberg test, 1123 in peptide-sequence determinations, 1230 preparation of, 1122-1 123 reductive cleavage of, 1161

Sulfonate esters, from acyltetracarbonyl- ferrates, 15 16

from alcohols, 628-629 of oximes, 1 180 with tetracarbonylferrate, 15 16

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, 13 18

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, 13 17

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, 143 1-1434 Synthesis, and natural products, 1461

principles in planning of, 5 13-530 Synthesis gas, 723 Synthetases, 1270-127 1 Szwarc, M., and "living" polymers, 145 1

2,4,5-T, 561 D-Tagatose, structure and configuration of, 906 D-Talose, structure and configuration, 905 Tanning of leather, 1459 Tannins, 1304 D-Tartaric acid, absolute configuration of, 876 Tartaric acid, biochemical resolution of, 869

conformations of, 135- 139 isomers of, 135-138 optical activity of, 118 physical properties of (table), 137-139 racemic form of, 1 18 resolution of, 118

Taste and stereoisomerism, 140 Tau (7) bonds, 165-167 Tedlar, 1432 Teflon, synthesis and uses of, 568, 1432 Terephthalic acid (see 1,4-Benzenedicarboxylic

acid) Termination, of radical polymerization, 1448- 1449 Terpenes (see also Sesquiterpenes, Diterpenes,

etc.), alcohols, 1465-1466 aldehydes, 1465-1466 as essential oils, 1462 examples of (table), 1462- 1464 isoprene rule, 1462-1463 ketones, 1466- 1467 oxygenated derivatives, 1465- 1466

Terpinol, 1466 Terramycin, 1482 Tertiary structures, of peptides, 1228 Terylene, 1433 Testosterone, structure and occurrence, 1473 Tetraalkylammonium salts, elimination reactions

of, 1126 formation of, 1125-1 126 nomenclature of, 1102

Tetracarbonylferrate, 15 16 2,2,3,3-Tetrachlorobutane, nmr spectrum of,

1345-1346 1,1,2,2-Tetrachloroethane, as polypropene

solvent, 143 1 Tetrachloroethene, Raman spectrum of, 285-286

reaction with bromine, 16 unsaturated character of, 16

Tetrachloromethane, from chlorination of methane, 100

physical properties of, 239 radical-chain addition to alkenes and

alkynes, 389 toxicity of, 563 uses of, 562-563

Tetracyanoethene, charge-transfer complex of, 1192-1 193

in [4 + 21 cycloadditions, 495 Tetrafluoroethene, biradicals from, 1014-10 17

bond energy of, 1017 1,3-butadiene cydloadducts of, 502 polymerization of, 568 polymers from, 391, 568, 1430, 1432 preparation of, 568

Tetrafluoromethane, 18 Tetrahydrocannabinol, 1305 Tetrahydrofuran (see Oxacyclopentane) Tetramethylammonium salts and hydroxide,

1125-1 126 N, N, N', N' -Tetramethyl- 1,4-benzenediamine,

oxidation of, 1307 Wurster's Blue from, 1307

2,2,3,3-Tetramethylbutane, heat of combustion of, 79

Tetramethylene glycol (see 1,4-Butanediol) cis-2,2,5,5-Tetramethyl-3-hexene, heat of

hydrogenation of, 4 15-4 16 trans-2,2,5,5-Tetramethyl-3-hexene, heat of

hydrogenation of, 4 15-4 16 2,2,4,4-Tetramethyl-3-pentanone, photochemistry

of, 1381 N, N, N', Nf-Tetramethyl- 1,4-phenylenediamine (see

N, N, N', N'-Tetramethyl- 1,4-benzenediamine) Tetramethylthiuram disulfide, 1429 1,1,2,2-Tetraphenyl-l,2-ethanediol, 1382-1383 Tetraterpenes, ,&carotene as example of, 1469 Tetrodoxin, 599 Tetroses, structures and configurations of, 904-907 Tetryl, 1192 Thallium salts, additions to alkenes, 380 Thermodynamic control, of additions to alkenes,

374-376 of aldol additions, 75 1-752 carbocation rearrangements, 633 of Claisen condensations, 829-832

Thermodynamics, applications to organic chemistry, 23, 76-88, 96-97

Thermoplastic polymers (see Polymers) Thermosetting polymers (see Polymers) THF (see Oxacyclopentane) Thiacycloalkanes, nomenclature systems for,

