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

A b initio calculations, for ethene, 180182 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, 14291430 Acenaphthene, from coal tar, 1080 Acetaldehyde (see Ethanal)

Acetaldol (see 3-Hydroxybutanal)

Acetals, from alcohols and carbonyl compounds, 621-624

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-Phenylethanamide) 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, 14811482

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, 12651266 Acetylene (see Ethyne)

Acetylenes (see Alkynes) N-Acetylglycine, 1222 Acetylketene (see Diketene) Achiral, definition of, 116

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, 615-6 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, 11391140

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 11

formulation of, 208-2 11

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, 1160 in Curtius degradation, 1156

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, 1516 from acylzirconocenes, 1514

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, 1150,

1153, 1156

with amino acids, 1222 anhydrides from, 857 carboxylic acids from, 855 carboxylic esters from, 856

with diazomethane, 692-693, 1200 esterification of, 615-6 18

as functional derivatives of carboxylic acids, 818 with Grignard reagents, 823-824

l~ydrolysisof, 820 infrared frequencies, 680

IUPAC rules of nomenclature for, 198 ketones from, with alkylcadmiums, 584

from alkylcoppers, 584

with alkylzirconocenes, 15141515 with cadmium alkyls, 731

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

Acyl hydrazides, amines from, by Curtius degradation, 1150, 1156

Acyl nitrates, with arenes, 1043

Acyl nitrenes, in Curtius degradation, 1156 in Hofmann degradation, 11551156

Acyl peroxides, decarboxylation of, radicals from, 812

Acyl phosphates, in biochemical esterifications, 636-637

Acylation, of amines, 11211122 of arenes, 1051-1053

Acyltetracarbonylferrates, 1516 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 B1, as carcinogen, 1164 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, 612-613 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, 611-6 12

alkyl halides from, with hydrogen halides, 625-627

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

from alkylzirconocenes by oxidation, 1514 amines from, 1125-1 126

with amino acids, 12211222 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, 611

by Meerwein-Ponndorf-Verley reduction, 611 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-eliminationreactions 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 SN2displacement,

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, 621-624

with alkyl halides, 614-6 15 ester formation by, 615-6 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,

651-653

proton exchange in, 311-313, 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, 912 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,718-7 19 with oxygen, 639

alcohols from, by Meerwein-Ponndorf-Verley reduction, 611

with Grignard reagents, 608-609 by reduction, 610-61 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, 717, 727

by rearrangement, 720

from alkenes, by carbonylation of alkylboranes, 725-726

by hydroboration and carbonylation, 729

by hydroformylation, 722-723, 729, 15181520 with ozone, 727

from alkyl halides, by methylsulfinylmethane oxidation, 718

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, 12231224

ammonia addition to, 700 azines from, 698

benzoin condensation of, 13241325 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, 1318

from N,N-dimethylrnethanarnide, and Grignard reagents, 729

electronic excitation of, 1375-1376 electronic spectra of, 681 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, 15181519

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, 1185

from nitriles, by hydride reduction, 728, 824 nmr spectra of, 684

from organoboranes, 428-429 oxidation of, Baeyer-Villiger, 713-7 14

oxygen, 712-7 13 permanganate, 712

peroxycarboxylic acids, 713-7 14 silver oxide, 712

oximes from, 698

from ozonization of alkenes, 431-433 physical properties of (table), 678-679 polymerization of, 696

preparative methods for (table), 717-729 protecting groups for, 715-7 16

proton chemical shifts, of, 311 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, 711

by Grignard reagents, 582 with hydrides (table), 705-708 by hydrogenation, 710 Wolff-Kishner, 711-7 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, 751

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, 751-753

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, 751-753

Aldolase, 760, 947-948 Aldonic acids, 912

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

Aldose-ketose interconversions, 918-9 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, 13871389 photochemistry of, 13871389 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, 611, 643 infrared spectra of, 605

properties of, 646-648

urethane foams kom, 14541455 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, 711-712

from alkenes, by zirconocene chlorohydride reduction, 1514

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, 102103, 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, 100102

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, 310-3 11 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, 511 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, 15201521 Alkene metathesis reaction, 15201521 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, 1518-15 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

amides from, 858, 1149, 1178-1 179 mines from, 1149

atomic-orbital models of, 165167 bromine addition to, mechanism of,

362-364, 367

stereochemistry of, 362, 365-366 bromine substitution on, with

N-brombutanimide, 103104 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, 138413.86 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 alkyland dialkylboranes, 423

general characteristics of, 420-424 hydroformylation, 15181519

hydrogen bromide addition to, stereochemistry of, 368

hydrogen chloride addition to, 367-368 hydrogenation of, catalysts for, 411-4 14,

