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

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, 186187, 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

singleor 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, 14961497 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, 621-624

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, 1381 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, 771

Keto-en01 equilibria, 736-741, 776-778, 827-828 Ketoketenes, 771

Ketones, acidities of (table), 736-738

from acyl halides, and alkyltetracarbonylferrates, 1516

and alkylzirconocenes, 15141515 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, 691-692

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, 611 by reduction, 610-61 1

aldol additions of, 752-754, 756-758, 760-761 from 1,2-alkanediols, by oxidation, 717, 730

by rearrangement, 720, 731

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, 10511053 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, 1317

a-halogenated, Favorskii rearrangement of, 748-749

reduction of, 748

SN1and S,2 reactivity of, 748 halogenation of, base and acid catalyzed,

742-745

mechanism of, 742-745 hemiketal formation from, 622 -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, 621-624

from lithium reagents and carboxylates, 583 mass spectra of, 684 Meerwein-Ponndorf-Verley reduction of,

709-7 10 nitriles from, 1185

from nitriles, with Grignard reagents, 731 nmr spectra of, 684

from Oppenauer oxidation, 730 from organoboranes, 428-429

oxidation of, Baeyer-Villiger, 713-7 14 oximes from, 698

from 3-oxoalkanoic esters, by hydrolysis, 731

from 3-oxobutanoic acids, 834

from ozonization of alkenes, 431-433 with phosphorus pentachloride, 704

photocl~emicalcycloadditions of, with alkenes, 1389-1390

photochemistry of, CIDNP effects on, 1353-1356 photoreduction of, 13821383

as photosensitizers, 13851386 physical properties of (table), 678-679

preparative methods for (table), 717-729 protecting groups for, 715-7 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, 711

by Grignard reagents, 582 with hydrides (table), 705-708 by hydrogenation, 7 10 photochemical, 13821383 by Wolff-Kishner, 711-712

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, 813

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, 511

P-Lactamases, 1492

Lactams, as functional derivatives of carboxylic acids, 819

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, 819

from hydroxy acids, 843

from unsaturated acids, 842-843 Lactose, properties and occurrence of, 907

structure and configuration of, 929

Ladder polymers, 14561457 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 displacement 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, 610

aldehydes from, acids and acyl derivatives, 728, 810-81 1, 824-825

amide and nitrile reductions, 719, 728, 824-825

amines from, 824-825, 11461148, 1154

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, 14511452 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, 13971399 Lucite, 1433

LUMO orbitals, 981 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, 12141215 properties, 1209

Lysozyme, carbon-13 spectrum of, 1286 disulfide bridges in, 12541255 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, 11061108 of amino acids, 1216

apparatus for, 340, 1361-1363 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, 13601365 hydrocarbons, chemical ionization of, 1362 isotopes and, 342-343

of ketones, 340-341, 684, 1362

methane, chemical ionization of, 13611362 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, 1135-1 136 Meerwein-Ponndorf-Verley reduction, 611,

709-7 10

Meisenheimer, J., and aryl addition complexes, 555 Melmac (melamine) resins, 1444

Melvalonic acid, in cholesterol biosynthesis, 14861488

in terpene biosynthesis, 1483-1485, 1488 Membrane lipids, 790, 805

Menadione, 1310 Menthol, 14661467 Menthone, 14661467

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, 12421247

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, 15201521

Methanal, alcohols from, with Grignard reagents, 577, 579, 608

in aldol additions, 753-754

ammonia addition to, 700 Bakelite resins from, 14421443 ball-and-stick model of, 35

with benzenol, 14421443 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, 1101 Methane, bonds and geometry of, 169

in chemical ionization mass spectrum of, 1361-1362

chlorination of, 81-85, 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, 31-32

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, 612 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, 1164 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, 1164 Methyl ethyl ketone (see 2-Butanone)

Methyl fluoride (see Fluoromethane) Methyl D-glucosides, 915

Methyl 2-hydroxybenzenecarboxylate, 13271328 Methyl iodide (see also Iodomethane)

amines from, 1125

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, 169170 Methyl salicylate, 13271328

Methyl vinyl ketone (see 3-Buten-2-one) Methylacetylene (see Propyne) Methylamine (see Methanamine) 4-N-Methylaminobenzenol, 1311

N-Methylaniline (see N-Methylbenzenamine) 4-Methylbenzenamine, base strength of, 1115 N-Methylbenzenamine, infrared spectrum of, 1104 Methylbenzene, benzenecarboxylic acid from, 1317

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, 10791083 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, 101102 chlorination of, 100102

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, 1081 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, 721-722, 1293 physical properties of, 1027 2-propanone from, 721-722, 1293

3-Methyl-3-hydroxypentanedioic acid (mevalonic acid), 14831488

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, 1164 1-Methyl-3-nitrobenzene,synthesis of, 1190 N-Methyl-N-nitrosourea, as carcinogen, 1164 N-Methyl-N-nitro-2,4,6-trinitrobenzenamine, 1192 Methylphenols (see Methylbenzenols) 2-Methylpropane, in alkylation of 2-methyl-

propene, 397-398 heat of combustion of, 79

yield calculations for bromination of, 515-5 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, 631-632 industrial preparation of, 607

