Organic chemistry ORGANIC CHEMISTRY methane to macromolecules JOHN D ROBERTS California ~nsiiitkeof Technology ROSS STEWART University of British Columbia MARJORIE C CASERIO University of California, Irvine W A BENJAMIN, INC New York 1971 Organic chemistry: Methane t o macromolecules Copyright 1971 by W A Benjamin, Inc All rights reserved Standard Book Number 8053-8332-8 Library of Congress Catalog Card Number 71-130356 Manufactured in the United States of America 12345K54321 Portions of this book appeared previously in Modern Organic Chemistry by John D Roberts and Marjorie C Caserio, published by W A Benjamin, Inc 1967, New York W A BENJAMIN, INC New York New York 10016 preface The success achieved by this book's forerunners, Basic Principles of Organic Chemistry and Modern Organic Chemistry, was to a considerable extent due to the rigor with which the subject of organic chemistry was presented In the present work we have tried to paint an interesting, relevant, and up-to-date picture of organic chemistry while retaining the rigorous approach of the earlier books Organic chemistry sometimes appears to be enormously complex to the beginning student, particularly if he must immediately grapple with the subjects of structural isomerism and nomenclature We have attempted to avoid this difficulty in the following way Chapter briefly relates carbon to its neighbors in the Periodic Table and reviews some fundamental concepts Chapter deals with the four C, and C , hydrocarbons-methane, ethane, ethene, and ethyne-and discusses their conformational and configurational properties and some of their chemical reactions The reader thus makes an acquaintance with the properties of some important organic compounds before dealing in an open-ended way with families of compounds-alkanes, alcohols, etc A heavy emphasis on spectroscopy is retained but the subject is introduced somewhat later than in the earlier books Important additions are chapters dealing with enzymic processes and metabolism and with cyclization reactions Many of the exercises of the earlier books have been retained and have been supplemented with drill-type problems It seems a shame to burden the mind of the beginning student with trivial names, some of them quite illogical, and throughout we have stressed IUPAC nomenclature, which is both logical and easy to learn The instructor, who may well carry lightly the excess baggage of redundant names, may occasionally find this irritating but we ask him to consider the larger good As a further aid to the student, each chapter concludes with a summary of important points The simple introduction to the subject and the emphasis on relevance, particularly to living systems, should make the book appealing to the general student At the same time we hope that the up-to-date and more advanced topics that are included-the effect of orbital symmetry on cyclization reactions, for example-will also appeal to the chemistry specialist We should like to acknowledge the help of many persons who read all or parts of the manuscript and offered sound advice Professor George E Hall read the manuscript at several stages of revision and we are particularly preface vi grateful to him Others who helped us were Drs E Caress, L D Hall, D N Harpp, J P Kutney, T Money, M Smith, T Spencer, and L S Weiler We conclude this preface on a mildly philosophical note The world of tomorrow will result from the interplay of powerful forces-some social, some technological Responsible public action requires public knowledge and there are few areas of science that impinge more on the life around us than does organic chemistry We hope that those who study this book will utilize their knowledge responsibly for 'the benefit of all who come after JOHN D ROBERTS ROSS STEWART MARJORIE C CASERIO Pasadena, California Vancouver, British Columbia Irvine, California contents Chapter I Introduction 1.1 Bonding in Organic Compounds 1.2 Methane, Ammonia, Water, and Hydrogen Fluoride Summary Exercises Chapter The C, and C, hydrocarbons 2.1 Molecular Shape of CH, , C2H6, C2H4, and C,H, 2-2 Rotational Conformations of Ethane 2.3 Space-Filling Models Chemical Reactions of the C , and C, Hydrocarbons 2.4 Combustion 2.5 Substitution Reactions of Saturated Hydrocarbons 2.6 Addition Reactions of Unsaturated Hydrocarbons Summary Exercises Chapter Alkanes Nomenclature Physical Properties of Alkanes-Concept Alkanes and Their Chemical Reactions 3.4 Cycloalkanes Summary Exercises of Homology Chapter Alkenes 4.1 4.2 4-3 4.4 Nomenclature lsomerism in C,H, Compounds Cis and Trans Isomers Chemical Reactions of Alkenes Summary Exercises Chapter Alkynes 5.1 Nomenclature 5-2 Physical Properties of Alkynes vii contents 5.3 5.4 5.5 5.6 viii Ethyne Addition Reactions of Alkynes Alkynes as Acids Synthesis of Organic Compounds Summary Exercises Chapter Bonding in conjugated unsaturated systems 6.1 6.2 6.3 6.4 6.5 6.6 6-7 Bonding in Benzene Conjugate Addition Stabilization of Conjugated Dienes Stabilization of Cations and Anions Vinyl Halides and Ethers Rules for the Resonance Method Molecular Orbital Method of Hiickel Summary Exercises Chapter Isolation and identification of organic compounds 151 7.1 Isolation and Purification 7.2 Identification of Organic Compounds Spectroscopy 7.3 7.4 7.5 7.6 159 Absorption of Electromagnetic Radiation Infrared Spectroscopy Ultraviolet and Visible Spectroscopy (Electronic Spectroscopy) N ~ ~ c l e aMagnetic r Resonance Spectroscopy Summary Exercises 159 161 165 168 179 180 Chapter Nucleophilic displacement and elimination reactions 8.1 Organic Derivatives of Inorganic Compounds 8.2 Alcohol Nomenclature 8.3 Ether Nomenclature 8.4 Carboxylic Acid Nomenclature 8.5 The