SIXTH EDITION Organic Chemistry

Robert Thornton Morrison Robert Neilson Boyd New York University

Prentice Hall, Englewood Clzffs,New Jersey 0 7632 Contents

Preface xxiii Acknowledgments xxvii

PART ONE The Fundamentals

l Structure and Properties Organic chemistry 1 The structural theory 3 The chemical bond before 1926 4 Quantum mechanics 5 Atomic orbitals 6 Electronic configuration. Pauli exclusion principle 8 Molecular orbitals 9 The covalent bond 9 Hybrid orbitals: sp l l Hybrid orbitals: sp 13 Hybrid orbitals: sp3 15 Unshared pairs of electrons 17 Intramolecular forces 20 Bond dissociation energy. Homolysis and heterolysis 21 Polarity of bonds 23 Polarity of molecules 23 Structure and physical properties 26 Melting point 2 7 Intermolecular forces 28 Boiling point 30 Solubility 31 vi CONTENTS

1.22 Acids and bases 33 1.23 Isomerism 36

2 Methane Energy of Activation. Transition State Hydrocarbons 39 Structure of methane 40 Physical properties 41 Source 41 Reactions 42 Oxidation. Heat of combustion 42 Chlorination: a substitution reaction 43 Control of chlorination 44 Reaction with other halogens: halogenation 44 Relative reactivity 45 Reaction mechanisms 45 Mechanism of chlorination. Free radicals 46 Chain reactions 48 Inhibitors 49 Heat of reaction 50 Energy of activation 51 Progress of reaction: energy changes 52 Rate of reaction 55 Relative rates of reaction 58 Relative reactivities of halogens toward methane 59 An alternative mechanism for halogenation 61 Structure of the methyl radical. sp2Hybridization 64 Transition state 65 Reactiyity and development of the transition state 67 Chlorofluorocarbons and the ozone shield 69 Molecular formula: its hndamental importance 72 Qualitative elemental analysis 72 . Quantitative elemental analysis: carbon, hydrogen, and halogen 73 Empirical formula 74 Molecular weight. Molecular formula 74

3 Alkanes Free-Radical Substitution Classification by structure: the family 77 Structure of ethane 78 Free rotation about the carbon-carbon single bond. Conformations. Torsional strain 79 Propane and the butanes 83 conformations of n-butane. Van der Waals repulsion 85 Higher alkanes. The homologous series 86 Nomenclature 87 Alkyl groups 88 Common names of alkanes 90 IUPAC names of alkanes 90 CONTENTS vii

Classes of carbon atoms and hydrogen atoms 92 Physical properties 92 Industrial source 94 Industrial source vs. laboratory preparation 96 Preparation 97 The Grignard reagent: an organometallic compound 99

Coupling of alkyl halides with organometallic compounds 101 d Reactions 102 Halogenation 104 Mechanism of halogenation 106 Orientation of halogenation 107 Relative reactivities of alkanes toward halogenation 109 Ease of abstraction of hydrogen atoms. Energy of activation 110 Stability of free radicals l l l Ease of formation of free radicals 113 Transition state for halogenation 113 Orientation and reactivity 114 Reactivity and selectivity 115 Non-rearrangement of free radicals. Isotopic tracers 116 Combustion 118 The greenhouse effect 119 Pyrolysis: cracking 120 Determination of structure 121 Analysis of allcanes 122

4 Stereochemistry I. Stereoisomers Stereochemistry and stereoisomerism 125 Isomer number and tetrahedral carbon 126 Optical activity. Plane-polarized light 128 The polarimeter 128 Specific rotation 129 Enantiomerism: the discovery 130 Enantiomerism and tetrahedral carbon 131 Enantiomerism and optical activity 133 Prediction of enantiomerism. Chirality 133 The chiral center 135 Enantiomers 136 The racemic modification 138 Optical activity: a closer look 139 Configuration 140 Specification of configuration: R and S 140 Sequence rules 141 Diastereomers 144 Meso structures 146 Specification of configuration: more than one chiral center 148 Conformational isomers 149 Reactions involving stereoisomers 150 Generation of a chiral center. Synthesis and optical activity 151 viii CONTENTS

4.23 Reactions of chiral molecules. Bond-breaking 153 4.24 Reactions of chiral molecules. Relating configurations 154 4.25 Optical purity 156 4.26 Reactions of chiral molecules. Generation of a second chiral center 156 4.27 Reactions of chiral molecules with optically active reagents. Resolution 158 4.28 Reactions of chiral molecules. Mechanism of free-radical chlorination 160

5 Alkyl Halides Nucleophilic Aliphatic Substitution Homolytic and heterolytic chemistry 165 Relative rates of competing reactions 166 Structure. The functional group 167 Classification and nomenclature 168 Physical properties 169 Preparation 170 Reactions. Nucleophilic aliphatic substitution 172 Nucleophilic aliphatic substitution. Nucleophiles and leaving groups 175 Rate of reaction: effect of concentration. Kinetics 177 Kinetics of nucleophilic aliphatic substitution. Second-order and first-order reactions 178 Nucleophilic aliphatic substitution: duality of mechanisms 179 The SN2reaction: mechanism and kinetics 181 The &2 reaction: stereochemistry. Inversion of configuration 182 The SN2reaction: reactivity. Steric hindrance 185 The S,1 reaction: mechanism and kinetics. Rate-determining step 188 Carbocations 191 Structure of carbocations 193 The &l reaction: stereochemistry 194 Relative stabilities of carbocations 196 Stabilization of carbocations. Accommodation of charge. Polar effects 199 The &l reaction: reactivity. Ease of formation of carbocations 200 Rearrangement of carbocations 203 &2 vs. &l 208 Analysis of alkyl halides 21 1 I 6 Alcohols and Ethers !l 6.1 Introduction 213 6.2 Structure of alcohols 214 6.3 Classification of alcohols 214 6.4 Nomenclature of alcohols 215 6.5 Physical properties of alcohols 215 CONTENTS

Industrial source 218 Fermentation of carbohydrates 21 9 Fuel from carbohydrates. Carbon dioxide balance 219 Ethanol 221 Preparation of alcohols 222 Reactions of alcohols 224

Alcohols as acids and bases 227 d Reaction of alcohols with hydrogen halides. Acid catalysis 229 Formation of alkyl sulfonates 233 Oxidation of alcohols 235 ETHERS Structure and nomenclature of ethers 237 Physical properties of ethers 238 Industrial sources of ethers. Dehydration of alcohols 238 Preparation of ethers 240 Preparation of ethers. Williamson synthesis 241 Reactions of ethers. Cleavage by acids 242 Analysis of alcohols 243 Analysis of ethers 244

7 Role of the Solvent Secondary Bonding Role of the solvent 249 Secondary bonding 250 Solubility: non-ionic solutes 252 Solubility: ionic solutes. Protic and aprotic solvents. Ion pairs 254 The &l reaction: role of the solvent. Ion-dipole bonds 258 The SN2reaction: role of the solvent. Protic and aprotic solvents 261 The &2 reaction: phase-transfer catalysis 264 &2 vs. & 1: effect of the solvent 26 7 Solvolysis. Nucleophilic assistance by the solvent 268 The medium: a message 271

8 Alkenes I. Structure and Preparation Elimination Unsaturated hydrocarbons 273 Structure of ethylene. The carbon-carbon double bond 273 Propylene 2 76 Hybridization and orbital size 276 The butylenes 277 Geometric isomerism 2 79 Higher alkenes 282 Names of alkenes 282 Physical properties 283 The organic chemistry of vision 285 Industrial source 287 Preparation 287 Dehydrohalogenation of *l halides: 1,2-elimination 290 Kinetics of dehydrohalogenation. Duality of mechanism 293 CONTENTS

The E2 mechanism 294 Evidence for the E2 mechanism. Kinetics and absence of rearrangements 294 Evidence for the E2 mechanism. Isotope effects 295 Evidence for the E2 mechanism. Absence of hydrogen exchange 297 Evidence for the E2 mechanism. The element effect 299 The E2 reaction: orientation and reactivity 300 The El mechanism 303 Evidence for the El mechanism 304 8.23 The El reaction: orientation 306 8.24 Elimination: E2 vs. El 308 8.25 Elimination vs. substitution 308 8.26 Dehydration of alcohols 310

9 Alkenes 11. Reactions of the Carbon-Carbon Double Bond Electrophilic and Free-Radical Addition Reactions of alkenes 31 7 Reactions at the carbon-carbon double bond. Addition 31 7 Hydrogenation. Heat of hydrogenation 323 Heat of hydrogenation and stability of alkenes 326 Addition of hydrogen halides. Markovnikov's rule. Regioselective reactions 327 Addition of hydrogen bromide. Peroxide effect 330 Addition of sulhric acid 331 Addition of water. Hydration 332 Electrophilic addition: mechanism 332 Electrophilic addition: rearrangements 334 Electrophilic addition: orientation and reactivity 335 Addition of halogens 339 Mechanism of addition of halogens 340 Halohydrin formation: addition of the elements of hypohalous acids 342 Addition of alkenes. Dimerization 343 Addition of aIkanes. Alkylation 344 Oxymercuration-demercuration 346 Hydroboration-oxidation 347 Orientation of hydroboration 348 Mechanism of hydroboration 349 Free-radical addition. Mechanism of the peroxide-initiated addition of HBr 351 Orientation of free-radical addition 352 Other free-radical additions 355 Free-radical polymerization of alkenes 356 Hydroxylation. Formation of 1'2-diols 35 7 Cleavage: determination of structure by degradation. Ozonolysis 358 Analysis of alkenes 360 CONTENTS

10 Stereochemistry 11. Stereoselective and Stereospecific Reactions 10.1 Organic chemistry in three dimensions 367 10.2 Stereochemistry of addition of halogens to alkenes. syn- and anti- addition 368 10.3 Mechanism of addition of halogens to allcenes 372 10.4 Stereochemistry ofthe E2 reaction. syn- and anti-elimination 377 10.5 Stereospecific reactions 381 10.6 Stereoselectivity vs. stereospecificity 382 10.7 A look ahead 383 11 Conjugation and Resonance Dienes The carbon-carbon double bond as a substituent 387 Free-radical halogenation of alkenes: substitution vs. addition 388 Free-radical substitution in alkenes: orientation and reactivity 390 Free-radical substitution in alkenes: allylic rearrangement 392 Symmetry of the allyl radical 393 The theory of resonance 394 The allyl radical as a resonance hybrid 395 Stability of the allyl radical 397 Orbital picture of the allyl radical 397 Using the resonance theory 399 Resonance stabilization of alkyl radicals. Hyperconjugation 401 The allyl cation as a resonance hybrid 402 Nucleophilic substitution in allylic substrates: %l. Reactivity. Allylic rearrangement 404 Stabilization of carbocations: the resonance effect 406 Nucleophilic substitution in allylic substrates: ,!&2 407 Nucleophilic substitution in vinylic substrates. Vinylic cations 407 Dienes: structure and properties 409 Stability of conjugated dienes 41 0 Resonance in conjugated dienes 41 1 Resonance in allcenes. Hyperconjugation 413 Ease of formation of conjugated dienes: orientation of elimination 41 4 Electrophilic addition to conjugated dienes. 1,4-Addition 414 1,2- vs. 1,4-Addition. Rate vs. equilibrium 41 7 Free-radical polymerization of dienes. Rubber and rubber substitutes 41 9 Isoprene and the isoprene rule 421 Analysis of dienes 421 12 Alkynes 12.1 Introduction 425 12.2 Structure of acetylene. The carbon-carbon triple bond 425 12.3 Higher alkynes. Nomenclature 428 xii CONTENTS

Physical properties of alkynes 428 Industrial source of acetylene 429 Preparation of alkynes 429 Reactions of alkynes 430 Reduction of alkenes 433 Electrophilic addition to alkynes 434 Hydration of alkynes. Tautomerism 435 Acidity of alkynes. Very weak acids 436 Reactions of metal acetylides. Synthesis of alkynes 438 Formation of carbon-carbon bonds. Role played by organometallic compounds 439 Analysis of alkynes 440

13 Cyclic Aliphatic Compounds Open-chain and cyclic compounds 443 Nomenclature 443 Industrial source 444 Preparation 447 Reactions 448 Reactions of small-ring compounds. Cyclopropane and cyclobutane 449 Baeyer strain theory 450 Heats of combustion and relative stabilities of the cycloalkanes 450 Orbital picture of angle strain . 453 Factors affecting stability of conformations 454 Conformations of cycloalkanes 455 Equatorial and axial bonds in cyclohexane 460 Stereoisomerism of cyclic compounds:.cis and trans isomers 463 Stereoisomerism of cyclic compounds. Confonnational analysis 466 Stereochemistry of elimination from alicyclic compounds 471 Carbenes. Methylene. Cycloaddition 473 Addition of substituted carbenes. l, l-Elimination 476 Cyclic ethers 478 Crown ethers. Host-guest relationship 478 Epoxides. Structure and preparation 481 Reactions of epoxides 482 Acid-catalyzed cleavage of epoxides. anti-Hydroxylation 483 Base-catalyzed cleavage of epoxides 485 Orientation of cleavage of epoxides 485 Analysis of alicyclic compounds 487

14 Aromaticity Benzene 14.1 Aliphatic and aromatic compounds 493 14.2 Structure of benzene 494 14.3 Molecular formula. Isomer number. KekulC structure 494 14.4 Stability of the benzene ring. Reactions of benzene 497 CONTENTS xiii

Stability of the benzene ring. Heats of hydrogenation and combustion 498 Carbon-carbon bond lengths in benzene 499 Resonance structure of benzene 500 Orbital picture of benzene 501 Representation of the benzene ring 503 Aromatic character. The Hiickel4n + 2 rule 504 Nomenclature of benzene derivatives 508 Polynuclear aromatic hydrocarbons. Naphthalene 510 Quantitative elemental analysis: nitrogen and sulfur 51 3

15 Electrophilic Aromatic Substitution Introduction 51 7 Effect of substituent groups 5 19 Determination of orientation 520 Determination of relative reactivity 521 Classification of substituent groups 522 Orientation in disubstituted benzenes 522 Orientation and synthesis 524 Mechanism of nitration 525 Mechanism of sulfonation 527 Mechanism of Friedel-Crafts allcylation 528 Mechanism of halogenation 529 Desulfonation. Mechanism of protonation 529 Mechanism of electrophilic aromatic substitution: a summary 530 Mechanism of electrophilic aromatic substitution: the two steps 531 Reactivity and orientation 535 Theory of reactivity 536 Theory of orientation 538 Electron release via resonance 540 Effect of halogen on electrophilic aromatic substitution 542 Relation to other carbocation reactions 544 Electrophilic substitution in naphthalene 545

16 Aromatic-Aliphatic Compounds Arenes and Their Derivatives The aromatic ring as a substituent 549 Aromatic-aliphatic hydrocarbons: arenes 549 Structure and nomenclature of arenes and their derivatives 551 Physical properties 552 Industrial source of alkylbenzenes 555 Preparation of alkylbenzenes 556 Friedel-Crafts alkylation 55 7 Mechanism of Friedel-Crafts alkylation 558 Limitations of Friedel-Crafts alkylation 561 Reactions of alkylbenzenes 561 xiv CONTENTS

Oxidation of alkylbenzenes 563 Electrophilic aromatic substitution in alkylbenzenes 564 Halogenation of alkylbenzenes: ring us. side chain 565 Side-chain halogenation of alkylbenzenes 566 Resonance stabilization of the benzyl radical 568 Triphenylmethyl: a stable free radical 570 , Stability of the benzyl cation 574 Nucleophilic substitution in benzylic substrates 575 Preparation of alkenylbenzenes. Conjugation with the ring 576 Reactions of alkenylbenzenes 578 Addition to conjugated alkenylbenzenes 579 Alkynylbenzenes 580 Analysis of arenes 580