1517-15 19

with diimide, 418-419 heats of (table), 415

homogenous catalysis of, 417-418, 15171519 mechanism of, 411-413, 1517-1519

selectivity in, 413-414 hydroperoxides from, 721 hydroxylation of, reagents for, 434-437

stereochemistry of, 434-436

hypohalous acid additions to, 360, 377-378 infrared spectra of, 351-353

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

l ndex

orientation in electrophilic additions to, 373-382

osmium tetroxide reaction with, 434 oxacyclopropanes from, 662 oxidation of, 43 1-437

ozonization of, 431-433 peroxidation mechanism of, 456 with peroxycarboxylic acids, 435-436 from phosphate esters, 634

photochemical cycloadditions of, dimerizations, 1389

with ketones, 1389

[2+21 type, 503 photochem~calisomerization of, 1384-1386

photoelectron spectra of, 13571358 physical properties of (table), 351-352 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,

14461453

monomers for (table), 391, 14321433 radical-chain mechanism for, 395-396,

14461449, 14521453

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, 1514 resonance structures for, 176

Ritter reaction of, 1149, 1178-1 179 rotation about the double bond of, 167,

13841386

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, 1512-1 514 Alkenic hydrogens, definition of, 60

Alkenols, alkenones from, by chromic acid oxidation, 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, 681

infrared frequencies of, 681 spectral properties of, 681, 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, 14391440 Alkyl cyanides (see Nitriles)

Alkyl halides, from alcohols, 625-627 alkylation of arenes with, 1056 from alkylzirconocenes, 1514 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, 718 nitrile alkylation with, 1185

nitriles from, 1184-1 185

nitro compounds from, 1187, 11901191 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, 614-6 15 organomagnesium compounds from, 576-577 organometallic compounds from, 572-573

b y halogen-metal exchange with halides, 573-574

physical properties of (table), 537-538 reactions of, 539-54 1

reactivities of (table), 539, 589

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, 1516

Alkyl phosphates (see Phosphate esters) Alkyl radicals, names for, 53

Alkyl shifts, with alkyl transition metal compounds, 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, 10521053

from arene alkylations, 10471050 detergents from, 10561057 industrial syntheses based on, 1083 ipso nitration of, 1067-1068

from petroleum, 10791083 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, 1514 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, 61-62

nucleophilic addition to, methanol in, 385 organometallics from, 574

oxidative coupling of, 441 physical properties (table), 351-352 proton chemical shifts of, 311

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, 512-5 13 hydration of, 512 isomerization of, 512-5 13 stability of, 512-5 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, 15251524 Alpha helix, peptides and, 1251-1252

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, 611

Aluminum, in Ziegler polymerization, 1444 Ambrette seed, oil of, 1468

Ameripol, 1433

Amides, from acid derivatives (table), 1176-1 178 acidity of, 1175-1 176

from acyl halides, 11771178

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, 1150, 1153,

1155-1 156

by hydrolysis, 1154

by reduction, 824-825, 1147, 1154 from amines, with acyl halides and

anhydrides, 822

and carboxylic acid derivatives, 1121-1 122, 1176-1 177

with ketene, 771 from azides, 11771178 basicity of, 1176

from Beckmann rearrangement, 1180-1 181 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, 12401241

in peptide synthesis, 12401241 dipole moments of, 1168

from esters, 1177-1 178 geometry of, 1167-1 168

with Grignard reagents (table), 579, 823-824 hydrogen bonding of, 1168

hydrolysis of, 820-82 1, 11821183 infrared spectra of, 680, 1170-1 171

IUPAC rules of nomenclature for, 199, 1169 from ketones, by Haller-Bauer cleavage, 747 nitration of, 11881190

nitriles from, 1185 from nitriles, 1178-1 179

N-nitroso compounds from, 1183, 1163 with nitrous acid, 1183

nmr spectra of, 11721175 from oximes, 11801181

in peptide structures, 1227-1228 from phenyl esters, 1177-1 178 physical properties of, 1168 planarity of, 1168

polarity of, 1168

polymers of, 1181, 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, 11461147 resolution of chiral forms of, 868

from Ritter reaction, 1149, 11781179 solvent properties of, 1168 stabilization energy of, 1159, 1168

synthesis of, from acid derivatives (table), 1176-1 178

types of, 1169 Amidol, 1311

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, 1112 acylation of, 11211122

alcohol comparisons with, 1095-1096 from alcohols, 11251126

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), 1101, 11111118 basicities of, alkanamines and, 10951096,