659-66 1 Thiamine chloride, 1099 Thiamine pyrophosphate, in Calvin cycle, 1269

decarboxylation function of, 1267- 1269 in glucose metabolism, 1269 hydrogen exchange of, 1268

Thiazine dyes, 1406 Thin-layer chromatography, for amino acids, 12 19 Thioesters, of coenzyme A, 837-840, 1480- 148 1 Thioglycolic acid, with wool, 1458

Thiohydantoins, in peptide sequence determina- tions, 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, 108 1 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 Thuj aplicin, 13 14 Thujone, 1467 Thymine, as DNA component, 1272- 1277

lactam-lactim isomerism of, 1273 photochemical dimerization of, 1394

Thyroxine, 535-536 Tin hydrides, reduction of halides with, 109 Titanium, in Ziegler polymerization, 1444 Titanocene, 1508 TNT, 1042, 1192 Todd, A., and vitamin B,,, 1490 Tollen's reagent, 9 13 Toluene (see Methylbenzene) Toluene-2,4-diisocyanate, 1454-1455 Toluenesulfonic acid and esters (see corresponding

derivatives of 4-Methylbenzenesulfonic acid)

Toluidines (see Methylbenzenamines) Torsional angle, definition of, 121 Tranquilizers, 1098- 1099 Transamination, of amino acids, 1224 Transfer RNA, 1279-1282 Transition state, and activation energy, 96-97

in aromatic substitution, 1041, 106 1 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, 15 10-15 1 1,

1513-1514, 1517-1519 Transition-metal organic compounds, alkyl

groups in, 15 10-1526 carbene type, 1512, 1521 with carbon monoxide, 15 12, 15 14-15 16,

1518-1520, 1522-1524 carbon monoxide binding in, 15 12 catalytic functions of, 15 17-152 1, 1523, 1526 cyclopentadiene derivatives, 1504- 1508,

1512-1515 and ferrocene, 1504- 1505 metallocenes as, 1504-1508, 15 12-15 15 nitrogen fixation by, 1508

l ndex

nucleophilic types, 15 16, 1520, 1525- 1526 pi ( 7 ~ ) complexes with, of cycloalkenes,

1510, 1523 with 2-propenyl groups, 1522-1524

as reagents, 1508, 1512-1516, 1521-1524 sigma (a) type, 1510-1511, 1513-1520,

1525- 1526 stability of, 1504-1508, 15 10-151 1

2,4,6-Triaminobenzenecarboxylic acid, 1304 2,4,6-Triaminotriazine, resins from, 1444 Triarylmethyl derivatives (see corresponding

Triphenylmethyl derivatives) Triazenes, from benzenediazonium salts, 1 137 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, 13 17 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, 13 18 4-Trifluoromethylbenzenamine, base strength

of, 1116 Trifluoromethylbenzenes, from arenecarboxylic

acids, 1318 Trifluoroperacetic acid (see Trifluoroperoxy-

ethanoic acid) Trifluoroperoxyethanoic acid, with alkenes, 662 Trifluralin, 1195 Triglyme, 656 Trihaloethanoates, dihalocarbenes from, 566 2,4,6-Trihydroxybenzenecarboxylic acid, 1303- 1304 1,2,3-Trihydroxypropane (glycerol), manufacture

of, 542

Trimethylamine (see N,N-Dimethylmethanamine) 1,3,5-Trimethylbenzene, charge-transfer complexes

of, 1192 Trimethylboron, bonding and bond angles of,

150-160 Trimethylene oxide (see Oxacyclobutane) Trimethylenemelamine, as carcinogen, 1 164 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-Trinitrobenzenecarboxylic acid, reduction

of, 1304 2,4,6-Trinitrobenzenol, arenes, picrates with, 1 192

charge-transfer complex formation with, 1192 as explosive, 1192 physical properties of, 1289

2,4,6-Trinitro- 1-methylbenzene, 1042, 1 189, 1 19 1 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, 132 1-1322 dyes derived from, 1404- 1406

Triphenylmethanol, triphenylmethyl cation from, 1321

Triphenylmethyl cations, colors of, 132 1 with 1,2,3-cycloheptatriene, 13 15 ease of formation of, 1320-1321 sulfur dioxide as solvent for, 1320 from triphenylmethanol, 132 1 from triphenylmethyl chloride, 1320