17 Spectroscopy and Structure Determination of structure: spectroscopic methods 585 The mass spectrum 586 The electromagnetic spectrum 589 The infrared spectrum 590 Infrared spectra of hydrocarbons 592 Infrared spectra of alcohols 594 Infrared spectra of ethers 596 The ultraviolet spectrum 597 The nuclear magnetic resonance (NMR) spectrum 600 NMR. Number of signals. Equivalent and non-equivalent protons 601 NMR. Positions of signals. Chemical shift 604 NMR. Peak area and proton counting 609 NMR. Splitting of signals. Spin-spin coupling 610 NMR. Coupling constants 620 . NMR. Complicated spectra. Deuterium labeling 623 Equivalence of protons: a closer look 625 Carbon- 13 NMR (CMR) spectroscopy 629 CMR. Splitting 630 CMR. Chemical shift 634 NMR and CMR spectra of hydrocarbons 639 NMR and CMR spectra of alkyl halides 640 NMR and CMR spectra of alcohols and ethers. Hydrogen bonding. Proton exchange 640 The electron spin resonance (ESR) spectrum 642

18 Aldehydes and Ketones Nucleophilic Addition 18.1 Structure 657 18.2 Nomenclature 658 18.3 Physical properties 660 18.4 Preparation 661 18.5 Preparation of ketones by Friedel-Crafts acylation 666 18.6 Preparation of ketones by use of organocopper compounds 668 CONTENTS

Reactions. Nucleophilic addition 669 Oxidation 675 Reduction 677 Addition of cyanide 678 Addition of derivatives of ammonia 679 Addition of alcohols. Acetal formation 680 Cannizzaro reaction 683 Addition of Grignard reagents 685 Products of the Grignard synthesis 686 Planning a Grignard synthesis 688 Syntheses using alcohols 692 Limitations of the Grignard synthesis 695 Tetrahydropyranyl (THP) ethers: the use of a protecting group 696 Analysis of aldehydes and ketones 697 Iodoform test 697 Analysis of 1,2-diols. Periodic acid oxidation 699 Spectroscopic analysis of aldehydes and ketones 700

19 Carboxylic Acids Structure 713 Nomenclature 714 Physical properties 717 Salts of carboxylic acids 718 Industrial source 719 Preparation 720 Grignard synthesis 723 Nitrile synthesis 724 Reactions 725 Ionization of carboxylic acids. Acidity constant 729 Equilibrium 730 Acidity of carboxylic acids 732 Structure of carboxylate ions 733 Effect of substituents on acidity 735 Conversion into acid chlorides 737 Conversion into esters 737 Conversion into amides 740 Reduction of acids to alcohols 740 Halogenation of aliphatic acids. Substituted acids 741 Dicarboxylic acids 742 Analysis of carboxylic acids. Neutralization equivalent 744 Spectroscopic analysis of carboxylic acids 745

20 Functional Derivatives of Carboxylic Acids Nucleophilic Acyl Substitution 20.1 Structure 753 20.2 Nomenclature 754 20.3 Physical properties 754 xvi CONTENTS

Nucleophilic acyl substitution. Role of the carbonyl group 755 Nucleophilic substitution: alkyl vs. acyl 759 ACID CHLORIDES Preparation of acid chlorides 760 Reactions of acid chlorides 761

Conversion of acid chlorides into acid derivatives 762 A ACID ANHYDRIDES , Preparation of acid anhydrides 763 Reactions of acid anhydrides 764 AMIDES Preparation of amides 766 Reactions of amides 766 Hydrolysis of amides 767 Imides 767 ESTERS Preparation of esters 768 Reactions of esters 770 Alkaline hydrolysis of esters 773 Acidic hydrolysis of esters 776 Ammonolysis of esters 778 Transesterification 778 Reaction of esters with Grignard reagents 779 Reduction of esters 780 Functional derivatives of carbonic acid 780 Analysis of carboxylic acid derivatives. Saponification equivalent 784 Spectroscopic analysis of carboxylic acid derivatives 785

21 Carbanions I Aldol and Claisen Condensations Acidity of a-hydrogens 797 Reactions involving carbanions 799 . Base-promoted halogenation of ketones 802 Acid-catalyzed halogenation of ketones. Enolization 804 Aldol condensation 805 Dehydration of aldol products 807 Use of aldol condensation in synthesis 808 Crossed aldol condensation 809 Reactions related to the aldol condensation 8 10 The Wittig reaction 81 1 Claisen condensation. Formation of p-keto esters 813 Crossed Claisen condensation 81 6

22 Amines I. Preparation and Physical Properties 22.1 Structure 821 22.2 Classification 821 22.3 Nomenclature 822 22.4 Physical properties of arnines 823 22.5 Salts of amines 823 CONTENTS xvii l

Stereochemistry of nitrogen 825 Industrial source 827 Preparation 828 Reduction of nitro compounds 832 Ammonolysis of halides 832 Reductive amination 834 Hofmann degradation of amides 836 Synthesis of secondary and tertiary amines 836 Heterocyclic amines 837 Hofmann rearrangement. Migration to electron-deficient nitrogen 838 Hofinann rearrangement. Stereochemistry at the migrating group 840 Hofmann rearrangement. Timing of the steps 841 1 23 Amines 11. Reactions Reactions 845 Basicity of amines. Basicity constant 849 Structure and basicity 850 Effect of substituents on basicity of aromatic amines 853 Quaternary ammonium salts. Hofmann elimination 854 E2 elimination: Hofmann orientation. The variable E2 transition state 855 Conversion of amines into substituted amides 857 Ring substitution in aromatic amines 860 Sulfonation of aromatic amines. Dipolar ions 862 Sulfanilamide. The sulfa drugs 863 Reactions of arnines with nitrous acid 864 Diazonium salts. Preparation and reactions 866 Diazonium salts. Replacement by halogen. Sandmeyer reaction 869 Diazonium salts. Replacement by -CN. Synthesis of carboxylic acids 870 Diazonium salts. Replacement by -OH. Synthesis of phenols 870 Diazonium salts. Replacement by -H 871 Syntheses using diazonium salts 871 Coupling of diazonium salts. Synthesis of azo compounds 873 Analysis of amines. Hinsberg test 876 Analysis of substituted amides 877 Spectroscopic analysis of amines and substituted amides 877 I 24 Phenols 24.1 Structure and nomenclature 889 24.2 Physical properties 890 24.3 Salts of phenols 893 24.4 Industrial source 893 24.5 Rearrangement of hydroperoxides. Migration to electron- deficient oxygen 895 xviii CONTENTS

Rearrangement of hydroperoxides. Migratory aptitude 896 Preparation 898 Reactions 899 Acidity of phenols 903 Ester formation. Fries rearrangement 905 , V Ring substitution 906 Kolbe reaction. Synthesis of phenolic acids 908 Reimer-Tiemann reaction. Synthesis of phenolic aldehydes. Dichlorocarbene 908 Formation of aryl ethers 909 Reactions of aryl ethers 91 1 Analysis of phenols 912 Spectroscopic analysis of phenols 912

25 Carbanions I1 Malonic Ester and Acetoacetic Ester Syntheses Carbanions in organic synthesis 923 Malonic ester synthesis of carboxylic acids 924 Acetoacetic ester synthesis of ketones 927 Decarboxylation of p-keto acids and malonic acids 930 Direct and indirect alkylation of esters and ketones 931 Synthesis of acids and esters via 2-oxazolines 932 Organoborane synthesis of acids and ketones 933 Alkylation of carbonyl compounds via enamines 935

PART TWO Special Topics

26 Aryl Halides Nucleophilic Aromatic Substitution Structure 943 Physical properties 944 Preparation 946 Reactions 948 Low reactivity of aryl and vinyl halides 949 Structure of aryl and vinyl halides 950 Nucleophilic aromatic substitution: bimolecular displacement 952 Bimolecular displacement mechanism for nucleophilic aromatic substitution 955 Reactivity in nucleophilic aromatic substitution 956 Orientation in nucleophilic aromatic substitution 957 Electron withdrawal by resonance 958 Evidence for the two steps in bimolecular displacement 959 Nucleophilic substitution: aliphatic and aromatic 961 Elimination-addition mechanism for nucleophilic aromatic substitution. Benzyne 962 Analysis of aryl halides 967 CONTENTS xix

27 &,B-Unsaturated Carbonyl Compounds Conjugate Addition Structure and properties 971 Preparation 973 Interaction of functional groups 974 Electrophilic addition 974

Nucleophilic addition 9 76 , d Comparison of nucleophilic and electrophilic addition 978 The Michael addition 979 The Diels-Alder reaction 982 Quinones 984

Molecular Orbitals. Orbital Symmetry Molecular orbital theory 991 Wave equations. Phase 992 Molecular orbitals. LCAO method 993 Bonding and antibonding orbitals 994 Electronic configurations of some molecules 996 Aromatic character. The Hiickel4n + 2 rule 1000 Orbital symmetry and the chemical reaction 1004 Electrocyclic reactions 1005 Cycloaddition reactions 1013 Sigmatropic reactions 1019

29 Symphoria Neighboring Group Effects. Catalysis by Transition Metal Complexes 29.1 Symphoria 1031 29.2 Neighboring group effects: the discovery. Stereochemistry 1032 29.3 Neighboring group effects: intramolecular nucleophilic attack 1035 29.4 Neighboring group effects: rate of reaction. Anchimeric assistance 1037 29.5 Homogeneous hydrogenation. Transition metal complexes 1042 29.6 Stereochemistry of homogeneous hydrogenation: diastereoselectivity 1046 29.7 Stereochemistry of homogeneous hydrogenation: enantioselectivity 1049 29.8 The 0x0 process 1052 29.9 Enzyme action 1054

30 Heterocyclic Compounds - 30.1 Heterocyclic systems 105 7 FIVE-MEMBERED RINGS 30.2 Structure of pyrrole, furan, and thiophene 1059 30.3 Source of pyrrole, furan, and thiophene 1061 30.4 Electrophilic substitution in pyrrole, furan, and thiophene. Reactivity and orientation 1062 xx CONTENTS

Saturated five-membered heterocycles 1065 SIX-MEMBERED RINGS Structure of pyridine 1066 Source of pyridine compounds 10&7

Reactions of pyridine 1068 , l Electrophilic substitution in pyridine 1068 Nucleophilic substitution in pyridine 1069 Basicity of pyridine 10 71 Reduction of pyridine l073

31 Macromolecules. Polymers and Polymerization Macromolecules 10 77 Polymers and polymerization 1078 Free-radical vinyl polymerization 1080 Copolymerization 1083 Ionic polymerization. Living polymers 1084 Coordination polymerization 1087 Step-reaction polymerization 1090 Structure and properties of macromolecules 1093

32 Stereochemistry 111. Enantiotopic and Diastereotopic Ligands and Faces 32.1 Introduction 1101 32.2 Biological oxidation and reduction. Ethanol and acetaldehyde l l01 32.3 Biological oxidation and reduction. Deuterium labeling experiments 1103 32.4 Biological oxidation and reduction. Stereochemistry 1104 32.5 Enantiotopic and diastereotopic ligands 1107 32.6 Enantiotopic and diastereotopic faces 11l0 32.7 Origin of enantiospecificity 1112

PART THREE - Biomolecules

33 Lipids Fats and Steroids The organic chemistry of biomolecules 1119 Lipids 1120 Occurrence and composition of fats 1120 Hydrolysis of fats. Soap. Micelles 1124 Fats as sources of pure acids and alcohols 1125 Detergents 1126 Unsaturated fats. Hardening of oils. Drying oils 1127 Phosphoglycerides. Phosphate esters 1128 Phospholipids and cell membranes 1130 CONTENTS xxi

33.10 Biosynthesis of fatty acids 1132 33.1 1 Steroids 1134

34 Carbohydrates I. Monosaccharides Introduction 1143 Definition and classification 1144 (+)-Glucose: an aldohexose 1144 (->Fructose: a 2-ketohexose 1146 Stereoisomers of (+)-glucose. Nomenclature of aldose derivatives 1146 Oxidation. Effect of alkali 1149 Osazone formation. Epimers l151 Lengthening the carbon chain of aldoses. The Kiliani-Fischer synthesis 1152 Shortening the carbon chain of aldoses. The RUE degradation 1 154 Conversion of an aldose into its epimer 1154 Configuration of (+)-glucose. The Fischer proof 1155 Configurations of aldoses 1160 Optical families. D and L 1162 Tartaric acid 1164 Families of aldoses. Absolute configuration 1166 Cyclic structure of D-(+)-glucose. Formation of glucosides 1168 Configuration about C- l 11 73 Methylation 11 74 Determination of ring size 11 76 Conformation 11 78

35 Carbohydrates 11. Disaccharides and Polysaccharides Disaccharides 1185 (+)-Maltose 1185 (+)-Cellobiose 1188 (+)-Lactose 1 189 (+)-Sucrose 1191 Polysaccharides 1192 Starch 1193 Structure of amylose. End group analysis 1193 Structure of amylopectin 1195 Cyclodextrins 1198 Structure of cellulose 1200 Reactions of cellulose 1200

36 Proteins and Nucleic Acids Molecular Biology 36.1 Proteins 1205 36.2 Structure of amino acids 1206 36.3 Amino acids as dipolar ions 1208 36.4 Isoelectric point of amino acids 1211 xxii CONTENTS

Configuration of natural amino acids 1212 Preparation of amino acids 1213 Reactions of amino acids 1215 Peptides. Geometry of the peptide linkage 1215 Determination of structure of peptides. Terminal residue, analysis. Partial hydrolysis 1217 Synthesis of peptides 1221 Proteins. Classification and function. Denaturation 1225 Structure of proteins 1226 Peptide chain 1226 Side chains. Isoelectric point. Electrophoresis 1227 Conjugated proteins. Prosthetic groups. Coenzymes 1228 Secondary structure of proteins 1229 Biochemistry, molecular biology, and organic chemistry 1235 l i Mechanism of enzyme action. Chymotrypsin 1236 l Nucleoproteins and nucleic acids 1241 1 Chemistry and heredity. The genetic code 1246 l l Suggested Readings 1251 Answers to Problems 1263 Index 1279 Index

Acetonitrile (ethanenitrile), 258, 725 Acetonylacetone, 930, 1062 )solute alcohol, 221 Acetophenone (methyl phenyl ketone), 546,557, )solute configuration, 155,183,1165,1166- 1168 581,660, t661 )solute ether, 240 infrared sDectrum. 700 xtraction of hydrogen, 60,66,566-567,805,838 preparation, 664 ' relative rates, 107 - 109 reactions, 672,801,808,835,935 :cornmodation of charge, 208,209 Acetophenoneoxime, 844 ztal, 674 (See also Acetals) Aceto-o-toluiede, 858 xtaldehyde, 247,659, t661,670, 11 14 Aceto-ptolui&de, 858 enzymatic reduction of, 11 12 - 11 13 preparation, 861 preparation, 432,435,661 reactions, 86 1,872 reactions, 673-674,687,800-801,805-808, Acetoxonium ions, 1040 830,988, 1102- 1103, 1214 o-Acetoxybenzoic acid (aspirin), 9 14 xtaldehyde diethyl acetal, 674 2-a-Acetoxycholestane-3-one,NMR spectrum, 623 xtaldoxune, 673 2-Acetoxycyclohexyl tosylate, 1039, 1040 :etals, 696 (+)-trans-2-Acetoxycyclohexyltosylate, 1040 formation of, 680-683, 1170,1174 NMR spectrum, 820 reactions, 674, 1175 - 1176 preparabon, 8 16 :etamide, 754, t755,757,764,77!, 778, 860 Acetylalanine, 1050 Acetarmdobenzenesulfonylchloride, 863 Acetylation Acetamidopropenoic acid, 1050, 11 13 of amines, 858 :etanilide. 546. 858.861 of cellulose, 1201 preparation, 848 ' Acetyl chloride, 754, t755,757 reactions, f520,522,863,947. . preparation, 726 xtate rayon, 1201 Acetylcholine, 882 :etic acid, 226,258,680,705,713, t715,725- Acetyl COA, 1132-1133, 1139 727,739,754,764,765,768,778,829,859,925 Acetyl CoA carboxylase, 1133 industrial preparation, 7 19 Acetylene, 43, t429 model-- -- - of.- - , 714 as acid, 436-438 reactions, 829 analysis, t607 substituted, synthesis of, 925 industrial source, 43,429 uses, 764 reactions, 38,432-433,435,438, 1181 xtic anhydride (ethanoic anhydride), 754, t755, structure, 276,425 -427 757 2-Acetylfuran, 1063 pr&kation, 763 Acetylides, 429-430,433,438 reactions, 664,764,765,769,859,900 Acetyl-S-ACP, 11 33 cetoacetic aad, 93 1 Acetylsalicylic acid (aspirin), 9 14 cetoacetic ester, 814-815,930,939 Acetylurea, 783 preparauon, 8 13- 8 15 Aad anhydrides, 753,763-766 reactions. 927-930 addition to aldehydes, 81 1 (See also'~th~1acetoacetate) conversion cetoacetic ester synthesis, 924,927-930 into acids and derivatives, 764 cetoacetvl-S-ACP. 1133 into amides, 764 :etobactir, 719 ' cyclic anhydrides, 765 cetolysis, 1039 - 1041 physical properties, 754-755, t755 cetone, 258,659, t661,670,673,688 preparation, 763 preparation, 432 reactions, 764-766,769,783,811 reactions, 436,687,690-692,704,705,800- structure, 753 806.816.829.990 Acid-base catalysis, 1239- 1240 substitutkd. svnthesis of. 928 Acid-base properties, used for separation, 7 18- 7 19 cetone cyanoliydrin, 673 Acid catalysis, 175,229-233, 771 Acid chlorides Alcohols

