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

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, 218 structural effects on, 224-234 thermochemistry of, 212-2 13

Nucleophilic reagents, definition of, 207-2 11 Nucleophilicity, and base strength, 210-2 11

and structure, 235-237 Nucleosides, structure of, 1274

Nucleotides, base-pairing of, 12741275 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, 14261427 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, 15231524 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, 518-522 Odors and stereoisomerism, 140141 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, 118120

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, 159161 Orbital phase, 156

Orbitals (see Atomic orbitals or Molecular orbitals) Organic chemistry, definition of 21-22

scope of, 21-22 uses of, 22

Organic photochemistry (see Photochemistry) Organic syntheses, principles in planning of,

513-530

Organoboranes (see also Hydroboration), acid cleavage of, 427, 429

alcohols from, 427-428

from alkenes and diborane, 420-424

alkyland 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, 581-582 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, 571-573

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, 15101516, 1520, 1525-1526

carbene complexes, 1512, 1521 sandwich type, 1505-1508 vitamin B,, as, 1525-1527

Organonilrogen compounds, types of (summary), 1184

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), 10601064 Osmium tetroxide, alkene additions of, 434 Osmium tetroxide-sodium periodate, ketones

from, with alkenes, 730 Overlap, of atomic orbitals, 155161

Oxacycloalkanes, nomenclature systems for, 659-66 1

Oxacyclobutane (trimethylene oxide, oxetane), reactions of, 661

Oxacyclobutanes, from photochemical cycloadditions, 13891390

Oxa-2-cyclobutanone, as carcinogen, 1164 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, 661-662 physical properties of, 654 polymerization of, 1423 reactions of, 661-662

Oxacyclopropanes, alcohols from, with Grignard reagents, 609

by hydride reduction, 610 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, 1110 Oxazine dyes, 1406

Oxidation (see also individual oxidizing agents, as Ozone, etc.), of arenes, with oxygen,

10771078

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, 11801181

Beckmann rearrangement of, 1149, 1153, 1180-1181

E,Z convention for, 887, 1181 nitriles from, 1185

reduction to amines, 1146, 1148 stereoisomerism of, 1131 sulfonate esters of, 1180

syn and anti isomers of, 1181

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, 14821488 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,

951-954

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, 1391 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, 13921393 chemistry of, 1391-1393

electronic configuration of, 1391 photochemical generation of, 1391-1392

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, 431-433 methanol reaction of, 432 reduction of, 43 1-432

Ozonization, aldehydes from, 727 of arenes, 10781079

ketones from, with alkenes, 730 mechanism of, 432-433 procedures for, 431-432

Palmitic acid, 789-790 Pantothenic acid, structure, 1211

Paper chromatography, for amino acids, 12181219 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, 153155 Pauli principle, bonding in hydrogen and, 961 Pauling, L., and alpha helix, 1251

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, 415 stabilization energy of, 986

1,4-Pentadiene, heat of hydrogenation of, 415 Pentaerythritol, 754

polyesters from, 1440 Pentalene, 10861087

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, 1231 chymotrypsin hydrolysis of, 1233 conventions for, 1228

with dansyl chloride, 1230 denaturation and, 1228

Edman degradation of, 12301231 formation of, in prebiotic evolution, 1284 helical structures of, 1251-1252

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, 12381240 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, 10101017 definition of, 419, 498

electrocyclic type, 10051014 and Hiickel rule, 999-1017

rules for prediction of, 10101012 sigmatropic type, 1006, 1010

of singlet oxygen, 1391-1392

Periodate, oxidation of 1,2-alkanediolswith, 717 Perkin, W. H., and founding of dye industry,

1405-1406 Perlon, 1433

Permanganate, aldehyde oxidation, 712 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, 1317 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, 13951399 chlorination induced by, 102103 decomposition of, 102103

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 Peroxytrifluoroethanoicacid, 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, 10711072 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, 12951296 from arenamines, 1293

from aryl halides, 557-559 with aryldiazonium salts, 1300 bromination of, 12961297

Bucherer reaction and, 1295-1296 C-alkylation of, 1297-1298

from coal tar, 1291

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, 12941295 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), 12881291 radicals in oxidation of, 1301-1302 resonance in, 1288

salts of, with alkyl halides, 1294 C-alkylation of, 12971300 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, 12301231

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, 1313

Phenyldiazane, synthesis and reactions of, 924, 1138, 1140

Phenylethanenitrile, from chloromethylbenzene, 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, 1138, 1140

N-Phenylhydroxylamine, from nitrobenzene, 1194 reactions of, 1140, 1194

Phenylmagnesium bromide, ferric chloride coupling of, 1505

Phenylmercuric ethanoate, from mercuration of benzene, 1058

Phenylmethanol, from chloromethylbenzene, 1318 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 SN2reactions, 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, 10131014

1,3-dienesto cyclobutenes, 1387

1,2-diphenyletheneto phenanthrene, 1387 stereochemistry of, 13871388

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, 13821383 of diphenylmethanone, 13821383 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, 13571358 principles and uses of, 1356-1357

Photoelectron spectrum, of benzene, 1357 of ethene, 1357

of ethyne, 1357

Photographic developers, chemistry of, black and white, 1310-131 1

chemistry of, color, 1411-1414 Photosensitization, "and energy transfer, 1377

ketones for, 1385-1386

in photographic films, 1411-1412 singlet oxygen from, 1392

Photostationary states, 1386

Photosynthesis, Calvin cycle, 941-943 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, 941-943

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, 14681469 occurrence of, 1468I469