Use of Greek Letters to Denote Substituent Positions 8.6 Single- or Multiple-Word Names Nucleophilic Displacenzent Reactions 8.7 8.8 8.9 8.10 8.1 General Considerations Mechanisms of S, Displacements Energetics of S,1 and S,2 Reactions Stereochemistry of S,2 Displacements Structural and Solvent Effects in S, Reactions 185 187 187 190 190 191 191 192 contents Elimination Reactions 205 8.12 The E2 Reaction 8.13 The El Reaction Summary Exercises Chapter Alkyl halides and organometallic compounds 9-1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 Physical Properties Spectra Preparation of Alkyl Halides Reaction of Alkyl Halides Vinyl Halides Allyl Halides Polyhalogen Compounds Fluorinated Alkanes Organometallic Compounds Summary Exercises Chapter 10 Alcohols and ethers 10.1 Physical Properties of Alcohols 10.2 Spectroscopic Properties of Alcohols-Hydrogen 10.3 Preparation of Alcohols Bonding Chemical Reactions of Alcohols 10.4 10-5 10.6 10.7 10-8 Reactions Involving the 0-H Bond Reactions Involving the C-0 Bond of Alcohols Oxidation of Alcohols Polyhydroxy Alcohols Unsaturated Alcohols Ethers 10.9 Preparation of Ethers 10.10 Reactions of Ethers 10.1 Cyclic Ethers Summary Exercises Chapter a I Aldehydes and ketones P Reactions at the carbonyl group 11.1 11.2 11.3 11.4 Nomenclature of Aldehydes and Ketones Carbonyl Groups of Aldehydes and Ketones Preparation of Aldehydes and Ketones Reactions of Aldehydes and Ketones Summary Exercises ix conte Chapter 12 Aldehydes and ketones 11 Reactions involving substituent groups Polycarbonyl compounds 12-1 Halogenation of Aldehydes and Ketones 12.2 Reactions of Enolate Anions Unsaturated Carbonyl Compounds 12.3 +Unsaturated 12.4 Ketenes Aldehydes and Ketones Polycarbonyl Compounds 12.5 1,2-Dicarbonyl Compounds 12.6 1,3-Dicarbonyl Compounds Summary Exercises Chapter 13 Carboxylic acids and derivatives 13.1 13.2 13.3 13.4 13.5 13.6 13-7 Physical Properties of Carboxylic Acids Spectra of Carboxylic Acids Preparation of Carboxylic Acids Dissociation of Carboxylic Acids Reactions at the Carbonyl Carbon of Carboxylic Acids Decarboxylation of Carboxylic Acids Reactions at the Positiod of Carboxylic Acids Functional Derivatives of Carboxylic Acids 13.8 Displacement Reactions of Acid Derivatives 13.9 Reactions at the Position (a position) of Carboxylic Acid Derivatives 13.10 Reactions of Unsaturated Carboxylic Acids and Their Derivatives 13.11 Dicarboxylic Acids Summary Exercises Chapter 14 Optical isomerism Enantiomers and diastereomers 14.1 14-2 14.3 14.4 Plane-Polarized Light and the Origin of Optical Rotation Specific Rotation Optically Active Compounds with Asymmetric Carbon Atoms Optically Active Compounds Having No Asymmetric Carbon Atoms 14.5 Absolute and Relative Configuration 14.6 Separation or Resolution of Enantiomers 14.7 Asymmetric Synthesis and Asymmetric Induction general index 594-596 rearrangements in, 595 Nucleophilic catalysis, 496-497,499-500 Nucleophilic displacement reactions (see also Nucleophilic aromatic substitution), 192-205 of activated aryl halides, 593-594 of alkyl derivatives, 193-195 of alkyl halides, 193-195 catalysis by heavy metal salts, 203 energetics of, 197-200 of heterocyclic compounds, 678679 kinetics of, 196-197 the leaving group in, 202-203 mechanisms of, 195-1 97 nature of solvent, 204-205 reagents for, 193-195 SNi,502 solvents for, 193-195 stereochemistry of, 200-201, 389 structural effects in, 201-204 synthetic utility of, 193-195 Nucleophilic reagents, and basicity, 203-204 list of, 193-194 Nucleosides, 480-48 Nucleotides, 48 Nylon, 750-751 hydrogen bonding in, 739 Octafluorocyclobutane, physical properties of, 226 as a propellant, 226 Octane, heat of combustion of, 24, 57, 510 infrared spectrum of, 163 isomers of, 48 octane rating of, 58 physical properties of, 53-55, 63 Octane rating, 57-58 1-Octanol, from 1-hexanol, 265 Oil of wintergreen, 658 Olefins (see also Alkenes), 81 Oleic acid, 330 Opium alkaloids, 684 Optical activity, origin of, 369-371 Optical isomerism, 369-392 and absolute and relative configuration, 381-384 of allenes, 379-380 836 of amine oxides, 434 of amines, 426 asymmetric induction, 386-387 of biphenyls, 380-381 in Zbutanol, 369 conventions for, 374-375,381-384 and optical rotatory dispersion, 389-391 of organophosphorus compounds, 525 of organosilicon compounds, 533 of organosulfur compounds, 524525 projection formulas, 374-375 resolution (see Resolution) and restricted rotation, 379-381 of spiranes, 379-380 Optical isomers, definition of, 369 diastereomers, 378 enantiomers, 384 meso forms, 377 resolution of, 384 threo and evythuo forms, 377 Optical rotatory dispersion, 389-391 of 10-methyl-2-decalone, 390 Oral contraceptives, 789 Orbital symmetry, and cycloaddition reactions, 726-730 Orbitals, antibonding, 141, 277 bonding, 145 definition of, 7, 129 in ethene, 34 nonbonding, 141 shapes of, 129, 517-518 d Orbitals, and chemical bonds, 517520 in organosilicon compounds, 533534 p Orbitals, 129 s Orbitals, 129 d2 sp3 Orbitals, 519 sp2 Orbitals, 131 sp3 Orbitals, 130, 519 ORD (see optical rotatory dispersion) Organic chemistry, definition of, Organic nitrogen compounds, 421426 Organic synthesis (see Synthesis) Organoboranes, as Lewis acids, 536 Organoboron compounds, 536-540 nomenclature of, 539 general index Organocadmium compounds, with acyl chlorides, 233, 279 ketones from, 233 Organofluorine compounds, physiological properties of, 226 Organolithium compounds, 234 Organomagnesium compounds, with acids, 230 with 1-alkynes, 229 with carbonyl compounds, 231233, 250 carboxylic acids from, 336 with cyclopentadiene, 229 with halogens, 230-231 with metallic halides, 229 with nitriles, 233 with oxygen, 230-231 with sulfur, 230-231 