Acid chlorides, 753,760-763 by benzyl chlorocarbonate, 1222 aromatic vs. aliphatic, 762 Friedel-Crafts, see Friedel-Crafts acylation carboxylic acid Acyl azides. 839 spectroscop~canalysis, 784-785, t786 Acjll carrier protein (ACP), 1133 structure, 753 Acyl compounds conversion of nomenclature, 753 -754 into acids and derivatives, 760,761,762,769 nucleophilic substitution, 755 - 760 into amides, 76 1, 857- 860 structure, 753 into esters, 761, 769 Acyl group, 728,753 Friedel-Crafts acylation, 663,666-667,761 compared wth allcyl group, 759 -760 with organocopper compounds, 664,668 - compared with phosphate group, 1129 669.762 ---a compared with sulfonyl group, 860 ketone formation, 663,761 -762 nucleophilic substitution, 666, 755-760 with orpnocopper compounds, 762 Acylium ions, 666,905 nucleophllic substitution, 760 Adamantane, 445 physical properties, t755 Addition polymerization, 1079 ~reuaration.760 Addition reactions - fiom carboxylic acids, 665,726,737 1,4-, 414-419 reactiqns, 760-762,783 vs. 1,2-addition, 417-419 redumon, 662 - 663 of aldehydes and ketones, 671 -684 spectroscopic analysis, 784-785, t786 of alkenes, 317-365 structure, 753 of alkenylbenzenes, 577 ~.ulfonicacid, 857 of alkynes, 430-433,435 Aadity, 33-35 of conjugated dienes, 414-41 7 alcohols, 227 - 229 of cycloallcanes, 448 alkynes, 436-438 of cyclopropane, 449 - 450 amides. 766. 859 defimhon, 3 18 carboxylic a'ci&, 718,725,732-736 of halogens to alkenes, mechanism, 368-372 dicarboxylic acids, t742,742 - 744 stereochemistry, 372- 377 hydrocarbons, 436-438, 1071- 1072 syn- and anti-, 368-372, 1047- 1048 g-hydrogen, 797-799,8 14-815,924,930, 1070 to a$-unsaturated carbonyl compounds, 974- ~mides,768 984 8-keto esters, 8 13-81 5.930 (See also Electrophilic addition; Free-radical ad- malonic ester, 924 . dition; Nucleophilic addition) phenols, 843,874-875,903-905 Adenine, 1182,1229, 1241 - 1243 phosphates, 1128 - 1129 -thymine, hydrogen bonding in, 1245 and rate of reaction, 680, 874, 1238 Adenosine. 1183.1241 relative series of, 34, 35, 38,228,437, 575, 729, ~denosinitriphdsphate(ATP), 1128 1146 Adenylic acid, 1182 sulfonamides, 860 Adipaldehyde, 844,9 17 sulfomc ac~ds,233,860 Adipic acid (hexanedioic acid), 489,742, t742, Acidity constants, 729 763,880, 1090 amjdes, 768 estenficabon. 738 amno aads, 1208- 12 11 preparation, 927 ammonia, 768 Adi~onitrile.830 benzamide, 768 (-)--Adrenalhe, 137,9 17 carboxylic acids, 729, t735 Adrenocorticotropic honnone (ACTH), dicarboxylic acids, t742 Agar, 1203 imides, 768 AIBN, 1082 phenols, 843, t890 Alanine, 144, 1209, 1223 phthalimide, 768 preparation, 1050,,833, 1213 substituted benzoic acids, t735 Strecker synthesis, 12 14 sulfonamides, 860 (+)-Alanine. t l206 Acids hbumin, l226 cleavage of ethers by, 242-243 Alcohol dehydrogenase, 1102 Lewis, definition, 34 A~co~o~s,2 13-247 Lowry-Brransted, definition, 33 as acids and bases, 227-229 and molecular structure, 35 addition to aldehydes and ketones, 674,680-683 (See also Acidity; Amino acids, Carboxylic aldehydes from, 226,235-237,662 acids, Fatty acids; Sulfonic acids) akyl halides from, 170, 17 1 Aconitic acid, 988 akyl sulfonates from, 234 ACP, 1133 analysis of, 243 - 244 Acrilan, 1094 iodoform test, 244 Acrolein, e72, 973 Lucas test 244 preparabon, 974 periodic akd oxidation, 699 reactions, 683,975,983 spectroscopic, 594-595 Acrylic acid, 713,750, 1972,973 carbocations from, 559 hydration, 975 carboxylif:acids from, 226,235-237 Acryloid, 973 cl-ficabon, 214-215 Acrylonitde, 1972,973 dehydration industrial preparation, 973 to alkenes, 225,288,289,306,310,313-315 reactions, 978, 988, 1080, 1083 to ethers, 552 ACTH, 1216, 1226 detergents from, 1126 Activating groups, 52 1- 522,537 - 540 estefication, 226,239, 726, 737-739,769-770 Activation energy, 5 1-52, tl l l, 324 ethyl, see Ethanol, Ethyl alcohol and reamon rate, 56 Grignard synthesis of, 685-692 and the transition state, 67-69,579 heterolytic bond dissociation energies, t22 Acylabon, 666 hydrogen bonding, 217-218 of amines, 858 industrial source, 21 8-221, 1089 ; Alkanes

:tones from, 236-237 preparation, 808 S%, 221 reduction, 808 -809 omenclature, 2 15 - 2 18 a,D-unsaturated, 978 (See also a,jhUnsatu- rder of reactivity of, 3 13, 306 rated carbonyl compounds) xidation, 226,235-237,694,699, 1101- 1106 vs. ketones, 657,697 hysical properties, 2 15 - 2 18, t2 16 Witti reaction, 801, 811-813 reparation, 222-223 ~olk~ishnerreduction, 672,677 aldol condensation, 808 - 809 Alditols, t 1149 Grignard synthesis, 222,685 -692,779 Aldohexoses hydroboration-oxidation, 222,321,347- 348 anomers, 1170, 1173 hydrolysis of halides, 222 configurations, 1155-1160, 1173-1174 oxymercuration-demercuration, 222,32 1, conformations, 1178 - 1180 346-347 conversion to epimers, 11 54 - 11 55 reduction of carboxylic acids, 727,740 cvclicstructure. 1168-1172 reduction of esters, 779 definition of, 1i44 reduction of fats, 1125- 1126 denvatives, nomenclature, t1149 rotonated, 176 (+)-glucose as, 1144- 1146 actions, 224-227 Kiliani-Fischer synthesis, 1152 - 1154 as acids, 225,228 ring size, 1176 with active metals, 225 Ruff degradation, 1154 with hydrogen halides, 170,224,229-233 (See also Aldoses; D<+)-Glucose) with phosphorus trihalides, 170, 17 1,225 Aldol :activity, 224-227,,726,769 preparation, 805 wth hydrogen hahdes, 224,230 reactions, 807-809 :solution, 160,766 Aldol condensation, 800- 801,805 -807,973 ~lubiityin water, 217-218, 238,1253 acid-catalyzed, 8 18 S solutes, 2 17,252 -253 crossed, 809- 8 10 S solvents, 217,255,256-257 related reactions, 8 10 - 8 11 xctroscopic analysis, t592,594-595,1607, t786 use in synthesis, 808 -809 mcture of, 2 14 Aldonic acids, t1149, 1150, 1154- 1155 se in synthesis, 692-694 Aldopentoses oholyis configurations, 1156- 1158, 1160- 1162 f acid anhydrides, 765 in Kiliani-Fischer synthesis, 1153 f acid chlorides, 761 from Ruff degradation, 1154 festers, 77 1-772,778-779 aric acids, t1149, 1150 Aldoses ehydes, 235,237,359,440,657-712, 1102- carbon-chain lengthening, 1152 - 1154 1103 carbon-chain shortening, 1154 ddition configurations, 115 1- 1152, 1160- 1162 of alcohols, 674,680-683 cyclicstructure, 1168-1172 of aldehydes and ketones, 805 - 8 11 definition, l l44 of ammonia derivatives, 673,679-680,697 derivatives, nomenclature, 1146- 1 149, t1149 of carbanions, 675 effect of alkali, 1150 of cyanide, 673,678-679 epimers, conversion into, 1154- 1155 of derivatives of ammonia, 673,679-680,697 families, 1166- 1168 of Grignard reagent, 124,222,675,686-687 Kiliani-Fischer,synthesis, 1152- 1154

Idol.-.- condensabon.~ ~ 800-801.805 -807 osazone fornabon. 115 1 - 1152 related reactions.' 8 10-8 11 ' oxidation, 1149- 1'150 li$hatic, preparation, 662,665 Ruff degradation, 1154 nalysis, 671,673,675-677,679,697-698 (See also Aldohexoses; D<+)-Glucose) romatic, prepqtion, 662,665 Alenic acid, 1203 :annizzaro reamon, 674,683 -684 Ahcyclic hydrocarbons, see Cyclic aliphatic corn- crossed, 674,683-684 pounds, Cycloalkanes lemmensen reduction, 672,677 Aliphatic compounds, see Alkanes, Alkenes, Al- xmation, 762 W? hoevenagel reaction, 927,s 10 - 8 11 defimaon. 493 omenclatyre, 658 -660 Aliphatic cyclic hydrocarbons, see Cyclic aliphatic ucleopbhc addbon, 669 -671,673 -675 compounds xidation. 671.676-677.697 Aliphatic hydrocarbon, see Alkanes, Alkenes, Al- kynes, Cyclic aliphatic compounds, Dienes henolic, 663 Aliphatic hydroperoxides, 898 hysical ,properties, 660-661, t661 Alizarin, 1202 reparabon, 66 l-663,665 Alkaloids, 75,159,164,918,1059,1066,1073, oxidation of alcohols, 235-237,662 1140 oxidation of methylbenzenes, 662,665 piperidine ring in, 1073 ozonolysis, 358-360 pyridine ring in, 1073 reduction of acid chlorides, 662-663 pyrrolidine rin in, 1066 Reimer-Tiemann reaction, 663,902,908 -909 in resolution of racemic acids, 159 xctions, 669-675,686-687,704 Alkanes, 39,77- 124 summary, 800- 802 addition to alkenes, 321,344-345 eduction, 677-678 analysis, 122, t592, 593-594, t607 to alcohols, 672,677-678 bond dissociation energies, 22 1, t22, 11 1 - 112 to hydrocarbons, 672,677 chlorination of, 104 - 118 eductive amination, 829-830,832,834-835 classification by structure, 77 pectroscopic analysis, t592, t607,700-701,2786 combustion, 103, 118 - 119 tructure. 657-658 common names, 90 &t for, 697 general formula, 87 lnsaturated halogenation, 104- 118, 160- 162 oxidation of. 676 mechanism of, 106-107, 116-118 1282 Alkenes B-*l-9.

Alkanes, (cont.) free-radical substitution, 390 orientation in, 107- 109 geometric isomerism in, 278- 280 relative reactivities, 109 - 11 1 halogenation, 323,388-392 homologous series, 86 - 87 higher, 282 industrial source, 94 - 96, 1 19 hydration, 218,320,332 vs. laboratory preparation, 96 - 97 hydrogenation, 3 19,323 -327 isomeric structures, 83 - 87 heats of, t326 isomerism, 89 - 90 hydroxylation, 223,323,357-358,484 IUPAC names, 90 - 92 stereochemistry,484 methylene insertion into, 476 hyperconjugation, 41 3 nomenclature, 87- 92, t88 industrial source, 119,287, 1089 physical properties, 92-94, t93, 122 nomenclature, 282-283 preparahon. 97 - 102 ozonolysis, 323, 358-360 - by coupling of alkyl halides with organometal- physical properties, 283-285, t285 lic compounds. 98 - 99. 10 1 - 102- .- polymerization, see Polymerization . by hydrogeliation of alkenk, 98 preparation, 246,288-290,310-315 by hydrolysis of Grignard reagent, 98,99- 101 dehalogenation of vicinal dihalides, 289 385 by redudon of alkyl halides, 98,99 - 10 1 dehydration of alcohols, 288,289,3 1013 15 by Wurtz rea&on, 102 dehydrohalogenation of alkyl halides, 288, ~~nfi~ation.332 289,290-293 ~Y~OIYSS,96,-io3,1 20 - 12 1 Hofmann elimination, 854-855 reactions, summary, 103 reduction of alkynes, 289,43 1,433 -434 reactivity, 103 Wittig reaction, 8 1 1- 8 13 solubility, 94 readons, 3 17 - 365 spectroscopic analysis, 122, t592, 593-594, t607 relative reactivity toward acids, 338 structure, determination of, 121 - 122 resonance in. 413 uses, 96 spectroscopic analysis, t592 599,592- Alkenes, 246,273-316,409-410 stability, 301,326-327.41j addition reactions, 3 19 - 32 1 structure, 273-283 ' of alkanes, 32 1,344-345 substitution reactions, 323,388 -390 anti-Markovnikov, 3 19,32 1,330 substitution vs. addition, 388 - 390 of bromine azide, 384,487 (See also Alkenylbenzenes; Dienes) of carbenes, 476-478 Alkenvlbenzenes character, 302,307 conjugated, 579- 580 dimerization, 320,343 -344 preparation, 576 -578 electrophilc, 3 18,332 - 344 reactions. 578 - 580 free-radical, 390 ring-halogenated, 578 of halogens, 319,339-342,372-376 (See also Arenes) halohydrin formation, 320,342,384 Alkoxides, 227,228,241 of halogens, 313,339-342,372-376 Alkoxymercuration-demercuration, 24 1 halohydrin formation, 320,342,384 Alkyd resins, 1090 hydration, 218,320,332 Alkyl acetates, rates of reaction, 776 hydroboration-oxidation, 222,321,347-348 Alkylacetoacetic esters, 927 hydrogenation, 3 19,323 - 327 Alkyl aryl ethers, 240 of hydrogen bromide, 319,329,351 -352 cleavaee. 242 -243 of hydrogen chloride, 327-329,329 Williamson synthesis, 902 of hydrogen halides, 3 19,327 - 329 Alkylation of hydrogen iodide, 3 19,328-329 of alkanes, 120 hydroxylation, 223,323,357-358,484 of alkenes, 321,344- 345 of iodine .zide, 384,487 of amines, 836-837,847,854-855 MarkoMlkov, 319,321,327-329,336-337, of carbonyl and acyl compounds, 923 -940 351.-352 of esters and ketones, 93 1-932 mechamsm B-Alkyl-9-BBN, 934 electrophilic, 332 - 342 Alkylbenzene derivatives, synthesis of, 689-690 free-radical, 322, 351 -356, 1081 - 1083 Alkylbenzenes, 55 1 hydroxylation, 484 analysis, 564,580: 58 1 of methylene, 474-476 electropec subsatution, 564 orientaaon in, 327-329,335-338 halogenahon, 562,565-568 oxymercuration-demercuration, 222, 32 1, hydro enation, 56 1 346 - 347 idendcation of, 564 peroxide effect, 330,351 -352 industrial source, 555-556 polymdtion, 356-357, 1081 - 1083, 1084- oxidation, 562, 563-564 1089 physical properties, 552-555, t553 stereochemistry preparation, 556 halogen azides, 384 Clemmensen reduction of ketones, 556-557, halogens, 372-377 677 halohydrin formation, 384 ~riedei&ft.s alkylation, 556- 56 1,564 hydroboration, 222, 321, 348 -349 WoH-Kishner reduction of ketones, 556- hydroxylation, 484 557,677 oxymercuration, 346-347 reactions, 550 of sulfUric acid, 320,331 -332 hydrogenation, 56 1 of water, 320, 332 oxidation, 562,563-564,721 alkylation, 32 1,344 - 345 ring vs. side chain, 565-568 alkyl halides from, 17 1 substitution in the ring, 562 analysis, 360- 362 substitution in the side chain, 562,565-568 carbocations from, 559 side-chain halogenation of, 566- 568 cleavage reactions, 323 spectroscopic analysis, 592- 594, t607,606 -607 dimerization of, 320,343-344 structure and nomenclature, 551 -552 ease of formation of, 301 (See also Arenes) free-radical halogenation, 388-390 B-Allcyl-9-borabicyclo[3.3.l]nonane,934 Alkylboranes Ally1 radical 1283