Pi (7~)bonds, of ethene, molecular-orbital treatment of, 964-965

valence-bond treatment of, 965-966 formulation of, 165167

Pi (7~)complexes (see also Charge-transfer complexes), from alkenes and halogens, 367

in arene halogenation, 10441045 of nitro compounds, 11921193

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, 1192

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, 15091510 cyclohexyne complex of, 1510

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, 14141415 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, 14811482

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, 14421443 epoxy resins from, 1444-1445'

of 1,2-ethanediol, 1423 melamine resins from, 1443-1444 polyamides from, 1441 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, 14511452 of methanal, 696

radical mechanism of, catalysts for, 395, 1447 chain transfer in, 1449

direction of addition in, 14471448 inhibitors for, 1449

initiation of, 395, 14471448 termination of, 396, 14471449

Polymers (see also Copolymers, and individual polymers), addition, of alkenes, 14461453

atactic, 504-505, 1430-1435

by anionic mechanism, 392-393, 1452-1453 by cationic mechanism, 393-395, 1451

copolymers from, 14521453

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, 14271435 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, 14561457 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, 14291430, 1435 emulsion, 1447

end groups on, 1420, 1448-1449, 1452 fiber formation, 1427-1428, 1435 fiberglass, 1440

flexibility of chains in, 14271429, 1435, 1456 gel, 1422

glass temperatures of (table), 1427-1435 graft, preparation of, 1455 high-temperature, 1456-1457

hydrogen bonding in, 14261427 importance of, 1419

isotactic; 504-505, 14301435 ladder, arenecarboxarnides as, 1457

polyimides as, 1456 quinoxalines as, 1456

melting points of (table), 1427-1435 of methanal, 696

molecular weights, number average, 14201421 weight average, 1421

oriented and unoriented, 1428, 1435 photodegradable, 1453 photoinitiation of, 1447

hhysical properties of (table), 14221423, 14251435

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, 14301435 structural elements of, 1419-1420 syndiotactic, 1430-1435

of tetrafluoroethene (Teflon), 568, 1430-1432 thermoplastic, characteristics of, 1422,

1425-1429

thermosetting, characteristics of, 14221423 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, 10781079 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, 14301435

carbon-13 nmr spectrum of, 1434 isotactic, 14301435

physical properties, 396, 1430-1435 stereoisonlers of, 1430-1435 syndiotactic, 1431, 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, 14541455

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, 12821284 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, 1217 properties of, 1210

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, 512-5 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, 1481 Propanenitrile, synthesis of, 1185

1,2,3-Propanetriol (glycerol), from fats, 790 manufacture of, 542

physical properties of, 239 polyesters from, 14391440 properties of, 648

uses of, 648

1,2,3-Propanetriyltrinitrate, 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, 771-772

keto-en01 equilibrium of, 736-740 mass spectrum of, 340-341

oxime of, rearrangement of, 1180 photochemistry of, 1379-1380 from photoreduction of

diphenylmethanone, 1383 physical properties of, 679 from 1,2-propadiene, 512

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, 15201521

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, 391, 396, 1432, 1435

radical-chain addition of HBr to, 385-389 radical-chain polymerization of, 396

Propenenitrile, anionic polymerization of, 1451 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 SN2reactions, 225 reactivity of (table), 589 SN1reactivity of, 228-229

2 - ~ r o ~ e n ~ l m a ~ n e sbromide,u m nmr spectrum of, 1524

Propenylnickel complexes, chemistry of, 15251524 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, 14931494 structure and function of, 1492-1493

synthesis of, 1493-1494, 1502-1503 Prostanoic acid, 1492

Prosthetic groups, of myglobin, 1256-1257 Protecting groups, for m i n e functions, 11571161

for carbonyl functions, 715-716 general characteristics of, 529

for hydroxyl function, 529-530, 651-653 illustration of use of, 529-530

in peptide syntheses, 12361239, 12441246 Proteins, biosynthesis of, DNA and, 1271, 1277

coiling of, 12491252 collagen as, 1458-1459

cystine linkages in, 12531254 denaturation of, 1259, 1270 fibrous, 1259

formation of, in prebiotic evolution, 1284 functions of (table), 1249-1250

industrial uses of, 12701271 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, 12241225

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, 1118

Quinoneimines, in photographic development, 1311 Wurster's Blue as, 1307

Quinones (see also Benzenediones, Naphthalenediones, etc.), addition reactions, 1311-1313

of benzene, 1301, 1303, 1305-1307, 1309-1312 biologically important examples, 13081310 of biphenyl, 1306

of 1,3-cyclobutadiene, 1313 electrochemistry of, 13061307 of naphthalene, 1305-1306, 1310

as photographic developers, 1310-13 11 as polymerization inhibitor, 1449 preparation of, 1145, 1301-1303

of pyrene, 1306 reduction of, 1306-1307

reduction potentials of, 13061307 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, 117-1 18 mechanisms for, 895-897

in peptide syntheses, 12381240 in SN1reactions, 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, 14521453 in addition polymerization, 395-396, 1444-1449 alkyl, relative stabilities of, 388

from azo compounds, 1198 bonding and geometry of, 169-170 in cycloadditions, 10141017

in phenol oxidations, 1301-1302

in photochemical reactions, 1353-1356, 13791381 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, 215-2 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, 215-2 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, 1513-15 14

in arene alkylations, 10491050 Beckmann, of oximes, 11801181 benzilic acid, 1326

carbocation, in alcohol dehydrations, 632-633 in mines with nitrous acid, 1131

in SN1and 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