thiols from, 522 Organomercury compounds, from Grignard reagents, 229 from methyl iodide, 228 as seed fungicides, 234 Organometallic compounds (see also individual types such as Organomagnesium compounds), 226-235 from aryl halides, 592-593 bonding in, 227, 230 preparation of, 228-229 toxicity of, 229 use of, 234 Organonitrogen compounds (see Organic nitrogen compounds) Organophosphorus compounds, 528531 asymmetry of, 525 Organosilicon compounds (see also indi~lidualtypes such as Silanes, Silanols, etc.), 531-536 asymmetry of, 533 preparation and properties, 534535 types of, 532 Organosodium compounds, 234 Wurtz coupling of, 228 Organosulfur compounds, 520-528 nomenclature of, 520-521 Orientation, in addition polymerizatioil, 754 in electrophilic aromatic subsitution, 567-574 in nitration of arenes, 568 837 Orlon (see Polyacrylonitrile) Ortho-Novum, 789 Osazones, formation of, 403 Osmium tetroxide, in alkene oxidation, 261 Oxalic acid, acid dissociation constant of, 357 decarboxylation of, 359 physical properties of, 357 Oxidation, of alcohols, 259-260, 523, 526 of alkenes with osmium tetroxide, 98-99 of alkenes with ozone, 97 of alkenes with permanganate, 98-99 of alkylboranes, 97 of amines, 432433, 523 of cholesterol, 784 of civetone, 770-771 of cumene, 627 of cyclohexane, 750 of enols, 292 of ethanol by NAD@, 506-508 of eugenol, 658 of glucose, 509 of hydroquinones, 638 and metabolic processes, 510 microbiological, 788 photochemical, 705-706 of sulfides, 525 of thiols, 523-524 Oxidation levels, of nitrogen, 421 Oxidative phosphorylation, 509 Oximes, formation of, 289 reduction of, 430 rearrangement of, 429430,439 Oxomalonic acid, 282 Oxonium ions, from carbonyl compounds, 285-286 in en01 formation, 304 from ethers, 264 in hemiacetal and acetal formation, 285-286 Oxygen, excited singlet state of, 705706 as inhibitor in chain reactions, 32 triplet state of, 705 Ozone, air pollution from, 58 as 1,3-dipole, 721-723, 731 Ozonides, 97 Ozonization, 97-98, 279 general index Palladium, in catalytic hydrogenation, 35 in reduction of acyl chlorides, 279 Palmitic acid, 330 acid dissociation constant of, 331 physical properties of, 33 Papain, properties and function of, 478 Papaverine, 684 Paper chromatography, in amino acid analysis, 466 Paraffin, 56 Paraformaldehyde, from formaldehyde, 287-288 Partial rate factors, in nitration of arenes, 569 Pasteur, L., 385 Patterson, A M., 552 Pauli exclusion principle, 130 Pelargonidin chloride, 687-688 Pencillin, in resolution of enantiomers, 385 Penicillin G ,p-lactam structure of, 468 X-ray diffraction analysis of, 468 Pentaborane, structure of, 537-538 Pentacene, uv spectrum of, 557 Pentadecane, physical properties of, 55 1,3-Pentadiene, 83 1,4-Pentadiene, 83 Pentaerythritol, preparation of, 324 Pentane, isomers of, 48-49 physical properties of, 55, 63, 424 2,3-Pentanediol, optical isomers of, 392 2,4-Pentanedione, acid dissociation constant of, 15 ~ e salt " of, 316 CU" salt of, 316 en01 form of, 314 nmr spectrum of, 314-31 tautomerization of, 315, 723 Pentanoic acid, acid dissociation constant of, 331 physical properties of, 331 cis-2-Pentene, heat of combustion of, 85 physical properties of, 85 trans-2-Pentene, heat of combustion of, 85 physical properties of, 85 4-Pentenoic acid, y-valerolactone from, 355 838 t-Pentyl chloride (see 2-Chloro-2methylbutane) n-Pentylamine, physical properties of, 424 Peptide synthesis, coupling reagents in, 472 protecting groups in, 471 solid-phase, 472 yields in, 471 Peptides, 468-474 amino acid sequence in, 470 analysis of, 469-470 with 2,4-dinitrofluorobenzene,593 naturally occurring polymers, 756-757 synthesis of, 470-474 Peracids, with amines, 433 in radical polymerization, 754 Perfluoro-2-methylpropene,toxicity of, 226 Perfumes, civetone in, 769 coumarins in, 687 cyclopentadecanone in, 772 exaltone in, 772 examples of, 658-659 ingredients in, 612 muscone in, 769 terpene alcohols in, 780 Perhydrophenanthrene, 551 Periodic table, 517 Permanganate oxidation, of alcohols, 260 of alkenes, 261, 287 of amines, 432 Peroxides, as radical initiators, 95 Peroxy radicals, 32 Persulfuric acid, in radical polymerization, 754 Pesticides, analysis for, 156 organochlorine derivatives, 596598 Petroleum, 56-58 Phenacetin, 659 Phenalenyl, 552 Phenanthrene, monosubstitution products of, 551 physical properties of, 553 reactions of, 577 resonance hybrid of, 575 general index 1-Phenanthrylamine, diazotization of, 591 Phenobarbital, 659, 685 Phenol, acid dissociation constant of, 629 from chlorobenzene, 595 commercial synthesis of, 627 physical properties of, 628-629 polymers from, 751-752 resonance hybrid of, 630 stabilization energy of, 605 tautomer of, 605 uv spectrum of, 556, 629 Phenol-formaldehyde resins, 751-752 Phenolphthalein, structure of, 710 Phenols, acidity of, 630 alkylation of, 631-632 from aromatic amines, 617 bromination of, 632-633 chemical properties of, 630-635 with ferric chloride, 631 hydrogen bonding in, 634 nmr spectra of, 635, 637 oxidation of, 635-636 physical properties of, 627-629, 633 polyhydric, 635-636 quinones from, 635-636 reduction of, 635 separation from carboxylic acids, 631 synthesis of, 627-629 Phenoxide anion, resonance hybrid of, 630 Phenyl acetate, formation of, 630 Phenyl ally1 ether, from phenol, 631 rearrangement of, 632 Phenyl azide, addition reactions of, 722 Phenyl halides, in S, reactions, 220 Phenyl radicals, from diazonium salts, 618 Phenylacetic acid, acid dissociation constant of, 331 physical properties of, 331 Phenylacetylene, 550 infrared spectrum of, 164 Phenylalanine, physical properties of, 459 synthesis of, 458 Phenylamine (see Aniline) p-Phenylbenzaldehyde, formation of, 652 839 1-Phenyl-2-butanol, 187 