ylboranes, 933-934 vs. aryl halides, 950-952 yl borate, 898 (See also Acetoacetic ester synthesis; Friedel- yl bromide, 104, 187, 190, 197,309 Crafts alkylation; Malonic ester synthesis) yl carbamates, 782 Alkyl hydrogen carbonate, 78 1 yl chloride, 104, 124 Alkyl hydrogen sulfates, 33 1 ylcyclohexanes, 463 Alkyl iodide, preparation, 172 lkylcyclopentenes, 703 Alkyllithium, 101 Ikyl-4,4-dimethyl-2-oxazoline,932 Alkylmagnes~umhalide, 99 yl free radicals, 47 - 49, 106- 109 Akylmalonic esters, 924 ase of formation, 113 Alkyl phosphates, 1137 , lyperconjugation, 401 -402 Alkyl shift, 206,934 elative stabiilities, 11 1 - 112 Alkyl sulfonates, 860 tereochemistry, 160- 162 in l ,2-elimination, 308 tructure, 64-65 formation of, 233-235 71 groups, 309 1 halides, 234-235 ~omenclature,88 - 90 AGl3ates, 246 ymbol for, 97 Alkynes, 425 -442 yl halides, 103, 165-212,429-430,909 acetyhdes, 429-430,438-439 malysis, 21 1, 640,950-952 acidity, 436-438 mnd dissociation energies, 221, t22,6 1, 299 alkyl halides from, 17 1 mnd lengths, t95 1 analysis, 440 mbocations from, 558-559 electrophilic addition, 434-435 :haracteristic proton chemical shifts, t607 and hydration, 432,435 -436 insidefront cover industrial source, 429 :lassif~~op,168 nomenclature, 428 mnvemon Into organometallic compounds, 175 non-terminal, 440 :oupling with organometallic compounds, 101 - physical properties, t429 102 preparation, 429-430,438-439, 692 jehydrohalogenation of, 288,289,290-293 reactions, 429-433 lipole moments, t95 1 as acids, 433,436-438 :limination (Seealsodehydrohalogenation above) admtion, 431,432 via carbanions, 297-298 reduaon to allcenes, 433-434 El, 293 stereoselective, 289,431,433-434 E2,293 - 294 spectroscopic analysis, 2592, 593, 594, 599, stereochemistry, 377-380 t607 vs. substitution, 175,308- 3 10 structure, 425 -427 ent from, 99 - 101 terminal, 437,440 z%$ii%ect of solvent, 260 AUcynylbenzenes, 550,580 (See also Arenes) hydrolysis, 178- 179 Allene, 410, t411,411,423 alcohol synthesis, 222-223 optidy active, 423 glycol synthesis, 222-223 Allinger, N.L., 468,490 NMR and CMR spectra of, 640 Allitol, 1162 nomenclature, 168 (+)-Nose, 1162 physical properties, 169 - 170, t169 Allyl, 283 preparation, 170- 172 My1 acetate, 1099 from alcohols, 170,224-225,229 -233 My1 a$ohol, t216,214, 365,404 from alkanes, 170 Ally1 amon from alkenes, 319,327-329,388-390 electronic configuration, 998 - 999 from alkynes, 17 1 molecular orbitals, 998-999 by halide exchange, 171 Allylbenzene, 551,577 reactions, 172 - 175 Ally1 bromide, t169,283,364,404 with acetylides, 429-430,438-439 Ally1 cation, 402-404 with allcoxides, 173,240,241 -242 from cyclopropyl cation, 1011 with amines, 174,847 electronic configuration, 998-999 with ammonia, 174,829,832-834 mo!eculq orbitals, 402-404,998-999 with cyanide ion, 173,722,724 orb~talp~cture, 403 with halide ion, 173 as resonance hybrid, 403 -404 with hydroxide ion, see hydrolysis above stability, 403,416 with nucleophiles, 172 - 175 symmetry, 403 with phenoxides, 240 Ally1 chloride, t169,404 with sodioacetoacetic ester, 174,927-929 preparation, 323,389,391 with sodiomalonic ester, 174,924-927 Allyldiazomethane, 645 with water, see hydrolyss above Ally1 ethyl ether, 404 reactivity, 23 1 Ally1 free radical, see Ally1 radical toward E2,299,302 Ally1 halide, t169 toward &l or &2,299 Allylic hydrogen, 390, 124 reduction, 98,99, 174 AUylic rearrangement, 392-393,405 solvolys~s,268 -271 Allylic spectroscopic analysis, t607 structure, 167 Allylic substitution, 323 substitution Allylic substrates, nucleophilic substitution in, nucleophilic, 172- 175, 178 404-406,407 kineucs, 178,230-231, 188- 191 Ally1 iodide, t169 relative reactivities 5-Allyl-5-(2-penty1)barbituricacid, 938 &l, 188-191,200-203,209-210 Ally1 radi@, 123,389:390 &2, 185-188,209-210 electromc configurauon, 998 - 999 &l, 188-191, 194-196,200-203,258-261 HOMO, 1020 compared with &2,208-210 molecular orbitals, 998 - 999 &2, 179-185,185-188,261-267 orbital picture, 397-399 comparedwth &l, 208-210 as resonance hybrid, 395-399 vs. alkyl sulfonates, 234-235 stability, 391,397 la 1284 a-helix W Ammonium salt

AUyl radical, (cont.) salts, 823,823-825,845 symmetry, 393 -394 spectroscopic analysis, t592, t607, 877-878 a-helix, 1230, 1232- 1234 stereochemistry, 826- 827 (+)-Altraric acid, 1162 S-ture, 82!,.850-852 (+)-+OX,, l l62 eArnmoacetamhde, 832 Alumlnum so prop oxide, 225 Aminoacetic acid, see Glycine Amanita rnuscaria, 164 pAminoacetophenone, 695 Amanita rubescens, 164 Amino acid residue Amides, 727, 753 C-terminal, 1216, 1218, 1220 analysis, NMR, 786, 877 N-terminal, 1216, 1218-1219 carboxylic acid, 727,728,740,766-767 terminal residue analysis, 12 18- 12 19 acidty, 766, 859 Amino acids, 741, 1049- 1051, 1205- 1250, 1247 analvsis. 784 a+dic, 1208 ~ofm&ndegradation, 836,838-843 acldity constants, 12 10 hydrolysis, 767 basic, 1208 nomenclature, 754 configuration, 12 12 nucleopbilic substitution, 755 - 760 as &polar Ions, 1208- 12 11 physical properties, 754-755, t755 essential, 1206, t1206 - 1207 preparation, 727, 740,76 1, 766,77 1,778 isoelectric point, 12 11 - 12 12 reactions, 766-767,838-843 natural, t1206 - 1207, 12 12 spectroscop~canalysis, 784-785, t786 physical ,properties, 1208- 12 11 structure, 753 preparaaon, 12 13- 12 15 vs. sulfonamides, 857-860 reactions, 1215 Hofmann degradation, 767,831,836,838-843 structure, 1206- 1208 physical properties, 754-755, t755 synthetic, 1214 substituted, 847 -848,857-859 1-Aminoalkanes, synthesis, 828 analysis, 877 m-Aminoanisole. 965 hydrolysis, 859 p~minobenzenesulfonamide, see Sulfanilic acid nomenclature, 858 pAminobenzenesulfonanilide, 879 preparation, 847-848,857-859 pAminobenzenesulfonic acid, see Sulfanilic acid spectroscopic analysis, 877-878 Aminobenzoic acids, 5 15 Amidol, 9 15 m-Aminobenzoic acid, t7 15 Amination formation, 970 ofa-halo acids, 1213-1214 c-Aminobenzoic acid, see Anthranilic acid pyridine, 1070 pAminobenzoic acid, t715, t824, 863, 1210 reuctive, 829,831,834-835,836, 1214 as essential metabolite, 864 Ammes, 821 -844,845 - 888 y-Aminobutyric acid, 822 aci&ty, 860 2-Aminoethanol (ethanolamine), 483, 514,822, acylaaon, 847, 858 1130 alkylation, 836,847,854-855 a-Aminoglutaric acid, 930 analysis, 876-878 Amino group, protection of, 1248 aromatic l-Aminoheptane, 835 acetylation, 848, 859, 861 a-Aminoisocaproic acid, 927 basicity, 850 2-Amino-4-methoxybiphenyl, 949 conversion intopiazonium salts, 864- 865, l-Amino-2-methyl- l-phenylpropane, 143 coupling with &azonium salts, 873-875 2-Amino-2-methyl- l-propanol, 932 mtrosaaon. 849.864 a-Amino-jLmethylvaleric acid (isoleucine), 2 19, ring substitdon. 848.860-862- 927. 1238 sulfonation, 8621863 6-~mino-2-naphthalenesulfonicacid, 5 10 baslclty, 823, t824, 845, 849-853, t850 2-Aminopentane, 835 . effect of substituents, 853 m-Aminophenol, t890 classiiication, 821 -823 c-Aminophenol, physical constants, t890 conversion into amides, 847,857-860, 1222 pAminophenol,t890 derivatives, 877 2-Amino-l-phenylpropane, 843 Hinsberg test, 876- 877 a-Aminopropionic acid, see Alanine Hofmann elimination, 849,854-857 FAminopropionitrile, 978 industrial source. 828 2-Aminopyridine, 1069, 1070 nitrosation, 849,'864 3-Aminopyridine, 1069 nomenclature, 822- 823 4-Aminopyridine, 969, 1070 optical activity, 825 Aminosuccinic acid, see Aspartic acid physical properties, t824, 823-824 Aminotoluene, see Toluidine preparation, 828-837 Ammonia, 17- 19,258,825,828,846 Curtius reaction, 839 aa&ty, 437 from halides, 829, 831,832-834, 836 constant, 768,860 Hofmann degradation of amides, 767,830, basicity, 33 831,836,838-843 compared with amines, 85 1 Lossen reaction, 844 constant, 850 reduction of nitriles, 830,831 bonding in, 18- 19,20,24-25 reduction of nitro compounds, 828,831,832 derivatives. addition to aldehydes and ketones, reductive amination, 829-830,83 1,834- 679-680 835,836 dipole moment,. t24,24-25 . of secondaxy and tertiary, 836-837 inkion, 19 protection of amino group, 861 unshared pair of electrons, quaternary ammonium salts, 854-855 Ammonium acetate, 764 reactions, 845 - 888 Ammonium carbamate, 782 with carbonyl compounds, 935-937 Ammonium chloride, 258 with nitrous acid, 849,864-866 Ammonium formate, 7 17 with sulfonyl chlondes, 847,857-859,876 Ammonium ion, 827,85 1 summary, 845 - 849 Ammonium salt. 265 Ammonium succinamate Aryl halides immonium succinamate, 764 Anomers, l l70 immonolysis Antarafacial reaction, 1016 of acid chlorides, 76 1 Anthocyanins, 1075 of anhydrides, 764 Anthracene, 5 10,580 direct, 1213- 1214 Anthpnlic acid (o-Aminobenzoic acid) t735,970, of esters, 77 1, 778 lLlU of halides, 829,831,832-834,836 ~hvsidconstants. t7 15 imphipathic, definition, 1124 an'ti-addition, 370-372,373,374,376,392-393, implitude, of wave, 992 1047- 1048 imyl alcohol, 2 18 Antiaromatic, 1003 rctive-Amyl alcohol, t2 16 Antibiotics, 863, 1247 imylopectin, 1193 Antibonding oybitals, 994-996 structure, 1195 - 1198 anti conformabon, 85 imylose, 1193- 1196 n-butane, 463 reactions, 1193 - 1196 in E2 elimination, 47 1-473 structure, 1193 - 1196 Apoenzymes, 1229 imytal, 938 Aprotic solvents, 254-258,926 inalysis Arabans, 1203 Carius method, 74,5 14 (+)-Arabinose, 1155 chromatographic, 12 17 (-Mrabinose. 1156- 1158. 1161 combustion, 72-73 i-~rabinose,1203 conformational, see Conformational analysis Aralkyl halide, 552 dansyl method, 1220 Arecaidine, 1076 by derivatives, 149- 150 Arenes, 549-584 determination of structure, 121 - 122,585-586 analysis, 580-581 Dumas method, 513-514 industrial source, 555 -556 elemental, qualitative, 72 -73 nomenclature, 55 1-552 elemental, quantitative, 73 - 74 physical properties, 552- 555, t553 Kjeldahl method, 5 13- 5 14 preparation, 556-561,576-578 mass spectrometric, 122,586-589 reactions, 561 -568,578-580 neutralization equivalent, 744-745 addition, 579 -580 by periodic acid, 699 hydrogenation, 562,578 saponification equivalent, 784 oxidabon, 562,563-564,578 Schoniger oxidation, 72 ring substitution, 562,565-566 sodium fusion, 72 side-chain substitution, 562, 566-568 spectroscopic, 121,585-655,700-701,877- structure, 55 1- 552 878 (See also individual types and individ- (See also Alkenylbenzenes; AUcylbenzenes; Al- ual families) kytylbenzenes) carboxylic acid derivatives, 784-785 (+)-Argume, t1206 structure, determination of, 121- 122,585-586 Amett, Edward, 202 ultraviolet, 597-598 Aromatic character, 1000- 1004 Van Slyke method, amino nitrogen, 1215 Aromatic compounds x-ray, 122 aliphatic, 549- 584 for configuration, 140 definition. 493 (See also individualfamilies and individual ele- heterocyclic, see Heterocyclic compounds . . polynuclear, 5 10 - 5 13 inchimeric assistance, 841,1035,1037 - 1041 sources, 446-447,555-556 indiron formula, of ethane, 80 Aromatic hydrocarbons indrogen, 1136 aliphatic, 549- 584 indrost-9(11)-ene, 1141 physical properties, 552-555, t553 inet. F.A.L.. 624 (See also Arenes; Polynuclear aromatic com- inethole, 894 ~ounds) ingle strain, 450-455 Aromiticity, 493 - 516 orbital picture, 453-454 of annulenes, 5 16,644, 1000 (See also Baeyer stmn theory; Bond angle) electronic configuration and, 1000- 1004 inhydrides, t755 experimental cnteria of, 494,504,604-608, acld, see Acid anhydrides 1000- 1001 carboxylic acid, structure, 753 geometry and, 504,506, 1000 physical properties, 754-755, t755 Hiickel rule and, 504-508, 1000- 1004 iniline, 508, 821,822, t824, 825, 830, 836, 839 NMR and, 504,605, 1000 industrial preparation, 827 -828 requirements for, 504 - 508, 1000 - 1004 preparation, 953,962,963 Aromatic properties, 493 -494,504 - 508 (See also protection of amino group, 861 Aromatiaty) reactions, 540-542,846,848,858,862,863,867 Aromatic proton, MMR chemical shift, t607 resonance, 540 - 542 Aromatic ring, 549 inilinium chloride (aniline hydrochloride), 823, spectra, t592, 593 827--., 846- -- Aromatic sextet, 504-507,511, 1001- 1003, 1060, ini!+um hydrogen sulfate, 546, 547, 862 l067 inhnmm ion, 85 1 Aryl bromides, see Aryl halides inionic polymerization, 1085 Aryl carbamates, see Urethanes inisaldehyde, t661,683 Aryl chlorides, see Aryl halides inis~qa%d, t7 15, 9 12, 9 18 n-All~sidme,t824,965 -967 "rdr%gn of, 909-9 11 ~Anisidine,t824 reactions of, 9 11 - 9 12 ~Anisidine,t824 AryI fluorides, in nucleophilic aromatic substitu- inisole (methyl phenyl ether), t238,546, 547,724, tion, 960 (See also Aryl halides) 874,909,911, 1204 Aryl halides, 552,943-970 innulenes, 5 16,644, 1000 ammonolysis, 831, 950,953 inomeric effect, 1180 analysis, 967 1286 Aryl iodides Benzene