1112-1113

arenamines and (table), 1113-1 116 azarenes and, 1117-1 118 cycloalkanamines and, 1112-1 113

from Beckmann rearrangement, 1149 with benzenesulfonyl chloride, 11221123 benzoylation of, as protecting group, 1159

benzyloxycarbonylation of, as protecting group, 1159-1160

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

carcinogenic, 11611162 chiral forms of, 11091110

chiral, as resolving agents, 866-867 from Curtius degradation, 1150, 1156 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, 1150, 1155 hydrogen bonding of, 1103

imines from, 1122

infrared spectra of, 277, 1104 inversion of, 11091110

IUPAC rules of nomenclature of, 200-201, 1100-1 102

ketone additions of, 697-699, 702 mass spectra of, 11061108

metal salts of, benzyne generation with, 1120 enolate salt generation with, 1120 nomenclature of, 1120

as nucleophiles, 11261127 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 nitrogen14 relaxation effects on, 1106

as nucleophiles, 1096, 1121-1 129 odors of, 1103

oxidation of, 1141-1145 phenylmethoxycarbonylation of, as protecting

group, 11591160

physical properties of (table), 1101-1 103 preparation of, by alkylation of amines,

1125-1 126

from amides, 824-825, 1146-1 147, 1150, 1154-1 156

Gabriel synthesis for, 1127 from nitriles, 11461147

from nitro compounds, 1146-1 147, 1151 by sulfonamide synthesis, 1127

protecting groups for, acylation for, 11581160 alkylation for, 1157-1 158

protonation for, 1157 sulfonylation for, 1161 table of, 1236-1239

proton exchange in, 311-3 13 protonation of, as protecting group, 1157

from reduction, amides, 1146-1 147, 1154-1 155 azides, 1146, 1150

imines, 1146, 1148, 1154 nitriles, 11461147

of nitro compounds, 11461147, 1151 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, 1108-1 110 sulfonamides from, 11221123 sulfonylation of, as protecting group, 1161 synthetic routes to (table), 11451156 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, 1212-1215 acidic type, 1207

with aldehydes, 1223-1225

from amination of halo acids, 1225 analysis of, fluorescamine, 12171218

ion-exchange chromatography, 1219 ninhydrin, 1216-1218, 1221

paper chromatography and, 12181219 thin-layer chromatography, 1219

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, 12231224 decarboxylation of, 12231224 diketopiperazines from, 1222

dip-olar forms of, 12121215 electronic spectra of, 1216

from enolate anion alkylations, 12251226 equilibria of, 1210-1215

esters from, 1221-1222 fluorescamine, reaction, 1217 imines from, 12231224

infrared spectra of, 1215

ion-exchange chromatography, 12191220 isoelectric points of (table), 1208-1210, 1212 isolation of, 1227

malonic ester syntheses of, 1225-1226 mass spectra of, 1216

melting points of, 1215 metabolism of, 12241225 from Michael additions, 1226 ninhydrin reaction, 1216-1217 with nitrous acid, 1223 nonprotein examples, 1211

paper chromatography, 1218-12 19 in peptides, conventions for, 1228

peptide bond of, 1228

physical properties (table), 1208-12 10, 1215 p K values of (table), 1208-12 10

protecting groups for, in peptide syntheses, 12361247

as protein constituents (table), 1206-1210 purification of, 1227

with pyridoxal phosphate, 1224-1225 reactions of, 12211225

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, 12251227

thin-layer chromatography of, 1219 Aminoacyl-tRNA, 1281-1282 4-Aminobenzenesulfonamide, 1123-1 124 4-Aminobenzenol, from phenylazanol, 1140

as photographic developer, 1311 physical properties of, 1290

4-Aminobutanoic acid, and nerve impulses, 1211 l-Aminoethanol, 700

Aminophenols (see Aminobenzenols) Aminophenylethanoic acid, synthesis of, 1225 4-Aminostilbene, as carcinogen, 1162 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, 14771478 [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, 914-9 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, 10971099

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, 1113-1 116

from Beckmann rearrangement, 1153 from benzidine rearrangement, 1153 from Bucherer reaction, 12951296 as carcinogens, 11611162, 1164 from Curtius degradation, 1153, 1156

from Hofmann degradation, 1153, 1155 from nitro compounds, 1193

nitro compounds from, 11871191 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, 11441145

from phenols, 12951296

as polymerization inhibitors, 1449 protecting groups for, 1157-1 161 quinones from, 1145