Triphenylmethyl chloride, amine alkylations with, 1158

ionization of, 1320 triphenylmethyl radical from, 1323

Triphenylmethyl group, hydrogenolysis of, 1158 Triphenylmethyl peroxide, 1323 Triphenylmethyl radicals, dimerization of, 1323

discovery of, 1322- 1324 reactions of, 1323 resonance and, 1323- 1324

Triphenylmethylation, of amines, as protecting group, 1158

Triphenylmethylsodium, formation of, 1321 Triphenylphosphine, as transition-metal ligand,

417, 1510, 1517-1519 Triphosphoric acid, esters of, formation and

reactions of, 634-637, 940-956, 1483-1485 Triple bonds, formulation of, 167- 168 Triplet states (see also Photochemistry, triplet

states in), 994, 1373-1375 Trisaccharides, definition of, 925

properties and occurrences of, 907

Triterpene, definition of, 1469 Trityl derivatives (see corresponding Triphenyl-

methyl derivatives) Trityl protecting group for mines, 1158 Tropocollagen, 1458- 1459 Tropolone, acidity of, 13 14-13 15

aromatic reactions of, 1315 copper salt of, 13 14 derivatives of, 13 14- 13 16 synthesis of, 13 14

Tropylidene (see 1,3,5-Cycloheptatriene) Tropylium anion, and Hiickel rule, 997-998 Tropylium cation, from 1,3,5-cyclohepta-

triene, 13 15 Huckel rule and, 997 hydroxide equilibrium with, 13 15 from methylbenzene in mass spectrometer, 345 spectra of, 13 15

Tropylium radical, esr spectrum of, 1369 Trypsin, in peptide sequencing, 1232-1233

precursor of, 1269 proteolytic properties of, 1260 serine function in, 1265- 1266

Trypsinogen, 1269 Trytophan, properties of, 1210 Tschudi, G., and morphine synthesis, 1499 Tungsten catalysis, of alkene metathesis, 1520- 152 1 Turpentine, 1464, 1467, 1469 Tyrian purple, 1407 Tyrosine, in carboxypeptidase, 1263-1264

properties of, 1210

Ultraviolet spectroscopy (see also Electronic spectra), elements of, 267

Uncertainty principle, and exchange lifetimes in nmr spectra, 1345- 1346

and Mossbauer spectroscopy, 1360 and nmr line widths, 1343-1344

Unimolecular reactions, 2 16-2 17 Units for wavelengths of electromagnetic radiation,

265-268 Unsaturated carbonyl compounds (see Carboxylic

acids, unsaturated; Aldehydes, unsaturated, etc.)

Unsaturated compounds (see respective Alcohols, unsaturated; etc.)

Uracil, in RNA, 1278 Uranocene, 1508 Urea, resins from, 1443- 1444 Urethane foams, 1454- 1455 Uridine, in RNA, 1278 Urushiol, 1304 Usnic acid, 1304

Valence, elementary ideas of, 4

Valence-bond treatment (see also Resonance), ab initio method and, 981-984

of benzene, 972-975 of 1,3-butadiene, 977 of ethene, 965-966 (;VB method and, 983-984 of hydrogen, 96 1-964 J and Q in, 974-975 of propenal, 977 of 2-propenyl cation, 978-979 Q and J in, 974-975 stabilization energies (table), 985-986

Valeric acid (see Pentanoic acid) Valine, in penicillins and cephalosporins, 1492

properties of, 1208 van der Waals forces, and cyclohexane equilibria,

454-456 and polymer properties, 1422, 1426- 1429

van Tamelen, E. E., and cantharidin synthesis, 1497-1498

van't Hoff, J. H., and asymmetric carbon, 116 and cis-trans and chiral isomers of polyenes, 5 11 and free rotation, 8 and tetrahedral carbon, 118-1 19

Vanillin and vanilla, 925 synthesis of, 1327

Vapor-phase chromatography (see Chromatography)