Aryl halides, (cont.) alkenes, 3 18 bond lengths, 851 alkoxidk ions, 228 charactenstic proton chemical shifts. 2607 and amines, 823, t824,849-853 inside.fioht cover benzene ring, 5 18 dipole moments, 851,95 1 carbanions, 436 -438 electrophilic substitution, 522,2522,542-544 carboxylate ions, 729 Grignard reagent, 695,948 piperidine, 1073 hydr~ly~i~,898- 899,949-950,952-953 pyridine, 1067, 1071- 1073 low reactivitv. 948 -950 pyrrole, 1059- 1064 structure and. 950-952 relative, 34,228, 437, 729, 1071- 1072 nomenclature, 508 -509 Basiqty constants, 849 -853 nucleophilic substitution, 949,952-967 amines, t824,849, t850 bimolecular displacement, 949,952 -967 amino acids, 1208- 12 11 elimination-addition, 949,962-967 ammonia, 849 orientation, t520,542-544 pyridine, 1073 physicalproperties, 944-946,845, 851 pyrrole, 1060- 1061 preparabon, 946 - 948 Basketane, 445 from diazonium salts, 867,869-870,947 9-BBN (9-borabicyclo[3.3. llnonane), 809, 8 18, by halogenation, 529,551,947 934-935 nitration, 2520 Beckmann rkgement, 88 1, 1098 reactions. 704.948 - 949 Beef insulin, 1249 reactivi$, 542 Beef tallow, tl l21 structure, 943 -944,950-952 Bender, Myron, 775 vs. alkyl halides, 910,943-944, 948 Benedict's reagent, 1144, 1149 vinyl halides, slrmlanty to, 949-950 Bedgroup, 80 1 Aryl iodides, see Aryl halides Benzalacetpne, 872,973,985 Arylmagnesium chlorides, 685, 1066 preparabon, 801 Aryl methyl ether, 909 Bedacetophenone (chalcone), 872 Aryloxyacetic acids, 9 12 preparation, 801 Ascarite. 73 reactions, 976, 979 ~spardne,137 Bedbromide, 2169 (-)-Asparagine, t 1206 Benzal-pbromoacetophenone, 982 Aspartic and, 977, 1214, 1247 Bedchloride. t169 (+)-Aspartic acid, 21206 preparation, 562, 566 Aspergillus niger, 1203 Benzaldehyde, 659, t661,673,674,681,704,835 Asphalt, 86 reactions, t520,680, 801, 810, 811, 812, 990 Aspirin, 9 14 Beddehyde diethyl acetal, 68 1 Associated liquids, 30, 2 17 -2 18 Benzaldehyde phenylhydrazone, 674, 115 1 Atactic polypropylene, 1088- 1089 Beddoxime, 844 Atomic orbitals, see Orbitals Bedgroup, 801 Atomic structure. 6 Benzgnide, 754, t755,767,839 Atomic weights, see inside back cover aa&tv constant. 768 ATP (adenosine triphosphate), 1128 infrarkd spectrum, 785 Atropa belladona, 750, 1075 preparation, 76 1 Atropge, 750, 1075 Benzanilide, 858 Atropisomers, 150 preparation, 858, 1098 Attractive forces, 20- 2 1 Benzedrine, 843 Aureomycin, 863 Benzene, 296, 399,447,493-516,643 Axial bonds in cyclohexane, 460-465 aromatic properties, 493-494,497-498,500, Azeotropes, 221,681,738 502- ..504 Azobenzene. 844 bond angles in, 50 1- 503 ' Azo compounds, 849,868,878,873-875 bond dissociation energy, 502 Azo dyes, 875 bromination, 498, 524 Azoisobutyronitrile, 1082 carbon-carbon bonds in, 499-500 chlorination, 498,529 derivatives, nomenclature, 508 - 509 "Dewar" formula, 1029 disubstitution products, 495 - 496 electronic configuration, 1000 Bacillus macerans, 11 98 electrophilic substi!ution, 497:498,504 (See Back-bonding, 1042 also Electrophhc aromabc subsfimbon) Bacterial enzymes, 7 19 Friedel-Crafts acylation, 498 Baeyer, Adolph von, 450 Friedel-Crafts alkylation, 498,528 Baever strain theory,-. 450-453 (See alsoS Angle halogenation, 498,529 -strain) heat of combustion, 498 - 499 Baeyer test, 36 1 hydrogenation, 447 Bakelite, 109 1 heat of, 498 -499 Barbital, 938 industrial source, 555 -556 Barbiturates, 783 isomer number, 494-497 Barbituric acid, 783 and structure, 500 - 50 1 Bartlett, P.D., 989 KeMB structure, 401 ,. 494-497 Base-catalyzed halogen dance, 944,970 Kerner methqd of absolute orientation, 509 Base-~romoted1.2-elimination. 246 Ladenbun! vnsm formula, 5 15 ~asei mass spe&m of, 588 Lewis definition, 34 nitration, 497,521 -522,524-527 Lowry-Brvnsted definition, 33 orbigs, 50 1- 503,999 and molecular structure, 35 physlcal properbes, t553 Basicity, 33-35, 175-178 "purple", 358 alcohols, 228 rate companson, 536 - 537 Benzenediazonium chloride 1

reactions, 497-498,529,530-531,560,575,689 Benzyl chlorocarbonate, 782, 1215 vs. cyclohexene, t497 acylation by, 1222 resonance, 500 - 50 1 in peptide synthesis, 1222 stability and, 500 - 50 1 Benzyl chloroformate, 782, 12 15, 1222 ring, 503,5 17,564 in mutide- svnthesis.-,-- 1222- 1223 reactivity, 520 ~e&ilGanide (phenilacetoniae), 722,830 as source of aromatic compounds, 555 Benzyl&(n-butyl)armne, 847 stability of, 497-499,500,503,507, 1002 Benzvldimethvlamine. 829 structure, 400,494,500-504 ~enzilethyl ether, 576 sulfonation, 498, 527 Benzyl free radical, see Benzyl radical thiouhene in, 106 1 Benzyl group, 552 vs. tbluene, 555 spectroscopic analysis, t607 3enzenediazonium chloride, 849,867-868,874 Benzylic hydrogen, 124,566 3ensenediazonium fluoroborate, 868 Benzylic substrates, nucleophilic substitution in, 3enzenediazonium ion, 880 575-576.. .- 1,4-Benzenedicarboxylicacid, see Terephthalic acid Benzyl iodide, t 169 3enzenesulfonamide,860 Benzylmagnesium chloride, 691 3enzenesulfonadde, 848 Benzylmalonic acid, 1213

3enzenesulfonic acid.,S,, 498.508.531.862 Benzyl methyl ketone, nitration, t520 formation, 1042 3enzenesulfonyl chloride, 858 nomenclature, 660 in Hins+rg lest, 876 Benzyloxycarbonylglycine, 1223 3enzenomum ions, 526 Benzoxycarbonylglycylalanine, 1223 3enzhydrol (diphenylmethanol) 704 Benzyloxycarbonyl group, 1222 3enzidme, t824 Benzyl phenyl ether, 909 3enzil, 684,988 Benzyl radical, 123 3enzilic acid, 684 resonance stabktion, 568-570 rearrangement, 684 stability and ease of formation, 567 3enzoic acid, 508, 564,667, 713, t715,716, 739, Benzyne (dehydrobenzene), 962,967 750.754.771 in nucleophilic aromatic substitution, 962-967 indushal source. 720 structure, 962 model of, 7 14 Bergmann, Max, 1222 preparation, 482,562,563,578,720,761 Berson, Jerome, 1023, 1029 reactions, t520, 725,726, 728,737, 739,748, Beryllium, 11 - 13 749,767,769,770 Beryllium acetylacetonate, 38 relative acidity, 73 1 Beryllium chloride, 11 3enzoic anhydride, 754 Beta arrangement, 1231 Betaines, 801,811-812, 1248 Bicyclic compounds, 449 nitration, t520 cis-Bicyclo[6.2.0]deca-2,9-diene,I012 3enzophenone, 660,967 trans-Bicyclo[4.4.0]deca-2,4-diene, 1012 preparation, 663 cis-Bicyclo[6.2.0]deca-2,4,6,9-tetraene,1025 in Wittig reamon, 8 11 Bicyclo[2.2.1 heptane, 445 3enzouhenone oxime. 844 Bicyclo[4.l.O]heptane, 489 geometric isomers, 844 l, l'-BicyclohexenyI, 986 reactions, 1098 cis-Bicyclo[4.3.0]nona-2,4-diene,1012 ~Benzoquinone,984 trans-Bicyclo[4.3.0]nona-2,4-diene,1012 reactions, 983 -984 Bicyclo[2.2.2]oct-2-ene,445 3enzotrichlonde cis-Bicyclo[4.2.0]octa-7-ene,1025 hydrolysis, 720 Bidentate, definition, 1042- 1043 physical constants, t169 Bijvoet, J.M., 140, 154, 155, 1164 preparation, 562,566 Bilayers, 1130-1131 3enzotduoride, 546 Bile acids, 1135 ~Benzoylbenzoicacid, 765 Bimolecular displacement mechanism, 959 -96 1 ~Benzoylbenzoicacid, 695 (See also Nucleophilic aromatic substitution) 3enzoyl chloride, 667,754, t755 Bimolecular elimination (E2 mechanism), 293 - preparation, 726,737 294 (See also Elimination reactions) reactions, 663,761,762,858,899 Biochemical processes 3enzoylglycylalanine acid, 1222- 1223 biosynthesis of fats, 1122 V-BenzoylglyGne (hippuric acid), 880, 1215 biosynthesis, of fatty acids, 1132- 1134 3enzoyl peroxide, 1084 chvmotrvus~nacaon. 1236- 1240 l-Benzoylthiophene, 1063 3enzvl acetate. 768. t769 hydroli&s, 1236- 1238 preparation, 726 . nucleoproteins and nucleic acids, 1241 3enzyl alcohol, 214, t216,552,576,768, 1097 vision, 285-287 esterificaaon, 726 Biochemistry, definition, 11 19 infrared spectrum, 595 Bi+egra&ble detergents, 1 126- 1 127 preparation, 222 Bio-inonose, 1182 3enzylamine Biological oxi&tion and reduction, 1103 physical constants, t824 Biomass, 2 ~re~aration.833.835 Biomolecules, 69, 11 19 Biosvnthesis offats, 1122 I of fatty acids, 1132 - 1134 3&$1 +on; 376. Biot, Jean-Baptiste, 130 stab&@ of, 574-575 Biphenyl, t553, 546,949 3enzyl chlonde, t169 1,2-B/s(4phenylphosp$no)butane, 105 1 preparation, 562,566 2,4-Bis(dIphenylphosphlno)pentane, 105 1 reactions, 222,557,574,722,829,830,833,847 1,2-Bis(diphenylphosphino)propane, 1051 2,2-Bis@-hydroxyphenyl)propane, 1099 Bromoalkanes, 104 Bisphenol A, 1099 3-Bromo-4-aminotoluene, 86 1 Block copolymer, 1084 m-Bromoaniline Boat conformation. 455 - 460 physical constants, t824 Boc-Glycine, 1224 ' preparation, 830 Boiling point, 30 - 3 1 reactions, 872 associated liquids, 30,2 17 - 2 18,89 1 eBromoaniline, t824 chain branching and, 94 pBromoaniline, t824,848 chain length and, 93 - 94 pBromoanilinium chloride, 859 hy,&ogen-bonding Bromoanisoles, 965 mtermolecular, 30,217-21 8,891 pBromobenzaldehyde, 662 intramolecular, 89 1- 892 m-Bromobenzamide, 830 ionic vs. non-ionic compounds, 30 Bromobenzene, 498,508,552,584,943,@45,951 molecular sham and. 94 nitration, t520 molecular size and, 3 l, 93 m-Bromobenzenediazonium chloride, 872 polarity, 217, t2 17 ' pBromobenzenesulfony1group, 272 Bombykol, 8 19 m-Bromobenzoic acld, t7 15 Bond angle, 13, 17 o-Bromobenzoic acid. t7 15. 72 1 Bond dissociation energy, insidefiont cover, 9,2 1- pBromobenzoic acid; t715; 716 '7'7 A7 L&, -t I o-Bromobenzovl chloride. 769 comparison of cations, 197- 198,403 m-~romobenzilalcohol, 552 heterolytic, t22 l-Bromobutane, see n-Butyl bromide homolytic, t2 1, 364 2-Bromobutane, see sec-Butyl bromide Bond energy, 2 1- 22 3-Bromo-2-butanol, 386, 1032- 1034, 1038 Bond length, 10 3-Bromo-l-butene, 417,423 Bond orb~tals,see Orbitals l-Bromo-2-butene,417,423 Bonds pBromo-sec-butylbenzene, 72 1 bending, infrared absorption and, 590, 593-594 PBromobutyric acid, 975 bent, 453 m-Bromochlorobenzene, 524,969 benzene, 500 l-Bromo-3-chlorocyclobutane,645 breaking, 153, 160, 165 2-Bromo- l-chloroethane, 34 1 cleavage, 22 Bromochloromethane, 133, 141 covalent, 4-59- 11 l-Bromo-2chloro-2-methylpropane, 124 dipole+lipole, 28-29, 259-260 3-Bromo-5-chloronitrobenzene,509 double, see Carbon-carbon double bonds l-Bromo-2-chloropropane, 124 hvbrid. 395 l-Bromo- l-chloropropene, 28 1 , , 2-Bromo- lchloropropene, 28 1 ionic, 4 Bro~~cyclohexane(cyclohexyl bromide), t169, one-and-a-half, 395, 500, 733 a53 orbitals, see Orbitals NMR and conformational analysis of, 628,644 from overlap of orbitals, 9- 11 2-Bromocyclohexanone, 800 R, 274-275,426-427 l-Bromocyclohexene, 492 polarity, 23 3-Bromocyclohexene, 323,391,414 U, 274-275,426 2-Bromo-2-cyclohexenol, 1012 single, see Carbon-carbon single bonds 2-Bromocyclohexyl brosylate, 1041 stretching, infrared absorption and, 593 - Bromocyclopentane, 448 tri~le.425 -427 l-Bromo-1,24chloroethene, 28 1 ~ondstrength, see Bond dissociation energy 3-Bromo-2,24methylbutane, 246 9-Borabicyclo[3.3. llnonane (9-BBN), 809, 8 18, 4-Bromo-2,44methylhexane, 168 934-935 trans- l-Bromo- 1,2&phenylethene, 385 Borane, 348 l-Bromo-1,2-diphenylpropane,377- 379 Borane-tetrahydrofuran complex Bromoethane, see Ethyl bromide Borate esters, 386 2-Bromoethanol (ethylene bromohydrin), 341, Borazole, 503 '342.482-, -- Boric acid, 347 2-~romoeth~lnitrate,341 Borneol, 118 1 o-Bromofluorobenzene, 967 Boron, 13- 14,350 Bromoform, 45, t169 Boron trifluoride, 13- 15 a-Bromoglutaric acid, 742 Boron trifluoride etherate, 1063 Bromohydrins, 342 Bosnich, Brice, 105 1 D-(-)-3-Bromo-2-hydroxypropanoic acid, 1163 Boyd, T.A., 119 pBromoiodoknzene, 509 Breslow, Ronald, 507 2-Bromo-l-iodoethane, 34 1 Bridged cation, 1036 a-Bromoisovaleric acid, 727 Bridged intermediate, 1036 Bromomesitylene, 724 Bromination 3-Bromo-4-methoxybiphenyl, 949 of alkanes, 104- 118 l-Bromo-3-methylbutane, 693 of alkenes, 339 - 342 2-Bromo-2-methylpropane, see tea-Butyl bromide of alkylbenzenes, 566-568 m-Bromonitrobenzene, 872 of methane, 44-4576 Bromonitrobenzenes, 524 stereochemistry, 1032- 1035 Bromonium ions, 340.374-375376, 1033- 1034 (See also Halogenation) Bromine, 370, t588 addhon to 2-butene, 371 -372, 1-Bromo-Zoctene, 392 Bromine water, 1150 3-Bromo-l-octene, 392 pBromoacetanilide 2-Bromopentane, 3 10 preparation, 947 3-Bromopentane, 3 10 reactions, 848, 859 2-Bromo~entanedioicacid. 742 Bromoacetone m-~romophenol,t890 ' preparation, 802,804 preparation, 872 react~ons,933 o-Bromophenol, t890,900,906 p-Bromophenol tert-Butyl bromide