1-Phenyl-3-buten-1-01, 189 Phenyldichloroborane, 539 p-Phenylenediamine, uv spectrum of, 614 Phenylethanone (see Acetophenone) Phenylethene (see Styrene) 2-Phenylethyl bromide, 589 Phenylhydrazine, osazones from, 403 N-Phenylhydroxylamine, 609 from nitrobenzene, 610 Phenyllithium, 191 preparation of, 593 Phenylmagnesium bromide, preparation of, 592 Phenylmagnesium iodide, 191 2-Phenylpyridine, from pyridine, 678 Phenyltrichloromethane, physical properties of, 535 Phenyltrichlorosilane, physical properties of, 535 Phenyltrimethylammonium salts, nitration of, 568 Phenyltrimethylmethane, physical properties of, 535 Phenyltrimethylsilane, physical properties of, 535 Phillips process, in coordination polymerization, 103 Phloroglucinol, reactivity of, 636 structure of, 635 Phosphate groups, in DNA, 479 Phosphines, asymmetric, 525 Phosphonate esters, hydrolysis of, 502 Phosphonium salts, with basic reagents, 530 formation of, 530 reactions of, 530 Phosphorescence, 696-699 Phosphoric acid, derivatives of, 528530 Phosphorous acid, structure of, 529 Phosphorus, in halogenation of acids, 343 organic compounds of, 528-53 Phosphorus halides, with carboxylic acids, 340 Phosphorus pentachloride, in Beckmann rearrangement, 430 with cyclopentanone, 290 Phosphorus pentafluoride, 17 I general index Phosphorus tribromide, in alkyl bromide formation, 256 Photochemistry, 695-709 Photodissociation, 703-704 Photographic developers, 639 Photosensitizers, benzophenone, 706 definition of, 706 2-naphthyl methyl ketone, 707 in photoisomerization, 707 Photosynthesis, of carbohydrates, 399 of glucose, 387 radicals in, 661 study of, 466 Phthalic acid, acid dissociation constant of, 357 anhydride from, 358, 715 physical properties of, 357 Phthalic anhydride, formation of, 358, 715 polymer from, 750 Phytol, 781 in chlorophyll, 781 in vitamin K, 781 Picric acid, 611-612 acid dissociation constant of, 629 charge-transfer complexes of, 612 uv spectrum of, 629 Pimelic acid, acid dissociation constant of, 357 from civetone, 770 cyclohexanone from, 358 physical properties of, 357 Pinacol, rearrangement of, 280 Pinacolone, from pinacol rearrangement, 280 a-Pinene, camphor from, 780 Piperidine, base dissociation constant of, 423 physical properties of, 423 Piperonal, 659 Plane-polarized light (see also Optical Isomerism), and origin of optical rotation, 369-371 Plasticizers, 748 camphor, 780 Plastics (see also Polymers), from cellulose, 410 from formaldehyde, 288 thermal moulding of, 740 Platinum, in catalytic hydrogenation, 35 Polarimeter, description of, 370-371 840 Polarizability, and SN reactions, 203 Pollution, atmospheric, 58 by detergents, 526 from paper pulping, 41 from petroleum, 58 by phosphates, 528 trace analysis for, 156 Polyacrylonitrile, 740 Polyamides, definition of, 469 nylons, 750-751 Polycyclopentadiene, 737 Polyesters, preparation of, 749-750 Polyethylene (see also Polythene), 102 Polyethylene glycol, from ethylene oxide, 266 uses of, 756 Polyhalogen compounds, 222-226 Polyhetero systems, examples of, 679680 Polyisobutylene, 101 Polyisoprene (see also Natural rubber), 98, 742-743 Polymerization, by addition, 753-756 anionic, 100 azo initiators in, 443 cationic, 101, 755-756 by condensation, 748-752 coordination, 103, 753 of cyclopentadiene, 737 ionic, 755-756 of isopentenyl pyrophosphate, 792 of isoprene, 743 radical, 102, 743, 753-755 of tetrafluoroethene, 225 vinyl, 753 Ziegler, 743 Polymers, 737-766 from aldehydes, 287-288 atactic, 744 cold-drawing, 740 cross linking, 738 crystalline state of, 740 definition of, 99 DNA, 479 dyeing of, 758-762 elastomers, 738, 741 glass temperature of, 740 glyptal resin, 750 isotactic, 744 melting temperature, 740 naturally occurring, 756-758 nylons, 750 general index in peptide synthesis, 472 phenol-formaldehyde resins, 751752 physical properties of, 738-748 preparation, 748-756 representative, 745-747 silicones, 533, 536 stereoregular, 753 syndiotactic, 744 thermoplastic, 738 thermosetting, 738 types of, 737-738 vulcanization of, 743 Polynitro compounds, 61 1-61 charge-transfer complexes of, 612613 Polynuclear aromatic hydrocarbons, double bond character in, 574 naming of, 551-552 substitution reactions of, 574 Polyoxymethylene (see Formaldehyde, polymers from) Polypeptides (see Peptides) Polypropene, 100 isotactic, 744 Polypropylene (see Polypropene) Polysaccharides (see Cellulose, Starch, etc.) Polystyrene, configurations of, 744 Polystyrene resin, in peptide synthesis, 472 Polytetrafluoroethene (see Teflon) Polythene, 745 from ethene, 102, 745 crystalline character of, 739 Polyvinyl chloride, 745 "Polywater", 11 Potassium bromide, in infrared spectroscopy, 161 Potassium t-butoxide, in E2 elimination, 252 Potassium permanganate (see Permanganate oxidation) Potential energy, of diatomic molecules, 697 Progesterone, 790 cortisone from, 788 Projection formulas (see also Optical isomerism), of 2-butanol, 374 conventions for, 375, 383 Fischer type, 405 Haworth type, 405 841 Proline, in ninhydrin test, 465 physical properties of, 461 Propadiene (see Allene) Propanamide, infrared spectrum of, 436 nmr spectrum of, 437 Propane, with bromine, 219 in natural gas, 57 nitration of, 61 physical properties of, 11, 55, 63 1,3-Propanedithiol, with acetone, 523 Propanethiol, occurrence, 522 Propanoic acid, 190 acid dissociation constant of, 331 cleavage of alkyl boranes, 97 physical properties of, 331 Propanone (see Acetone) Propanoyl chloride, with benzene, 566 Propargyl chloride (see 3-Chloro-lpropyne) Propenal (see Acrolein) Propene, addition reactions of, 104 with chlorine, 220 hydroboration of, 539 with hydrogen halides, 219 from isopropyl iodide, 252 polymer from, 745 from propyne, 121 Propenoic acid (see Acrylic