Vasopressin, 1242-1243 Verbena, oil of, 1462, 1464 Verbenone, 1467 Vibrational relaxation, 1374 Vicinal, definition of, 662 Victor Meyer method of molecular weight

determination, 27-28 Vinyl alcohols (see Enols, Ethenol, etc.) Vinyl bromide (see Bromoethene) Vinyl cations, formation of, 549 Vinyl fluoride (see Fluoroethene) Vinylacetic acid (see 3-Butenoic acid) Vinylacetolactone (see Diketene) Vinylacetylene (see 1-Buten-3-yne) Vinylamines (see Enamines) Vinylite, 1435 Viscose rayon, 933 Visible spectroscopy (see also Electronic spectra),

elements of, 267 Vision, chemistry of, 1416-1417 Vistanex, 1432 Vitamin A, as diterpene, 1468-1469

structure of, 50 Vitamin B,, 1099 Vitamin B,, 1099 Vitamin B,,, alkylation of with ATP, 1526

biological function of, 1526 coenzyme form of, 1525-1526 methylpropanedioyl to butanedioyl coenzyme A

with, 1526 and pernicious anemia, 1489 reduction of, 1526-1527 structure and function of, 1489-1490 synthesis, 1490

as transition-metal compound, 1525- 1526 Vitamin C, structure of, 938 Vitamin D, from ergosterol on irradiation, 1394 Vitamin D,, structure and occurrence of, 1472 Vitamin K,, 1310 Viton, 568, 1432 Vol'pin, M., and nitogen fixation by

titanocene, 1508 von Laue, M., and x-ray diffraction structure

determinations, 1249 Vulcanization, 1429- 1430, 1435

Wacker process, 1528 Wald, G., and chemistry of vision, 1417 Walden, P., inversion in S , reactions, 219-223 Wallach, 0. and isoprene rule, 1462 Warfarin, as blood anticoagulant, 336

nmr spectrum of (carbon-13), 336 Water, addition to alkenes, 368-370

addition to alkynes, 383-384 atomic-orbital model of, 162- 164 bond angles of, 163-164 ionizing power of, 238 as leaving group, 232-234 nmr spectrum of, and paramagnetic ions, 1344 physical properties of, 60, 239

Watson, J. D., and DNA structure, 1249, 1275 Wieland, H., and structures of steroids, 1476-1477 Wilds, A. L., and equilenin synthesis, 1495 Wilke, G., and propenylnickel derivatives,

1521-1524 Wilkins, M. and x-ray diffraction structure

determinations, 1249 Wilkinson, G. homogenous hydrogenation catalyst

of, 417-418 and hydroformylation catalysis, 15 19

Williamson ether synthesis, 6 14-6 15 Willstatter, R., and chlorophyll structure, 1258

cyclooctaetraene synthesis of, 990 Windaus, A., and structures of steroids, 1476-1477 Wintergreen, oil of, 1327- 1328 Wittig, G., an ylide reaction, 692 Wohl degradation, 910 Wohl-Ziegler bromination, 542-543 Wolff-Kishner reduction, of aldehydes and

ketones, 7 1 1--7 12 of Huang-Minlon modification, 7 1 1-710

Wood, 933 Woodward, R. B., cortisone synthesis, 1495-1497

and orbital symmetry rules, 1005 and reserpine synthesis, 1500- 1502 and vitamin B,,, 1490

Wool, chemistry of, 1457- 1458 Wurster's Blue, 1307

X-ray diffraction, and protein structures, 1249 reference works for, 347 structure determination by, 262-265

Xanthene dyes, 1406 Xylenes (see Dimethylbenzenes) Xylenols, from coal tar, 108 1 D-Xylose, furfural from, 938

in hemicellloses, 937-938

Yams, diosgenin from, 1478 Yeast sterol, 1472 Yellow dye, 1410-1414 Yields, in parallel vs. sequential reactions, 516-517

procedures for calculating, 5 15-5 17 Ylides, additions to aldehydes and ketones,

69 1-693 definition of, 691

Zeise's salt, 1509-15 10 Ziegler, K., catalysts for alkene polmerization,

396-397 Ziegler catalysts, copolymers from, 1435 Zinc, in carboxypeptidase, 1263- 1264 Zinc chloride, as catalysis for alkyl halide

formation, 626 in chloromethylation of arenes, 13 19

Zingiberene, 1464 Zirconocene, decamethyl, nitrogen fixation

by, 1508 Zirconocene chlorohydride, with alkenes, 15 13

structure and preparation of, 15 13 synthetic reactions of, 15 12-15 15

Zytel, 1433