7-Bromophenol, 509, t890 addition of hydrogen halides, 329 preparation, 901,906 dipole moment, 284 I-Bromo-l-phenylethane (a-phenylethyl bromide), hydrogenation, 277 t169, 857 heat of, t326,326 preparation, 170,550,566 ozonolvs~s.323 !-Bromo-l-phenylethane, 566 X-@-Bromopheny1)ethylalcohol, 967 ieadvity, 338, 348 hBromopheny1 ptoluenesulfonate, 900 2-Butene, 268-272,277-278, t277,279, -Bromopropane, see n-Propyl bromide t285, 311,314,375, 384,386,883 !-Bromopropane, see Isopropyl bromide adhtion of hydrogen hahdes, 329 !-Bromopropanoic acid, 7 13 cyclopropane from, 476 -Bromo-2-propanol, 2 15 geometric isomerism, 278 -280 -Bromo-l-propene, 429 hydrogenation, 277 !-Bromopropene,NMR signals, 602 - 603,617 ~re~aration.288 I-Bromopropene,see Ally1 bromide ~ea&vity,338- K-Bromopropionicacid, 7 13 cis- and trans-2-Butenes, 277-280, 284-285, 372, preparation, 833 ?RA reactions, 12 13 adztion of bromine, stereochemistry, 368-372 -Bromopropyne, t 169 addition of carbenes, stereochemistry, 476478 -Bromopyridine, 1070 addition of methylene, stereochemistry, 475 -Bromopyridine, 1068 CMR spectra, 637-638 -Bromopyridine, 1073 diol formation, stereochemistry, 372 -Bromopyridine N-oxide, 1073 dipole moments, 284 1-Bromosuccinimide (NBS), 323,390,392 heats of hydrogenation, 326 r-Bromotoluene, 664,845 stability and, 326 synthes~s,872 hydroxylation, stereochemistry, 372 -Bromotoluene, 72 1, t945 physical properties, t277,284-285, t285 synthesis, 867, 871 Butenedioic acid, 384, 1046 -Bromotoluene. 662, t945 cis-Butenedioic acid (maleic acid), 973 synthesis, 87 1' . trans-Butenedioic acld (fumaric acld), 973 lromotrichloromethane, 322,583 cis-Butenedioic anhydride, 973 -Bromo- l, l, l-trichloronane, 322 2-Butenolc acid, 7 16 2-Buten-l-01,423 Irosyl group, 234 3-Buten-2-01,283,423 ,rown,H.C., 117, 161-162,347,349,389,933 tert-Butoxycarbonylglycine, 1224 -)-Brucine. 160 tert-Butoxycarbonyl group, 1223 'S; 234 ' Butter, t112 1 uckminsterfullerene, 3, 5 12 Butvar, 1093 structure of. 512-513 n-Butvl acetate. t769 uckyball, 5 12 tert-Bbtyl acetate, 778 unnett, Joseph, 299,855-857,944,948,960,970 n-Butylacetylene (l-hexyne), 429, t429, 635 -636 ,2-Butadiene, 4 10, n-Butyl alcohol, 38, t216, t217,218,229,238, ,3-Butadiene, 397, 399, 406, 410, 412, 414,419, t272, 307, 314,660, 691, 883 -983 --> ----1005 dehydrauon, 239,288,311 ~~polymerizationof, 1095 industrial preparation, 808 - 809 cyclization, 1009 oxidation. 662 cycloaddition, 983, 1014- 1015 677,348, 1051 Diels-Alder reaction, 982-983, 1014- 1015 sec-Butyl alcohol, t216,235,765,774,787,883 electronic configuration, 997 - 998 dehydration, 288,3 11 electrophilic addition, 4 15,417 -4 19 infrared spectrum, 595 heat of hydrogenation, t4 10,41 1 optical activity, 159,246 molecul~orbitals, 997 - 999 preparation, 243,689 polymenzahon, 419, 1081 tert-Butyl alcohol, 124, 188, 215, t216,224, 225, preparation, 4 14 229,310,313,584,724,778 stabilization, 410-41 1 dehydration, 3 11 (See also Dienes) Friedel-Crafts allcylation with, 559 utanal, see n-Butyraldehyde hydrogen halides reaction, 224 utane preparation, 33 1-332 gauche interactions, 85 - 86,462,467 n-Butylamine, 212, t824, 836, 883 1,3-diaxial interactions, 467 sec-Butylamme, t824 .Butane, t84, t93 tert-Butylamine, 822, t824 chlorination, 109, 152 nButylbenzene, 653, 825 conformations, 85-86,455,463 i@ared spectrum, 59 1 halogenation, 109 oxldahon, 562 isobutane, 84 preparation, 559,672 physical constants, t84 sec-Butylbenzene, t553,559 preparation, 98,431,447 tert-Butylbenzene, t553, 559-560 thio~henefrom. 106 1 sec-Butvl benzoate. 787 utane-2-d, 247 ' psec-~utylbenzoicacid,72 1 utanedioic acid, 384, 1046 (See also Succinic acid) n-Butyl bromide (l-bromobutane), 122, 168, t169, 3-Butanediol, 372 229,291,429,722,724 ltaqes, 83-85, sec-Butyl bromide (2-bromobutane), 92,98, 310 stenc factors m, 86 analysis, CMR spectra Butanol, 662 proton-coupled, 633 -)-2-Butanol, 1164 protondecoupled, 630-63 1 ltanone (ethyl methyl ketone), 659, t66 1,679,836 dehydrohalogenation, 300 Butanone, 247,441,679 physical constants, t169 Butenal (crotonaldehvde)..,, 677. , 800. , 807.808., , tert-Butvl bromide. 124. t169. 187. 197.310.330 t972,973 ease df elimination, 724 Butene, 277-278, t277,280,282, t285,638, 883 hydrolysis, 188- 189 1290 trans-4-tert-Butyl-l-bromocyclohexane Carbocations tert-bromide, (cont.) in aldol condensation, 808 rate of reaction, 179 infrared spectrum, 700 reaction, with cyanide ion, 724 preparation, 662 &l reaction, relative rate, 200-201 Butyramide, 767 &2 reaction, relative rate, 186 - 187 n-Butyramide, t755 trans-4-tert-Butyl-l-bromocyclohexane, 644 Butync acid, 714, t715,736 nButyl tert-butyl ether, 365 n-Butyric acid, 720 sec-Butylcarbinol, see 2-Methyl-l-butanol n-Butyrophenone (phenyl n-propyl ketone), 660, tert-Butyl cation, 19 1 t66 1, 672 NMR spectrum, 192 n-Butyryl chloride, 664,t755 in &l reactions, 188 n-Butyryl-S-ACP, 1134 n-Butyl chloride, t169,883 from n-butane. 104. 109 dehydrohalogenation, 288 Friedel-Crafts alkylation with, 559 sec-Butyl chloride, t169,385,883 Cadaverine, 844 from n-butane, 104, 109,15 1- 152 Meic acid, 9 15 dehydrohalogenation, 288 Cahn-Ingold-Prelog sequence, 140- 144,28 1,1212 enantiomers of, 132, 135, 140, 142, 152 Cahn, R.S:, 134,. 140 lithiumdialkylcopper from, 102 Calcite. Nicol Dnsm. 128 stereochemistry, 153, 157- 158 calcium acetaie, 7 17 tea-Butyl chloride, 103, 116, 124, t169,229,3 10 Calcium aldonate, 1154 dehydrohalogenation,3 10 Calcium carbide, 38,438 Fnedel-Crafts alkylahon with, 901 Calcium carbonate, 396,734 from isobutane, 104, 108 Calcium cyanamide, 782 lithiumdialkylcop r from, 99 Camphoronic acid, 941 preparation, 224, $6 Cannizzaro reaction, 674,683-684, 806 trimethylacetic acid from, 723- 724 crossed, 674 tert-Butylcyclohexane, 463 Capric acid, 7 14, t7 15 4-tert-Butylcyclohexene, 49 1 Caproaldehyde, t66 1 4-tert-Butylcyclohexyl ethyl ether, 491 Caproamide, 830 cis-4-tea-Butylcyclohexyltosylate, 49 1 Caproic acid, 714, ~715,745,901 trans-4-tert-Butylcyclohexyl tosylate, 49 1 Caprolactam, .l098 sec-Butyldimethylamine, 822 Ca~rovlchlonde. 663 n-Butyldimethylcarbinol(2-methyl-2-hexanol), capryiic acid, 7 1'4, t7 15 687,688,690 Carbamates (urethanes), 780-781, . 782,. 1223 Butylenes, 277-278 Carbamic add, 78 1 '- physical properties, t277 Carbamide (urea), 779 -783 structure, 277-282 Carbanionoid compounds, 100, 102,775,811 - (See also Butene; Isobutylene) 812.967 n-Butylethylamine, 836, 837 carbzdns; 100,797-820,856,923-940 (R)-sec-Butyl ethyl ether, 246 from acetoacetic ester, 8 14- 8 15,927 - 930 tert-Butyl ethyl ether, 241,309 addition to aldehydes and ketones, 800-801, n-Butyleth lmethylamine, 837 805-807,809-811,816 tea-Butyl koride, NMR spectrum, 192,645 in aldol condensaQons, 800- 80 1,805 - 807, tert-Butvl free radical. see tert-Butvl radical 809-810 Butyl &ups, 89 ' basicity, relative, 1071 - 1072 sec-Butyl hydrogen phthalate, 765 charge accommodation, 798,8 13 tert-Butyl hydrogen sulfate, 33 1 in Claisen condensation, 802,8 13- 8 16 tert-Butyl hydroperoxide, 1055 from cyanoacetic ester, 980-981 tert-Butyl hypochlorite, 124,393 definition, 297 . n-Butyl ihde, t169 in dehydrohalogenation, 298 sec-Butyl iodide, t169,328 in halogenation of ketones, 803 tert-Butyl iodide, t169,328 from malonic ester, 924-927,980-981 n-Butyl isopropyl ketone (2-methyl-3-heptanone), in Michael reaction, 979-982 664. in nucleophilic acyl substitution, 802 n-Butylhthium, 932, 1085 in nucleophilic addition, 976-978 n-Butylmagnesium bromide, 687,688,690 in nucleophilic aliphatic substitution, 102. sec-Butylmagnesium bromide, 98,687 927-933 sec-Butylmethylamine, 836 in nucleophilic aromatic substitution, 955 n-Butyl methyl ether, 212 962-963, 1070- 1071 sec-Butyl methyl ether, 243 sbitals, 438, 1072 tert-Butyl methyl ether, 237,241 in organoborane synthesis, 933-935 tert-Butyl methyl ketone (3,3-dimethyl-2-butan- in Perkin condensation, 8 11 one), 705,800,935 from pyridine, 1069- 107 1 ptert-Butylphenol, 90 1 reactions, summary, 800 - 802 tert-Butyl peroxide, 124,584, 1055 resonance, 797 -798 sec-Butyl phenyl ketone, 805 shape, 827 (+)-sec-Butyl phenyl ketone, 803 in Wittig reaction, 8 11 - 8 12 tert-Butyl radical, 116, 117,402 from ylides, 811-812 Butyl rubber, 1085, 1096 (See also individual carbanions) sec-Butyl tosylate, 235 Carbazole, 1057 m-(n-Buty1)to uene, 667 Carbenes, 473-478 pmButylto!uene, NMR spectrum, 609 addition of substituted, 476 -478 1Butyne (ethylacetylene), 428, t429 Carbenium ions, 19 1 preparahon, 438,440 Carbenoid compounds, 477 -478 2-Butyne (dimethylacetylene), 428, t429,43 1 2-Carbethoxycyclopentanone,8 15 1,4-Butynediol, 1062 Carbitol, 484 - - l-Butyn- l-yllithium, 438 Carbocations, 175, 188- 191,304,347,354,373, n-Butyraldehyde, t217, t272,659,660, t661, 734 682, 1033, 1037, 1040 Carbohydrates Carboxyl group