acid) 2-Propen-1-01 (see also Ally1 alcohol), 262 Propionamide (see Propanamide) Propionic acid (see Propanoic acid) n-Propyl alcohol, from tri-n-propylborane, 97 Propyl bromide, from propane, 219 from 1-propanol, 219 from propene, 95 n-Propyl chloride, physical properties of, 217 n-Propylbenzene, formation of, 566 physical properties of, 553 Propylene (see also Propene), 82 3-Propyl-1-heptene, naming of, 81 Propyne, acid dissociation constant of, 229 addition reactions of, 121 hydration of, 114 Prosthetic groups, 503 in hemoglobin, 680 metals as, 476 in proteins, 469 general index Protecting groups, benzyloxycarbonyl, 471 t-butoxycarbonyl, 472 in peptide synthesis, 471 removal of, 471,473 Proteins, biological functions of, 477 biosynthesis of, 477 conformations of, 474 denaturation of, 469 heat of combustion of, 510 in hemoglobin, 680 isoelectric points of, 476, 478 as peptides, 469 structures of, 474-477 Proton magnetic resonance spectroscopy (see Nuclear magnetic resonance spectroscopy) Protonium ions, 91-92 Prototropic change, 315 Pteridine, 679, 686 Purification, by chromatography, 156 by crystallization, 153 by distillation, 153 by extraction, 153 Purine, 679 derivatives of, 407, 480 natural products related to, 686 Pyran, natural products related to, 686-688 structure of, 406 Pyranose, definition of, 406 Pyrene, 552 3,lO-Pyrenequinone, 638 Pyridine, base strength of, 423, 427, 43 1,674 chemical properties of, 673-679 natural products related to, 684 nucleophilic substitution reactions of, 678-679 physical properties of, 423, 431, 671 Pyridinium salts, formation of, 674 a-Pyridone, catalysis by, 503 from pyridine, 678 tautomers of, 503, 723 Pyridoxine, 684 Pyrimidine, 679 derivatives of, 407 natural products related to, 685686 Pyrogallol, structure of, 635 842 u-Pyrone, 686 y-Pyrone, resonance hybrid of, 686-687 Pyrrole, acid dissociation constant of, 674 aromatic character of, 672-673 atomic orbital description of, 672673 chemical properties of, 673-679 hydrogen bonding in, 671 physical properties of, 671 natural products related to, 680682 resonance hybrid of, 672 Pyrrylmagnesium bromide, formation of, 674 Pyrrylpotassium, 674 Pyrryl anion, resonance hybrid of, 674 Quantum yield, definition of, 703 Quartz, in separation of tautomers, 352 Quebrachamine, mass spectrum of, 772-777 pyridines from, 773-775 structure determination of, 772777 Quercitin, 687 Quinhydrone, 638 Quinine, as resolving agent, 385 Quinoline, 679-680 natural products related to, 684 Quinone-hydroquinone equilibrium, 638 Quinones, 636-641 addition reactions of, 639-640 naturally occurring, 640 from phenols, 635-636 reduction of, 638 Quinuclidine, basicity of, 622 Racemization, by acid-catalyzed enolization, 388 by base-catalyzed enolization, 388 definition of, 373 mechanisms of, 388 by an S,1 process, 388 Radiation, effects of, 695 Radical addition, to alkenes, 94-96 Radical halogenation, of alkanes, 2832, 59-61 of alkylbenzenes, 650 general index Radical polymerization, 753-755 Radicals, acetyl, 703 anion, 613 alkoxy, 95 benzhydrol, 704 coupling of, 655 methyl, 32, 703 in photosynthesis, 661 semiquinone, 638-639 stabilities of, 96 stable triarylmethyl, 654 Raney nickel, 36 Rayon acetate, 410 Reaction ( p ) constants, of Hammett equation, 663-664 Reaction intermediates, types of (see also Intermediates), 32 Reaction rates,diffusion controlled, 495 and entropy of activation, 30 and heat of activation, 30 and mechanism, 28 and rate-determining step, 29 and S, reactions, 196-197 Reactions (see also individual types such as Hydrogenation, Nucleophilic displacement, etc.) addition of unsaturated hydrocarbons, 34 additions to alkynes, 113-1 15 alkylation of esters, 354 chain-termination in radical types, 31 Claisen condensation, 352-354 combustion, 23 condensation of carbonyl compounds with amines, 288-289 conjugate addition, 127, 133-135 cyclization, 715-730 cycloaddition, 718-723 electrophilic addition to alkenes, 87-96 electrophilic aromatic substitution, 559-577 elimination, 205-208, 252, 256 endothermic, 23 esterification, 252-255 of excited states, 695-709 exothermic, 23 heat of, 23 hydrogenation, 35 nucleophilic addition to alkynes, 115 843 nucleophilic displacement, 192205 oxidation of alcohols, 259-260 polymerization of alkenes, 99-103 propagation, 31 solvolysis, 197 substitution, 26, 252 thermodynamics of, 26 Rearrangement, of benzilic acid, 313, 321 of cumene hydroperoxide, 627628 of glyoxal, 313, 321 of hydrazobenzene, 611 of cc-pinene, 798 of squalene, 795 Rearrangements, of alkyl groups, 258, 565 in alkylation of arenes, 565 Beckmann, 429430 Claisen, 632 Cope, 723-724 of dienes, 723-724 of 1,2-glycols, 280 in mass spectrometry, 778 of N-nitroso compounds, 617 of oximes, 429430 of phenyl ally1 ethers, 632 photochemical, 707 of terpenes, 798 of P,y-unsaturated carbonyl compounds, 312 Reducing sugars, definition of, 406 Reduction, of carboxylic acids, 279280, 340 of civetone, 771 of diazonium salts, 619 of nitriles, 280 of nitro compounds, 608-61 photochemical, 704-705 of quinones, 638 Relative configuration, of optical isomers, 381-384 Reserpine, 683 Resolution, crystallization procedure for, 385 definition of, 373 of enantiomers, 384 of optically active acids, 385 of optically active alcohols, 385 of optically active bases, 385 Pasteur method for, 385 general index Resonance, in carboxylate anions, 337 in excited state of 1,3-butadiene, 168 Resonance energy (see also Delocalization energy and Stabilization energy), 132 of benzene, 549 Resonance method, 13 rules for, 140 Resorcinol, acid dissociation constant of, 629 reactivity of, 636 structure of, 635 uv spectrum of, 629 Restricted rotation, and optical activity, 379-381 Rf value, definition