2 - ~ e t h ~ l ~ r o ~alkylationee , by 2-methylpropane: 397-398

cationic polymerization of, 393-395 copolymer with 1,3-butadiene, 506, 508 from dehydration of 2-methyl-2-propanol,

631-632

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, 1189 1,3,5-trinitrobenzenefrom, 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, 271 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, 31-34 determination of, 2, 3

three-dimensional representations of, 125130 Molecular geometry (see Bond angles, Bond

lengths, and specific compounds) Molecular-orbital treatment, ab initio method and,

981-984

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, 961-963 and electronic spectra, 980-98 1 of ethene, 964-965

GVB method and, 983-984

of 1,3,5-hexatriene with bromine, 971 of hydrogen, 961-964

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, 1318

Monosaccharides, definition of, 902-903 Morphine, 1097

synthesis of, 14991500

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, 917-9 18 Mylar, polyester film, 1433

Myleran, as carcinogen, 1164

Myoglobin, function, 12491250, 12541259 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, 1162 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), 10691071 sulfonation, 1070

triplet state of, 1377 1,2-Naphthalenedione, as quinone, 1305

1,4-Naphthalenedione, blood coagulants from, 1310 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, 14301435 Natural products, approaches to study of,

1461-1462

biosynthetic pathways for, 1461-1462 definition and classification of, 14601461 structure determination of, 1461

and synthetic chemistry, 1461 Natural rubber, 507-508

biosynthesis of, 1485, 1488 vulcanization of, 14291430 NBS (see N-Bromobutanimide)

Neopentane (see 2,2-Dimethylpropane) Neopentyl derivatives, rearrangement of, in

solvolysis reactions, 250 solvolysis of, 250

steric hindrance in SNreactions of, 224-225 Neopentyl iodide, synthesis, 587

Neoprene, 506, 1433 Neral, 1465-1466 Nerol, 1465-1466

Neryl pyrophosphate, 14841485 Neutron diffraction, 265 Newman projections, 125-126 Niacin, 1099

Nickel, 1,3-butadiene trimerization with, 1523 1,5-cyclooctadienecomplex of, 1510 T-propenyl complexes of, preparation of, 1522

reactions of, 15221524 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, 1481

in terpene biosynthesis, 1485 Nicotinic acid, 1099 Ninhydrin, 779

with amino acids, 1216-1218, 1221 Nitrate ion, and resonance, 176177 Nitration, of alkanes, 105

of arenes (see also Electrophilic aromatic substitution), acyl nitrates in, 1043

alkyl substituted, 10421043 ips0 mechanism for, 10661068 mechanism of, 1041

nitric and sulfuric acids in, 1041-1042 nitronium salts in, 1041, 1044 orientation in, 10411042, 10581072

Nitrenes, in Curtius degradation, 1156 in Hofmann degradation, 11551156

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, 719, 728, 824

alkylation of, 1185

amides from, 858, 1177-1178 from amides, 1185

amines from, by hydride reduction, 824-825 from arenediazonium salts, 1134, 1185

as carboxylic acid derivatives, 202, 819 carboxylic acids from, 854, 1185 dipole moments of, 1185

from halides, 11841185 infrared spectra of, 1184

infrared stretching frequencies for, 276 IUPAC rules of nomenclature for, 202 ketones from, with Grignard reagents, 731 from oximes, 1185

preparation of, 11841185 reactions of, 1185

reduction to aldehydes, 719, 728, 824 reduction to amines, 11461147 Ritter reaction and, 1149, 1178-1 179 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, 11951196 aldol additions of, 1196

from aldol and Michael additions, 758, 1196 from alkanes, 1187

from alkyl halides, 11901191

from arene nitration, 10391044, 10581072, 1187-1188

from arenes, 11871190

charge-transfer complexes of, 1192-1 193 diazene oxides from, 1194

dipole moments of, 1186 electronic spectra of, 1187

as explosives, 11911192 as herbicides, 1195 infrared spectra of, 1187 Michael additions of, 1196

as polymerization inhibitors, 1449 reduction of, amines from, 11461147,

1151, 1193 azanols from, 1194

nitroso compounds from, 11931194 resonance and, 1186

by Sandmeyer reaction, 1191 thermochemistry of, 1191

unsaturated, in [4+21 cycloadditions (table), 493-494

volatility of, 1186-1 187 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, 10411044, 10591060, 10651071 2-Nitrobenzenamine, from