in acetal formation, 68 1 free rotation about, 79- 82 in addition to a,P-unsaturated carbonyl com- infrared spectra, 592- 594 pounds, 975 -976 length, 276 from alcohols and allcenes, 559 in methylacetylene, 276 in ablation of alkenes, 345 rotational banier, 82 from alkyl halides, 558 - 559 Carbon-carbon triple bonds, 425-427 definition, l9 1 Carbon-chain lengthening from dehydration of alcohols, 3 12 aldol condensahon, 805- 8 10 delocalization, 415 -417 ofaldoses. 1152-1154 ease of formation, 201 -203,335-338 of alkanes, 10 1 electronic effect in, 193,202 of alkynes, 429 -430,438-439 in electrophilic addition, 332-338 synthesis of amines, 83 1 in electrophilic aromatic substitution, 526-527, of carboxylic acids, 870 528,529,531 -544 Carbon-chmn shortening encumbered, 270 of aldoses, 1154 formation, 335 degradation of alkenes, 358 - 360 intermediacy of, 205 Hofmann degradation, 836 loss of proton from, 3 14 Carbon dioxide. 119 from naphthalene, 545 -546 Carbon dioxide'balance, 120,2 19 -221 nucleophilically solvated, 269, 270 Carbon-halogen bonds, 408,544,951 from pyridine, 1069 Carbonyhy@ogen bonds, 63 rate of elimination from, 3 18 Carbomc aad, 780,78 1 rate of formation, 201,304,336,338,405,575 functions! derivatives of, 779 - 783 reactions, 208, 304, 344-345, 560 Carbonium Ions, 19 1 (See also Carbocations) rearrangement of, 203-208,305-306 Carbon monoxide, 720 relative stabilities, 196- 198,402 Carbon-oxygen double bond, 669 resonance-stabilized, 975 - 976 Carbon tetrabromide, 45, t169 in &l reactions, 188, 195- 196 Carbon tetrachloride, 32,44, t169 in solvolysis, 268 addition to alkenes. 355 stability, 198, 199, 304-305, 336,403,574-575 carbon-13 nucie&magetic resonance (CMR) stabilization, 199,406-407 ~pectro~~opy,629 -639 structure, 193 a-effect. 636-637 and transition state, 202 analysis (See also individual cations) of alcohols, 639,640 arbohydrates, 676, 1132, 1143- 1204 of aldehydes and ketones, 639,701 classification, 1144 of alkanes, 639 definition, 1144 of alkenes, 639 disaccharides, 1185 - 1192 of alkyl halides, 639,640 esterification, 764 of alkynes, 639 fermentation, 2 19 of carboxylic acids, 639,747 fuel from, 2 19 -22 1 of hydrocarbons, 639 methylation, 1174- 1176 P-effect, 636.-637 monosaccharides, 1143 - 1184 chemcal sh&. 634-638.639 nomenclature, 1144,1146- 1149, 1177- 1178 effect of methjl group, 637 ovone formation, 1151 - 1152 effect of subsfituents, 636-637 ondahon, 1149- 1150 y-effect, 636 -637 polysaccharides, 1192- 120 1 geometric isomerism, 637-638 (See also Aldohexoses; Aldoses; Monosaccha- hybridization of carbon, 634-636 rides; etc.) off-resonance, 63 1 arbon~--- proton-coupled, 63 1-633 Age of, 3 proton-decoupled, 630 - 63 1 a-, 291,294,380, 1049 splitting of sipals, 630-633,640 analysis for, 72 Carbonyl chloride, see Phosgene B-, 291,294, 379 Carbonyl compounds, 657 addihon to, 800 - 801,974 - 984 Diels-Alder reaction, 982 - 984 electrophilic, sources of, 485 electrophilic addition, 974- 976, 978 - 979 migration, 1022, 1035 interaction of functional groups, 974 nucleophilic, 936 Michael addition, 979 - 982 tetrahedral. 126- 128. 131 nucleophilic addition, 976-978 Gbosds; 297,798 ' preparation, 973 arbonate ion, 396 proton chemical shift, t607 arbonahon of ~henols,902 structure and properties, 971 -973 arbon-carbon bonds (See also Aldehydes; Keto acids; Ketones; in benzene, 499 - 500 a, Unsaturated carbonyl compounds) comparison of, 427 -428,499 - 500 Carbony6,up, 669 formation, 439,923 and acidty of a-hydrogens, 797-799 'arbon-carbon double bonds, 283,288,399,578- in aldehydes and ketones, 669-671 G70 in aldol condensation, 807 an;& for, 324,340,358-359,360-362,637- bonding in, 756 638 in carboxylic acid derivatives, 755-759 in ethylene, 273 -275 in carboxylic acids, 728 hindered rotation about, 275,278 geometry, 657-658,756 infrared spectra, 592 -593 Carbowax, 1080 length, 276 Carboxylate anion protecting, 290 basic~ty,729 reactions, 3 17 - 365 structure, 733-734 as substituent, 387-388 Carboxylate ions, structure of, 733-734 :arbon-carbon-. slnde bonds Carboxyl group, 713,725,739 in ethane, 78-82- electron withdrawal by, 728-729 1292 Carboxylic acid anhydrides Chao

Carboxylic acid anhydrides, see Acid anhydrides structure, 7 13 Carboxy$c acjd chlorides, see Acid chlorides substitution, aa, 727 Carboxyhc aads, 713-752,1125 Hell-Volhard-Zelinsky reaction, 727,74 1- acidity, 728-729,732-736 742 effect of substituents, 735 -736 ring, 2520, 728 acidity constants. 729.2735 unsaturated a,/?-unsaturated, 872, 972-973 electrophilic addition, 974 - 975 from fats, 719,1122-1123, 1125-1126 nucleophilic addition, 976-978 a-amino, see Amino acids preparation, 973 analysis, 744-747 (See also Dicarboxylic acids) aromatic Carboxylic acids, functional derivatives of, 753- acidity, 736 796 (See also Acjd aphydrides; Acid chlorides; nomenclature, 7 16 Amides; Carbo~ucacld, fundonal derivatives qreparation, 563,721 -722 of; Esters; Fats; Imides) nng substitution, 2520,728 Carboxypeptic@se, 1220 sources, 7 19 - 720 Cardiac glycosides, 1135 biosynthesis, 1132 - 1134 Carius method conversion analysis for halogen, 73 into acid chlorides, 726 analysis for sulfur, 5 14 into amides, 727 a-Carotene, 488 into esters, see este@c+ion below pcarotene, 286,488,599 into functional denvahves, 725-727 y-Carotene, 488 into salts, 7 19,725 &rvacrol, 9 16 effect of substituents, 735 - 736 3,8-Carvomenthenediol, 704 estenficahon, 726,737-739 (See also Esters) Carvomenthol, 705 mechanism, 776-777 Carvomenthone, 705 reactivity, 738 (+)-Carvotanacetone, 705 from fats, 7 19 Castile soap, 1124 functional derivatives, 725 - 727,744,753 -796 Catalvsis (See also individualfamilies) acid, 229-233 analysis, 783-785 in 0x0 processes, 1052- 1053 carbonyl group m, 756-759 phase-transfer, 264-266 compared with sulfonyl derivatives, 859 -860 by transition metal complex, 105 1 hydrolysis, 761,764, 767-768, 771 Ziegler-Natta, 1087- 1088 nomenclature. 754 Catalytic cracking, 119, 120 nucleophilic acyl substitution, 755 - 760 Catalytic hydrogenation, 325 (See also Hydrogena- physical properties, 754-755, t755,2769 ban) spectroscopic analysis, 784-785 ~atal$:c'reforming, 96, 119, 555-556,720 structure, 753 of alicyclic hydrocarbons, 446 halogenation, a, see Hell-Volhard-Zelinskv re- of alkanes. 120 action Catechol, 889 hy+ogen bonding in, 7 17 Cationic polymerization, 1084- 1085 lolluabon, 729 Cell membranes, 1130- 113 1 keto, see Keto acids (+)-Cellobiose, 1185, 1188- 1189 neutralization eqmvalent, 744 - 745 Cellobiose octaacetate, 1188 nomenclature. 7 14- 7 17 Cellobiuronic acid, 1203 odor, 717 ' Cellophane, 120 1 physical properties, t715, 717 Cellulose, 220, 1143 - 1144, 1192 preparation, 360,720-723,811 molecular weights, 1200 acetoacetic ester synthesis, 939 properties, 1200 carbonation of Grignard reagents, 72 1- 722 reactions, 1200- 120 1 via diazonium salts, 870 structure, 1200 Grignard synthesis, 723 - 724 Cellulose acetate, 120 1 halofotm reaction, 676,698 Cellulose ethers, 1201 hydrolysis of nitriles, 722, 724-725, 870 Cellulose nitrate, 120 1 Kolbe reaction. 908 Cellulose trinitrate, 120 1 malonic ester synthesis, 924-927 Cellulose xanthate, 1201 organoborane synthesis, 933-935 Cerebrosides, 1137 via 2-oxazolines, 932 CFCs 69,71, 119 oxidation- .. .. - chair;-initiating steps, 70, 7 1, 1081 of alcohols, 226,235 -237,72 1,722 Chain-propagating steps, 70,71, 108 1 of alkenes, 359- 360,699 Chain-reaction polymerization, 1078, 1087 - 1089 of alkylbenzenes, 563 -564,72 1 coordination polymerization, 1087- 1089 of arena. 562.563.721 copolymerization, 1083- 1084 of methyl ketones, 6761677 free-radical vinyl polymerization, 1080- 1083 periodic acid oxidation, 359 -360,699 ionic polymerization, 1084- 1086 Perkin condensation, 8 10- 8 11 (See also Free-radical polymerization) reactions, summary, 725 -728 Chain reahons reduction to alcohols, 727, 740 chlorination of methane, 48-49 salts, 717,718-719,725 combustion of alkanes, 118 nomenclature, 7 17 formation of ozone shield, 70- 7 1 physical properties, 7 18- 7 19,744 - 745 halogenation of alkanes, 104- 106 solubility, t715,717-719 photolysis of CFCs, 7 1 salts, 718-719 Chain-terminating steps, 7 1, 1081, 1086 sources Chain transfer, 1082 aliphatic, 7 19 Chair conformation, 455-460,463,467 aromatic, 720 Chalcone, 872 spectroscopic analysis, t592, t607,745-747, t786 Chao, T.H., 161- 162 Chavibetol Cinnamaldehyde

Zhavibetol, 9 18 2-Chloro-3-hexene, 41 5 Zhelation, 891, 1043 Chlorohydrins, 342,384 3hemical bonds, see Bonds 2he4cal pgeogenetics, 1227 -hemcal sm.604-608. t607 ~hloroiodomethanesuifonicacid: 142 Shichibabin reaction, l070 enantiomers, 132,134 Zhirality, 133-136, 140-141, 151-153 Chloromethane, see Methyl chloride bond breaking and, 153- 154, 160- 162 l-Chloro-2-methylaziridine, 827 chiral centers, 135- 136, 148 l-Chloro-2-methylbutane generahon of, 151- 153, 1050 chirality, 154, i56 generation of second, 156 - 158 photochemical halogenation of S-(+)-isomer, 16 1 1,2-dimethylcyclohexanes,468-469 2-Chloro-2-methylbutine. see tert-Pentyl chloride optical activity and, 139, 154- 155 y-Chloro-a-methylbutyricacid, 716 reagents, chiral and achiral, 138 2-Chloro-l-methylcyclohexane, 445 reactions of chiral molecules, 153- 162 3-Chloro-2-methylpentane, 142, 168 Zhiraphos, 105 1 l-Chloro-2-methylpropane, see Isobutyl chloride Zhlorination. 43 -44 2-Chloro-2-methylpropane,see tert-Butyl chlonde of alkanes,' 104- 118 3-Chloro-2-methyl-l-prouene,364 of alkylbenzenes, 565 - 568 Chloromycetin, i37,863- aromatic, 529 m-Chloronitrobenzene, 509,943, t945,957-958 mechanism of, 46 - 48 preparation, 947 of methane, 43 -44,48 -49,76 o-Chloronitrobenzene, t945,954, and stereochemistry, 160- 162 pChloronitrobenzene, t945,953, (See also Halogenahon) 2-Chloro-4-njtrophenol, 509

Zhlorine, 364 4-Chloro-2-n~trotoluene.. - - ~ 523 abundance of, 37C1, t588 4-~hloro-3-nitrotoluene;523 36Clas tracer, 118 Chloronium ions. 376 Clhloroacetic acid, 750,829 2-~hloronorbornene,473 preparation, 727 l-Chloropentane, 636 - 637 reactions, 743,902 2-Chloropentane, 246 relahve ac~hty,736 3-Chloropentane, 246 Clhloroacetone, 364 m-Chlorophenol, 898, t890 z-Chloroacrylonitrile, 990 o-Chlorophenol, 889, t890 ,hloroalkanes (alkyl chlorides), 104, 124 pchlorophenol, t890 Fhloroallybenzene, 967 3-(pChloropheny1)butanoic acid, 7 16 ,hloroanilines, t824 l-Chloro-l-phenylethane,see a-Phenylethyl chlo- Clhloroanisoles, 1204 ride z-Chlorobenzaldehyde, 674 2-Chloro-l-phenylethane, seePPhenylethy1 chlo- ,hlorobenzene, 508, t945,968 ride nitration. t520 fi(pChloropheny1)ethyI alcohol, 967 prepadon, 498 Chlorophyfl, 220, 1007, 1059, 1122 reactions. 542-544,827,894,953,970 Chloroprene, 420 resonan&, 950 l-Chloropropane, see n-Propyl chloride W-Chlorobenzenediazoniumhydrogen sulfate, 898 2-Chloropropane, see Isopropyl chloride 7-Chlorobenzenesulfonic acid, 509 l-Chloro-2-propanol (propylene chlorohydrin), W-Chlorobenzoateion, 674 231,320,487 W-Chlorobenzoicacid, t7 15, t854 preparation, 342 ~Chlorobenzoicacid, t715,745,749,750,943,970 l-Chloropropene, 442 ~Chlorobenzo~cac~d, t7 15,750 3-Chloro-l-~ro~ene.see Allvl chloride . W-Chlorobenzylalcohol, 674 ~ndo-2-Chloro-exo-2-bromobicyclo[3.l .O]hexane, In17 h-~hlordvrdpionicacid, 750 -~hiGbutane,see n-Butyl chloride :-Chlorobutane, see sec-Butyl chloride pchloroityrene, 578 a-Chlorotoluene, see Benzyl chloride m-Chlorotoluene, 584, t945 nitration, 524 ;khl&ro-2-butene, tl69 o-Chlorotoluene. 584. t945.947 I-Chloro-2-butylfree radical, 159 preparation, 565,867 . :hlorobutyriccacid, 736 ~Chlorotoluene,523, 584, t945 :hlorocarbomc acid, 78 1 preparation, 565 :hlorocyclopropane, 444,448 Chlorot@uoromethane, 69,76 Cholecalcfierol, 1030 Cholestane-3/3,6adol, 1140 - 114 1 3-Cholestanone, 1140 2-Cholestene, 1141 Aloroethane.-7- see ~thvlchloride Cholesterol. 421. 1134- 1137. 1140- 1141 -~hloroethane,92, tf69 Choline, 882, l130 I-Chloroethanol (ethylene chlorohydrin), 214,223, Choline phosphoglyceride, 1130 1054 Chromatography, 1217 Chloroethene, 329 Chro+c anhydride, test for alcohols, 244,362 (l-Chloroethyl)benzene, see a-Phenylethyl chloride Chromum(VI), 236 Chlorofluorocarbons, 43, 119 Chymotrypsin and ozone shield, 69 - 7 1 action, 1236- 1240 Chloroform, 44, 124, t169,583,902,908 m-stmcture.------~--~> 1234. - 1236- 1237 addition to alkenes, 355 ~hymotrypsino~en,'122 1, 1237 test for akylbenzenes, 580 (+)-Cinchonine, 160 l-Chloro-2-halopropane, 23 1 Cinnamaldehvde. 677.872.973 4-Chloro-2-hexene. 4 15 synthesis, 80 l 1294 Cinnamic acid Crystallinity