of, 466 Ribofuranose, in vitamin B,, ,681- 682 Ribonuclease, properties and function of, 478 synthesis of, 474 Ribonucleic acid (RNA), 484 bases in, 485 classes of, 485 differences from DNA, 489 D-ribose in, 400 Ribonucleosides, as glycosides, 407 D-Ribose, in NAD@,506 in RNA, 400,484 structure of, 400-401 in vitamin B,, 400 Ribosomal RNA, 485 Ribosomes, 484 RNA (see Ribonucleic acid) Robinson, R., 683 Rosenmund reduction, 279-280 Ruff degradation, 416 Ruzicka, L., 769, 779 SN reactions (see Nucleophilic displacement reactions) S-S linkages, in proteins, 457458 Saccharides, classification of, 400402 Salicylaldehyde, acid dissociation constant, 629 coumarin from, 687 uv spectrum of, 629 Salicylic acid, acetyl derivative of, 658 formation of, 633 methyl ester of, 658 physical properties of, 633 844 Salmonella bacteria, 413 Sandmeyer reaction, 591, 618-619 Sanger, F., 475 Santonin, 780 Saponification, 345 Schiemann reaction, 591, 619 Schiff's base, formation of, 289 Schmidt reaction, 430 Selection rules, spectroscopic, 698 p-Selinene, 780 Semicarbazide, 289 Semicarbazones, formation of, 289 Semiquinone radicals, 638-639 epr spectra of, 661 Sensitizers (see Photosensitizers) Serine, in ester hydrolysis, 505 in hydrolytic enzymes, 500 physical properties of, 459 Serotonin (see 5-Hydroxytryptamine) Sesquiterpenes, 779-780 Sex attractants, farnesol, 780 Sex hormones, 788-789 Silane, physical properties of, 535 Silanes, examples of, 532 physical properties of, 535 Silanols, examples of, 532 preparation and properties of, 534-535 Silica gel, in alcohol dehydration, 257 in thin-layer chromatography, 467 Silicon compounds, bond strengths of, 532 organic compounds of, 531-536 resolution of, 533 tetrahedral structure of, 533 Silicones, 536 Silk, 756-757 Siloxanes, examples of, 532 preparation and properties of, 534-535 Silver, as catalyst in ethene oxidation, 261 Silver bromide, in photography, 639 Silver ion, complexes with alkenes, 235 Singlet state, nature of, 697 of oxygen, 705 Sitosterol, 783 Skew-boat (see Twist-boat) Smog (see Pollution, atmospheric), 58 Soap, cleansing action of, 332 formation of, 330 general index 845 Sodium bisulfite, with aldehydes, 294, 527 Sodium borohydride, decomposition of, 291 diborane from, 97 with formaldehyde, 291 with ketones, 291 in reduction of metal salts, 36 Sodium chloride, bonding in, in infrared spectroscopy, 161 physical properties of, Sodium dichromate, in oxidation of alcohols, 259 Sodium ethoxide, formation of, 251 Sodium fluoroacetate, toxicity of, 226 Sodium phenoxide, with carbon dioxide, 633 Sodium phenyl carbonate, rearrangement of, 633 Sodium sulfide, in Kraft process, 41 Sodium sulfonates, as detergents, 526 Sodium triphenylmethide, formation of, 654 Soluble RNA, 485 Solvents, polar aprotic in SNreactions, 205 for SN reactions, 194-195 Sorbitol, from glucose, 404 Specific rotation, definition of, 371 Spectroscopy, 159-1 78 electronic absorption, 165-1 68 elucidating structures with, infrared, 161-1 65 methods in structure detemination, 772-778 microwave, 160 nuclear magnetic resonance, 168178 X-ray diffraction, 159 Spiranes, examples of, 380 optical isomerism of, 379 Spiro[2.2]pentane, structure of, 380 Squalene, 781 biogenesis of, 792-795 conversion to lanosterol, 792-795 epoxide, 794 Stabilization energy (see also Delocalization energy andResonanceenergy) of benzene, 128-129, 549 of p-benzoquinone, 636 of 1,3-butadiene, 135 of heterocyclic compounds, 673 Staggered conformations (see Conformations, staggered) Starch, heat of combustion of, 510 hydrolysis of, 408 structure of, 412 Stearic acid, 330 acid dissociation constant of, 331 physical properties of, 331 Stereochemistry (see also individual types such as Optical isomerism and Geometrical isomerism) of allenes, 379-380 of amines, 425-426 of biphenyls, 380-381 definition of, 369 of electrophilic addition to alkenes, 89 geometric isomerism or cis-trans, 69-71, 84 of nucleophilic displacement reactions, 200-201, 389 and optical isomerism, 369-392 of organophosphorus compounds, 525 of organosilicon compounds, 533 of spiranes, 379-380 Stereoisomers, definition of, 39 Stereospecificity, of biochemical reactions, 387 Steric acceleration, in SN reactions, 202 Steric hindrance, in acetal formation, 287 in additions to a,P-unsaturated carbonyl compounds, 311 in alkylation of phenols, 631 in biphenyls, 381 in boat cyclohexane, 65 in carbonyl additions, 281-282 in cis-alkenes, 85 in hemiacetal formation, 287 relief of, 10 Steroids, 782-789 biogenesis of, 789-794 representative types, 788-791 Stigmasterol, 790 Stilbene, photoisomerization of cistrans isomers of, 707 uv spectrum of, 556 Stoll, synthesis of civetone, 772 Strecker synthesis, 458 Streptomycin, 402 general index Structural isomers, 83, 369 Structure, definition of, 21, 84 Structure determination, 156-178 Strychnine, 683 as resolving agent, 385 Styrene, 128, 550 polymerization of, 754-755 polymers from, 746 uv spectrum of, 556 Suberic acid, from civetone, 770 Substituent (cr) constants, of Hammett equation, 662-663 Substituent effects, in base strengths of amines, 616 in electrophilic aromatic substitution, 567-574 in light absorption, 701-702 in nucleophilic aromatic substitution, 594 Substitution reactions (see also Nucleophilic displacement reactions, Nucleophilic aromatic substitution, etc.) electrophilic aromatic, 559-577 of 2-halo acids, 343-344 radical mechanisms of 28-32 S,1 with aryl compounds, 617 of saturated hydrocarbons, 26 Succinic acid, acid dissociation constant of, 357 anhydride from, 358, 715 catalyst in aldol addition, 309 formation of, 358, 715 physical properties of, 357 Succinimide, 439 Sucrose, structure of, 408-409 Sugars (see also