N-nitrobenzenamine, 1140 4-Nitrobenzenamine, base strength of, 1115 N-Nitrobenzenamine, rearrangement of, 1140 Nitrobenzenamines, base strengths of, 1115-1 116 Nitrobenzene, from benzene, 1041

electronic absorptions of, 14021403 nmr spectrum of, 1036-1037

reduction of, azanols from, 1193-1 194 azo compounds from, 1194

azoxy compounds from, 1194 benzenamine from, 11931194 diazanes from, 1194 hydrazines from, 1194 reagents for, 11931194

as solvent, in arene acylations, 1052, 1070 Nitrobenzenecarboxylic acids, and Hammett

equation, 13291330

4-Nitro-l,2-benzenedicarboxylic acid, 1317 4-Nitrobenzenol, acidity of, 1294

and anion, electronic absorptions of, 1402 electronic absorptions of, 14021403 physical properties of, 1289

Nitrobenzenols, hydrogen bonding in, 1291-1292 nmr spectra of, 1291-1292

4-Nitrobiphenyl, as carcinogen, 1162 Nitroethane, 1187

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, 1191 physical properties of, 239 thermochemistry of, 1191

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, 11291131 Nitrosamines, rearrangement of, 1139 Nitrosation, of alkanand benzenamines,

1129-1130, 1136 N-Nitrosazacyclohexane, as carcinogen, 1164 Nitroso compounds, azo compounds from, 1194 N-Nitrosoamides, diazomethane from, 1199 Nitrosobenzene, from

N-phenylhydroxylamine, 1194 N-Nitroso-N-methylbenzenamine, rearrangement

of, 1139

Nitrosyl chloride, additions to alkenes, 380 Nitrous acid, with alkanamines, 1129-1 131 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, 176177 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, 11721173 cis-trans isomerism and, 11721173 nitrogen-15 in, 1175

proton exchange and, 1172

of amines, chemical shifts in, 1105 hydrogen exchange in, 1105-1 106 inversion effects on, 11101111

of arenes, ring current effects on, 1034-1035 spin-spin splittings in, 10361037

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, 917-9 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, 311-3 13

averaging by conformational equilibration, 303-304, 456, 460-46 1, 1345-1347

and carbon bond types, 310-3 11

and chemical exchange of protons, 311-3 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, 13451346 general characteristics of, 300-3 15 and hydrogen bonding, 311

and infrared for structure determination, 313-3 14

magnetic field strength and, 304-306 pprn scale for, 306

proton values for (table), 306-3 11 reference standard for, 304 shielding parameters of, 300-301 Shoolery7srule for, 310

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, 871-872 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, 461 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, 1175 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, 10341035

in annulenes, 1035, 1088 ringing in, 298-299

and rotation about single bonds, 303-304, 13451347

shift averaging in, 13451346 shift reagents and, 872-873

spin quantum numbers for, 297-298 spin-spin splitting in, alkenes, 320, 325-326

of benzene protons, 10361037 binomial coefficients and, 319 calculation of, 1348-1353 characteristics of, 316-322

chemical-shift effects on, 305, 317, 332-333 and conformations, 321-32 1

coupling constants for, 317, 319-321, 325-326 and decoupling, 322, 336

equivalent nuclei and, 316, 319, 332 ethyl groups, 316-3 18

first-order, 316

intensities of lines with, 318-3 19, 325-326 iodoethane, 316-3 18

line multiplicities in, 316-318, 325-326 long-range, 320

n +1 rule for, 317-3 19 patterns of, 316-3 19, 325-327

proton structural variations of, 319-32 1, 325-327

saturated systems, 319-32 1 second-order, 316-3 17, 333 and structural analysis, 322-327 theory of, 13481353 three-bond, 319-32 1 two-bond, 319-320

in structural analysis, 322-327 7 scale for, 306

and uncertainty principle, 13431346 Nmr spectrum, of Zbromobutane, 328

of 3-bromopropene, 324

of I-buten-3-yne-4-D, 1353 carbon13, of D-glucose, 918

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, 319

of (2,2-dimethoxyethyl)benzene, 328

of ethanol, 295-296, 311-3 12 of ethyl 3-oxobutanoate, 827 of N-ethylethanamine, 1105 of ethynylbenzene, 357

of D-glucose, carbon-13, 917-9 18 iodoethane, 316

of methyl methoxyethanoate, 313-3 14 of 2-methyl-2-butanol, 305

of methylcyclohexane, carbon13, 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, 12911292

nitrogen15, of N-methylmethanamide, 1175 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-trimethylazacyclopropane, 1111 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

singleor 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, 1314

iron tricarbonyl complex of, 1510 quadricyclene from, 503 synthesis of, 1314

thermal rearrangement of, 1314 Norbornene, 999

Nordel, 1432

Norrish, R. G. W., and type I and I1 photodissociations of ketones, 13791380

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, 1120 mechanism of, 553-555, 1120

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, 551

of cyclopropylmethyl halides, 551 electrophilic catalysis of, 233-234 general characteristics of, 213-2 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, 214-2 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 11 references for, 252

reversibility of, 236-237

1130-1131, 1133

of haloalkanoic acids, 817 ion pairs in, 223

kinetics of, 215-2 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 stereochemistry 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, 815-8 16 kinetics of, 215-217

nitriles from, 11841185