Monosaccharides, Disaccharide~,Carbohydrates, e t ~ ) ,4 Sulfa drugs, 527 Sulfadiazine, 527, 685 Sulfaguanidine, 527 Sulfate esters, 528 Sulfenic acids, and derivatives, 526 Sulfinic acids, and derivatives, 526 Sulfonation, of arenes, 566 of heterocyclic compounds, 674677 of naphthalene, 575-576 of phenanthrene, 577 Sulfones, 525-526 from thioethers, 524-526 Sulfonic acids, acid strengths of, 527 846 and derivatives, 526 preparation of, 527 Sulfonium salts, formation of, 524 resolution of, 524-525 Sulfonyl chlorides, 527 Sulfoxides, 525-526 from thioethers, 524-526 Sulfur, in catalyst poisoning, 279 electronegativity of, 522 elemental, 519 organic compounds of, 520-528 Sulfur hexafluoride, 517 Sulfur-sulfur bonds, in proteins, 457458 Sulfur tetrafluoride, with cyclopentanone, 290 Sulfur trioxide, in aromatic sulfonation, 567 Sulfuric acid, in ester formation, 253254 esters of, 256-258 Super acids, 13 and carbonium salts, 200 Synthesis, of cyclic ketones, 771 of organic compounds, general considerations, 117-120 overall yields in, 471 of peptides, 470-474 prebiotic, 486 Synthetic fibers (see also Polymers, types of), 2,4,5-T, ecological effect of, 598 Tartaric acid, absolute configuration of, 382 optical isomers of, 377-378 physical properties of, 374 resolution of, 385 as resolving agent, 385 from threose, 379 meso-Tartaric acid, from (-)-erythrose, 379 Taurine, 784 Tautomer, definition of, 315 ' Tautomers, of aniline, 427, 605 of barbaralane, 724 of barbituric acid, 723 of bullvalene, 725 of 1,3,5-cyclooctatriene, 723 of ethyl acetoacetate, 351-352 of hydroxypyridine, 503, 723 of hydroxypyrimidines, 480-48 general index of 2,4-pentanedione, 723 of phenol, 605 valence bond, 723 of vinyl alcohols, 605 of vinylamines, 605 Teflon, 743, 745 properties of, 225 from tetrafluoroethene, 225 Terephthalic esters, polymers from, 747 Terpenes, 778-782 biogenesis of, 789-794 in wood, 41 Testosterone, 791 Tetraborane, 537 1,1,2,2-Tetrabromo-4,4-dimethylpentane, from 4,4-dimethyl-1-pentyne, 113 1,2,5,6-Tetrabromohexane,from 1,shexadiene, 127 Tetra-t-butylmethane, 117 2,3,7,8-Tetrachlorobenzodioxin,teratogenic agent, 598 Tetrachloromethane (see also Carbon tetrachloride), 28 Tetrachlorosilane, physical properties of, 535 Tetracyanoethene, charge-transfer complexes of, 613 as a dienophile, 719 Tetracyanomethane, 117 Tetraethyllead,from ethyl chloride, 234 in gasoline, 58, 234 physical properties of, 234 Tetrafluoroethene, from chloroform, 225 dimerization of, 726 polymer from, 745 polymerization of, 225 Tetrafluoromethane, bond angles in, bonding in, Tetrahedrane, 117 Tetrahydrofuran, peroxides from, 265 properties of, 266 physical properties of, 263 solubility in water, 264 as a solvent, 264 Tetralin, 551 Tetramethylene glycol (see 1,4-Butanediol) Tetramethylene oxide (see Tetrahydrofuran) 847 Tetramethylene sulfone, dielectric constant of, 205 Tetramethylethylene, 81 formation of, 258 2,2,5,5-Tetramethyl-cis-3-hexene (see cis-sym-Di-t-butylethylene) Tetramethyllead, physical properties of, 14 2,2,4,4-Tetramethyl-3-pentanol, 189 Tetramethylsilane, in nmr spectroscopy, 170 physical properties of, 535 Tetranitromethane, 442 N,2,4,6-Tetranitro-N-methylaniline, 611-612 Tetraphenylmethane, physical properties of, 535 Tetraphenylsilane, physical properties of, 535 1,2,4,6-Tetraphenylthiabenzene, 520 Tetraterpenes, 782 Tetrazotization, of diamines, 618 Tetryl (see N,2,4,6-Tetranitro-N-methylaniline) Thalidomide, 440 Thermodynamics, equilibrium constafits, 26-28, 93 free energy of reaction, 26-28 entropy of reaction, 26-28 heat of reaction, 26-28 Thiamine, 685 pyrophosphate, 685 Thiazole, 679 Thietane, 520 Thin-layer chromatography, in amino acid analysis, 467 Thiobenzophenone, 521 Thioesters, from thiols, 523 Thioethers, nucleophilic properties of, 524 preparation of, 524-525 from thiols, 523 Thiols, 521-524 acid strength of, 522 hydrogen bonding in, 522 infrared spectra of, 522 mercury salts of, 522 from organomagnesium compounds, 230-23 oxidation of, 523-524, 527 in paper manufacture, 522 in petroleum, 522 general index 848 preparation, 522 Thionyl chloride, with carboxylic acids, 340 in preparation of alkyl chlorides, 255-256 Thiophene, aromatic character of, 672673 chemical properties of, 673-679 physical properties of, 671 Thiophenol, 520 Thorium oxide, in ketone synthesis, 772 Threonine, configuration of, 384 physical properties of, 459 Threose, oxidation of, 379 projection formulas of, 378 /?-Thujaplicin, 641 Thymine, in DNA, 480 Thyroxine, physical properties of, 461 Titanocene, with nitrogen, 511 TMS (see Tetramethylsilane) Tobacco mosaic virus, properties and function of, 478 Tollen's reagent, 404 Toluene, 550 infrared spectrum of, 554-555 iodination of, 563 nitration of, 562, 568, 606 physical properties of, 553 radical chlorination of, 650 sulfonation of, 566 p-Toluenesulfonic acid, formation of, 566 p-Toluenesulfonyl chloride, in sulfonate ester synthesis, 527 p-Toluic acid, preparation of, 650 o-Toluidine, diazotization of, 591 p-Toluidine, basicity of, 614 nitration of, 608 uv spectrum of, 614 p-Tolyl methyl ketone, oxidation of, 650 Transfer RNA, 485 Transition states, in electrophilic aromatic substitution, 569-571 in SNreactions, 198-200 Triacontane, isomers of, 48 physical properties of, 55 2,4,6-Tribromoaniline, formation of, 616 2,3,3-Tribromo-2-methylpropanoic acid, 191 2,4,6-Tribromophenolformation of, 633 Tri-n-butylamine, base dissociation constant of, 423 physical properties of, 423 Trichloroacetaldehyde, 282 Trichloroacetic acid, acid dissociation constant of, 331, 338 decarboxylation of, 341 physical properties of, 331 Trichloroethane, physical properties of, 535 Trichloroethene, 81 from ethene and ethyne, 223 Trichloromethane (see Chloroform) Trichlorosilane, physical properties of, 535 Triclene, 223 Tricresyl phosphate, as plasticizer, 748 Triethyl phosphate, 530 Triethylamine, base dissociation constant of, 423 physical properties of, 423-424 Triethylborane, from ethene, 96 Triethylene glycol, 264 Trifluoroacetic acid, acid strength of, 331, 337 physical properties of, 331 Trifluoromethylbenzene, nitration of, 568 Triglyme, 264 2,3,4-Trihydroxybutanal, disastereomers of, 378 Triisopropylcarbinol, from isopropyllithium, 234 Triisopropylmethane, 51 Trimethylaluminum, 228 Trimethylamine, physical properties of, 12 Trimethylamine borane, 539 1,3,5-Trimethylbenzene, charge-transfer complexes of, 613 physical properties of, 553 Trimethylborane, 536 2,2,3-Trimethylbutane, naming of, 52 Trimethylene oxide, 266 with organomagnesium compounds, 234 Trimethylenemethyl, n electron systems of, 141-143 resonance structures of, 142 2,2,5-Trimethyl-3-hexyne,naming of, 111 2,2,4-Trimethylpentane, heat of - general index combustion of, 57 in gasoline, 57 octane rating of, 58 Trimethylphospl.iine, basic properties of, 530 Trimethylsilanol, physical properties of, 535 Trimethylsulfonium bromide, 521 1,3,5-Trinitrobenzene, charge-transfer complexes of, 613 preparation of, 606-607 1,3,5-Trinitrobenzoicacid, decarboxylation of, 606-607 2,4,6-Trinitrophenol (see Picric acid) 2,4,6-Trinitrotoluene (TNT), 442, 61 1612 formation of, 562 Trioxymethylene, 288 Triphenylamine, uv spectrum of, 614 Triphenylborane, 539 Triphenylcarbinol, with sulfuric acid, 654 Triphenylmethane, 191 with sodium amide, 654 Triphenylmethyl chloride, physical properties of, 653 Triphenylmethyl peroxide, 655 Triphenylmethyl radical, coupling of, 655 epr spectrum of, 661 resonance hybrid of, 655 Triphosphoric acid, derivatives of, 528 Triplet state, of benzophenone, 705 of oxygen, 705 nature of, 697 Tri-n-propylborane, from propene, 97 Triterpenes, 781-782 Trityl chloride (see Triphenylmethyl chloride) Tropane alkaloids, 684 Tropilidene (see 1,3,5-Cycloheptatriene) Tropolone, acid dissociation constant of, 641 hydrogen bonding in, 642 preparation of, 641 resonance hybrid of, 642 Tropolones, 641-642 complexes with ferric chloride, 642 electrophilic substitution reactions of, 642 849 Tropylium cation, formation of, 642 hybrid structure of, 642 Tryptophan, 682 physical properties of, 461 Tschitchibabin reaction, 678 Twist-boat form, of cyclohexane, 65 Tyrian purple, 760 Tyrosine, physical properties of, 461 Ultraviolet light, absorption of, 160 Ultraviolet spectra (see Electronic absorption spectra) Undecane, physical properties of, 55 a,P-Unsaturated carbonyl compounds (see also Carboxylic acids, unsaturated, Aldehydes, a$-unsaturated, etc.), conjugate addition to, 311, 355 Unsaturated compounds (see Alkenes, Alkynes, Aldehydes, Carboxylic acids, etc.) Uracil, in RNA, 485 Urea, barbituric acid from, 686 heat of combustion of, 51 hydrolysis of, 504 Urease, 504 Valence tautomerization, 723 n-Valeric acid (see Pentanoic acid) y-Valerolactone, formation of, 355 Valine, physical properties of, 459 van der Waals forces, 36, 39, 475, 739 and physical properties, 10 Van Slyke aminonitrogen determination, 463 Vanillin, structure, occurrence and synthesis, 658 van't Hoff, J H., and tetrahedral carbon, 386 Vaseline, from petroleum, 58 Veronal, 685 Vibrational and rotational states, 695 Vinyl acetate, polymer from 746 Vinyl alcohol, acetaldehyde from, 262 polymer from, 746 Vinyl alcohols, derivatives of, in polymerization, 262 tautomers of, 605 general index Vinyl amines, resonance in, 140 tautomers of, 605 Vinyl bromide, 589 Vinyl butyral, polymer from, 746 Vinyl chloride, from ethene, 220 from ethyne, 220 polymers from, 745 Vinyl ethers, bromine addition to, 139 resonance structures in, 139 Vinyl fluoride, from ethyne, 114 polymer from, 745 Vinyl halides, preparation of, 219-220 resonance structures in, 139 in SNreactions, 220 Vinyl polymerization, 753 Vinylacetic acid (see 3-Butenoic acid) Vinylacetylene (see Butenyne) Vinylboranes, alkenes from, 115 from alkynes, 115 Vinylidene halides, polymers from, 743 Viscose rayon, 410 Visible light, absorption of, 160 Vitamin A, 781 Vitamin B, (see Thiamine) Vitamin B6 (see Pyridoxine) Vitamin B,,, D-ribose in, 400 structure of, 681-682 Vitamin C (see Ascorbic acid) Vitamin D, , 790 from ergosterol, 789 Vitamin K,, 640 phytol in, 781 Vitamins, Viton, 225 Vulcanization, 743 Walker, D F., 552 Wallach, O., 778 Water, acid dissociation constant of, - 13, 122 base ionization constant of, 13 bond angles of, 7-8 derivatives of, dielectric constant of, 204 dipole moment of, physical properties of, 10 shape of, Watson, J D., 483 Wave equations, 130 850 Waxes, from petroleum, 58 Whiskey, proof of, 245 Whisky (see Whiskey) Williamson synthesis, 252, 263, 267 Willstatter, R., 681 Wittig reaction, 531 Wohl degradation, 417 Wohler, A., Wolff-Kishner reduction, 292 Wood, cellulose in, 410 con~positionof, 41 Wood alcohol (see Methanol), 245 Woodward, R B., 681, 683, 726 Wool, 757 Wurtz coupling, 654 X-ray diffraction, of boron hydrides, 538 of cholesterol, 787 of glucose, 405 of insulin, 476 of naphthalene, 574 of penicillin G , 468 and structure determination, 4, 159 of vitamin D , 789 m-Xylene, infrared spectrum, 554-555 physical properties of, 553 o-Xylene, infrared spectrum, 554-555 physical properties of, 553 p-Xylene, infrared spectrum of, 554555 physical properties of, 553 Xylenes, 550 D-Xylose, structure of, 400-401 Yields, in organic synthesis, 471 Ylids (see Alkylidene phosphoranes) Ziegler, K., 103 Ziegler catalysts, in polymerization, 744, 753 Ziegler process, in coordination polymerization, 103 Zinc chloride, in alkyl chloride formation, 255 Zwitterions, 462