Cinnamic acid (3-phenylpropenoic acid), 8 11,8 17, Conformational analysis, 79-82,85 - 86, 1 t972.977 149-150 cinnamyl alcohol, see 3-Phenyl-2-propen-1-01 aldoses, 1178-1180 cis and trans isomers, see Geometric isomerism amylose, 1194- 1196 Cit*, 705,9 15 angle strain, 454 Citnc aad, 1114, 1139 anomeric effect, 1180 Citronellol, 412 butanes, 85-86 Claisen condensation, 772,802,81 1,8 13 - 8 16 cyclobutane, 459 crossed, 8 16 cyclohexane, 455 -463 Cleavage derivatives, 466 -47 1 acid-catalyzed, 482,483 -484,910 1,3-diaxial interaction, 46 1 by acids, 242 -243 1,2-dimethylcyclohexanes,466 - 470 of alkenes, 358-360 dipole-dipole interachon, 454 base-catalvzed. 483. 485 E2 elimination, 472-473 ofbonds, 22 ' ' ethane, 82 of epoxldes, 482,483-484 factors in, 454-455 of esters, 775, 777 D-(+)-glucose, 11 78 - 11 80 of ethers, 242 -243 methycyclohexane, 462-463 of ketones, 676 NMR and, 644, 1184 ozonolysis, 358- 360 proteins, 1229 by periodic acid, 699 pyranoses, 1178 - 1180 by permanganate, 359 -360 torsional strain, 82. Sw2.485-487 van der Wads swan, 86 chik spectroscopy, 629 -639 Conformational isomers, definition of, 149 Coal, 1,94,555 Conformers, 149- 150 as source of aromatic compounds, 555 Coniferyl alcohol, 9 19 Coal gas, 555 Conjugated double bonds, 977-978 Coal tar, 555 in al@nylbenzenes, 578 as sokof carboxylic acids, 720 ultraviolet absorphon band shift, 599 Cocaine, 159, 1073 in a,p-unsaturated carbonyl compounds, Coconut oil, t 112 1 Conjugated proteins, 1228- 1229 Cod liver oil, t 112 1 Conjugation, 387-424,576-578 Codons, 1247 Conjugative effect, 406 Coenzyme A, 882, 1128, 1132 Conrotatory motion, 1007- 1009 Coenzvmes. 1229 Converters, 119 coke, 355 ' Coordination polymerization, 1087 - 1089 Collagen, 1225, 1234 Coordination sphere, 1043 Collision energy, 57 - 58 Cope reaction, 8 11,927 Collision frequency, 55-58, 108 Cope rearrangement, 10 19 Collisions, 5 1 Copolymerization, 1083- 1084 Combustion of hydrocarbons, 42-43,72,1 l Copolymers, 1083 119 Copper chromite, 780 ~ombustiontrain, 73 Corey, Robert B., 1230 Concentration, and reaction rates, 177 - 178 Corey-House synthesis, 101- 102 Concerted reactions, 1004, 1005 - 1024 Corn oil, t1121 Condensation polymerization, 356, 1079 a-Corticotropin, 1217 Conessine. 1140 Cortisone, 984, 1135, 1136 configuration Colynebacterium diphtherium, 1138 absolute, 155, 183, 1165, 1166- 1168 Corynomycolenic acid, 1138 of aldoses, 1160- 1162 Cottonseed oil, t112 1 of amino acids, 12 12 Coulson, C.A., 6,453 . of carbohydrates, 1155- 1167, 1173- Coumarane, 9 16 cis and trans, 279 Counter-ion, 257 D and L, 1162-1164, 1166 Coupling, of diazonium salts, 866,878 definition. 140 Coupling constants, 6 14 Eand Z, 281-282 Covalent bonds, see Bonds of (+)-glucose, 1155 - 1160 C&phthienoic acid, 1138 inversion of, 182, 183, 367 Craclun~.96. 120- 121 and optical rotation, 141 R andS, 140-141, 1108, 1163 relative, 155 retention of, 840 sequence rules for, 140- 143, 148 - infrared spectrum, 9 13 x-ray analysis, 140 m-Cresyl acetate, 901 Configurational isomers, definition, 150 Cresols, industrial source, 555 -556 Conformation Crick, F.H.C., 1242- 1246 anti, 85, 472 Crossed aldol condensation. 809 - 8 10 boat, 455 -460 Cross formulas, 1148 chair, 458,463,467 Cross-links, in rubber, 420 definition, 79 Crotonaldehyde, see 2-butenal eclipsed, 79 trans-Crotonic acid, 75 1, t972,975,978 envelope, 490 Crotonyl-S-ACP, 1134 gauche, 85 Crotyl alcohol, t216 half-chair, 458 Crotyl chloride, t 169 NMR and, 644, 1184 Crotyl iodide, t169 skew, 79 Crown ethers, 272,478-481,916 stability, factors affecting, 454-455 Crystallini staggered, 79 degree or1094 twist-boat, 455 -460 of polymers, 1088, 1093- 1094 ~pentadienylfree radical

Cyclodextrins, 1198- 1200, 1204 stal structure uses, 1199, 1200 f macromolecules, 1093- 1094 Cycloheptane, t444 nd melting points, 27 1,3,5-Cycloheptatriene, 1076 nd physical properties, 945 Cycloheptatrienyl anion, 505 . Cycloheptatrienyl cation (tropylium ion) umahnone, 916 electronic configuration, 505,1000,1002 nene (isopropyl+nzene), t553,559,894, 895 molecular orbitals, 1002 nene hvdro~eroxlde,894.895 n electrons, 505, 1000 :arranpkmeit, 895 -897 ' Cycloheptatrienyl radical, 505 nulated double bonds, 410 Cyclohexadiene, 499 xic bromide, 935 1,3-Cyclohexadiene, 400 - 40 1,414,444, t44 tius rearrangement, 839 1005 rnarn.de, 781,783,784 reactions, 983 mnic acid, 78 1 1,4-Cyclohexadiene, t444 mnides, see Nitriles Cyclohexane, t444,445,446,461 noa acetic ester, see Ethyl cyanoacetate aqalysis, 487 yocompou.nds, see Nitriles mal bonds, 460-463 .yam- 1,3-d1phenyl- l-propanone, 976 bond dssociabon energy, 503 inohvdrins. 678-679.1146 configuration, 456 ?rm&on, 673 conformational analvsis.. . 455 -463. .yano-7-trifluoromethylnorcaradiene,10 12 derivatives :yano-7-trifluoromethyltropylidene,1012 conformational analysis, 466 -47 :lic aliphatic compounds, 443-492 stereoisomerism, 463 -473 .nalysis, 487-488 equatorial bonds, 460-463 .ngle strain, 450-454 heat of combusbon, 45 1 5aeyer strain theory, 450-454 industrial source, 446 :onformationalanalysis, 455-463,466-471 NMR spectrum, 628-629 :ycload&fion, 473-476, 1013-1018 puckered ring, 452 lefinition. 1057 shape, 456 lehydrogenation, 446 Cyclohexanecarboxylicacid, 7 13,7 14, t7 15 ,3-dimal interaction, 46 1-463 1,2-Cyclohexaned$arboxylic acid, 764 :lectrocyclic reactions, 1005 - 1013 1,2-CyclohexanedIol, 445,470 ieats of combustion, 450-453, t451 1,2-Cyclohexanediol decetafe, 1039 ndustrial source, 446 -447 trans- 1,2-Cyclohexane&ol &acetate, 1040 nethylene ad&bon, 473 - 478 Cyclohexanol, 2 14, t2 16 iomenclature, 443 -446 industrial source, 446 - 447 ~hysicalproperties, t444 NMR spectrum, 624 )reparation, 447 -448 reactions, 835 cycloaddition, 473-476, 1013- 1018 Cyclohexanone, 98 1 methylene addIbon, 473 -478 preparation, 835 ring closure, 447-448,452, 1005- 1013 reactions, 680,800,801,937 .eactions, 448 ;449 Cyclohexatriene, 497,499 .elative stabhbes, 450-453,458-459,466- Cyclohexene, 323,391,400-401, t444,448, 467 A99 ing closure, 447-448,452, 1005- 1013 pr&&ation, 835 ing opning, 449 Cyclohexene oxide, 1054 ;mall nng, 449 -450 3-Cyclohexenol, 445 ;tereoisomerism, 463 -47 1 Cyclohexylamine, t824 See also Cycloalkanes; Cycloalkenes) preparation, 835 $c anhydrides, 765 Cyclohexyl bromide (bromocyclohexane), t169, chc bromo~numions, 374- 376 628.644.835 clic compounds, see Arenes, Aromatic com- ~~clohexylbiosylate, substituted, 1041 ~ounds,Cyclic aliphatic compounds, Hetero- Cyclohexyl chloride, t169 cyclic compounds hydrolysis and neighboring group effects, 1038 clic esters (lactones), 770 Cyclohexyl tosylate, 1040 ~licethers, 478 (See also Crown ethers; Epoxides) cis,cis-Cyclonona- l ,3-diene, 1027 rclic halonium ions, 340,376,487,952 cis,cis,cis-Cyclonona- 1,3,5-triene, 1012 ~licmercurinium ions, 347,487 cis,cis,trans-Cyclonona-1,3,5-triene, 1012 clization. 447. 556 (See also Cycloaddition reac- Cyclooctadecanonaene, 1000 tions; ~1ectroc~clicreactionsj cis,cis-Cycloocta- l ,3-diene, 1025 cloaddition reactions, 473 -476 cis,trans-Cycloocta-1,3-d+ne,1025 [2 + 21, 1014 1,5-Cyclooctadiene, reactions, 934 [4 + 21,983 Cyclooctane, t444 definibon, 448 1,3,5,7-Cyclooctatetraene,516 Diels-Alder reaction, 982 - 984 Cyclooctatetraenyl dianion, 1000 and orbital symmetry, 1013 - 10 18 1,3,5-Cyclooetriene, 1024 rcloalkanes, 94,443-445, t444 (See also Cyclic Cyclopentadene, 505,1028 aliphatic compounds) 1,3-Cyclopentadiene, t444, 445,982 rclobutane, 444, t444,45 1 Cyclopentadienyl anion conformations, 459 electronic configuration, 505 - 506, 507, 1000 - reactions, 449 -450 inn? 3-Cyclobutanedicarboxylicacid, 464 molec;1'& orbitals, 1001- 1002 rclobutenes, electrocyclic reamons, 1005- 1024 Cyclopen@dienyl cation rclodecane, 460 electroluc configurabon, 505, 1002 puckered ring, 452 molecular orbitals, 1001 - 1002 5-Cyclodecanedione, 492 Cyclopentadlenyl free radical zns,cis,cis-Cyclodeca-1,3,5-triene, 10 12 electronic configuration, 505,1001 - 1002 Cyclodextrin, 1199, 1200, 1204 molecular orbitals, 100 1 1296 Cyclopentane Diastereomers

Cyclopentane, t444, 445,448,45 1 Dehydrogenation conformational analysis, 459 of alicyclic hydrocarbons, 446 preparation, 672 industrial, 555-556,576-577 stereoisomerism, 464 -466 Dehydrogenahon enzymes, 1228 Cyclopentanecarboxylic acid, 927 Dehydrohalogenation cis-1,2-Cyclopentanedicarboxylicacid, 764 of allcyl dihalides, 429 -430 1,3-Cyclopentanedicarboxylic acid, 464 of alkyl halides, 174,288,290-293 1,2-Cyclopentanediol,704 E2,293-294,302 chirality, 465 -466 kinetics of, 293 cis and trans isomers, 2 17,464-466 order of reactnity in, 302 Cyclopentanol, t2 16,445 orientation of, 30 1- 302,306 preparation, 672,677 use in synthesis, 973 Cyclopentanone, 672,763 of vicina! dihalides, 429-430 formation, 763 Delocalizatmn energy, 398 (See also Resonance reactions, 672,677 energy) Cyclopentene, t444 Delocahzation of electrons, 200, 398, 401 -402, reactions, 482,935 413,501 -502,568 Cyclopentene-l-carboxaldehyde, 9 17 Demercuration, 346-347 Cyclopentene oxide, 482 Denaturant, 22 1 B-Cyclopentyl-9-BBN, 935 Denaturation Cyclopentenyl cation, 101 1 of nucleic acids, 1226 Cyclopropane, 444, t444, 448,45 1 of proteins, 1226 preparation, 447 Denatured alcohol, 221 (See also Ethanol; Ethyl reactions, 449-450 ' alcohol) Cyclopropanecarboxylic acid, 927 D,L-Dendroketose,l l83 Cyclopropenones, 1003 Deoxyribonucleicacid, see DNA Cyclopropenyl anion, 1002, 1003 ~-2-Deoxyrib0~,1241 Cyclopropenyl cation, 1000, 1002, 1003, 101 1 Derivative, definition, 12 1 Cyclopropenyl free radical, 1002, 1003 Desulfonation, 529- 530 Cyclopropyl cauon, 10 11 Detergents, 1126- 1127 2-Cyclopropyl-2-propanol,646 biodegradable, 1126 - 1 127 2-Cyclopropyl-l, l, l-trideuterio-2-propanol 646 manufacture of, 1089 Cycloreversions, 10 17 non-ionic, 1126 m-, o- and pCymene, 1200 solubility and cleansing power, 253 pCymene, t553 m-Deuterioaniline, 839 (-)-Cysteine, t1206 m-Deuteriobenzamide, 839 Cysteinylglycine, 1220 o-Deuteriobromobenzene, 964 (-)-Cystine, t1206 a-Deuterioethylbenzene, 132, 135 Cytochrome c, 1248 a-Deuterioethylbromide, 142 Cytosine, 1243 o-Deuteriofluorobenzene, 964 in nucleic acids, 1241- 1243, 1245,1246- 1247 3-Deuterioindene, 1021 Deuterium isotope effects, 295-297, 532-535,964,969, D r nwa label& ;or NMR spectra.-. 623 -625 D, prefix, 1162-1164, 1166-1167 separation, 117 d, prefix, 1163 tracer studies, 117,298, 364, 380, 807, 839, Dacron, 744, 1090, 1094 1056, 1103- 1106, 11 13, 11 14 "Dansyl" method, 1220 Deuterium exchange, 297-298,807,969 Deactivating groups, 520,522,538-539 Deuterium oxide, 117,334 Decalin (decahydronaphthalene), 489 Deuteron. 298 cis-Wn, 644-645 "Dewar" benzene structure, 495,497, 1029 n-Decane, i93 Dewar, Jarnes, 497 cis,cis,cis,cis,trans-Deca-1,3,5,7,9-pen,1025 Dewar, M.J.S., 414, 952 Decarbonylation, 106 1 Dextrans, 1198 Decarboxylation Dextrorotatory, definition, 129 of aromaucacids, 729 Dextrose, 119 1 of keto aclds and malonic acids, 930 - 93 1 DHP (dihydropyran), 788 2,4,Q~eeatetraene, 101 1 Diacetannde, 860 l-Decene, t285 Diacylglycerol phosphate, 1128 - 113 1 n-Decyl alcohol, t216 Dialkylacetoacetic esters, 927 - 929 l-Decyne, t429 Di3lkylmalonic esters, 925 5-Decyne, t429 Diallyl ether, t238 Degenerate pairs, 1001 Diamides, 1092 Degradation, 12 1 1,4-Diaminobutane (putrescine), 844,986 determination of structure by, 358-360 Diaminobenzenes, 5 14,5 16 Hofmann, see Hofmann degradation Diaminobenzoic acids, 5 16 by oxidation, 359-360 1,4-Diaminobutane, 987 by ozonolysis, 358- 360 1,6-Diaminohexane,830, 880 Ruff, 1154. 2,4-Diaminophenol (amidol), 9 15 Dehalogenauon, of vicinal dihalides, 288,289 Diamond, 3 Dehydrafion, 3 12- 3 13 structure, 446,5 12 of alcohols, 288,289,306,310-315 Diarylmethanols, 704 mechanism, 3 12 Diastase, 1185 order of reactivity, 3 11 Diastereomers, 125, 133, 144- 146, 159, 381 of aldol products, 807 - 808 comparison of properties, 145 - 146 Dehydrobenzene, see Benzyne definition, l45 7-Dehvdrocholesterol. 1030 formation, by generation of second chiral Enter, 156-158 Diastereoselectivity Dienes

geometric isomers as, 279, 281 physical constants, t742 m resolution, 158 - 160 preparation, 743 (See also Anomers; Epimers) Dichloroacetic acid, 750 Diastereoselectivity, 383, 1046- 1049 preparation, 727,741 Diastereospe&%city,38 1, 1046 - 1049 2,4-Dichloroaniline, 868 Diastereotopic faces, 110 1- 11 15 m-Dichlorobenzene, 868, 845,946 Diastereotopic ligands, 110 1- 11 15 o-Dchlorobenzene, 845,946 Diastereotopic protons, 603 pDichlorobenzene, 845,946 1,3-Diaxial interactions, 461 -463,468 2,6-Dichlorobenzoic acid, 745 Diazo coupling, 519,878 1,2-Dichlorobutane,chirality, 153 Diazocyclopentadiene-2carboxylicacid, sodium 1,4-Dichlorobutane,830 salt, 990 2,3-Dichlorobutane, 146- 147, 156- 158,384 Xazomethane, 474,475 meso-2,3-Dichlorobutane,157, 1107 xazonium fluoroborates, 869 Dichlorocarbene, 477,908 -909 3azonium hexafluoro~hos~hates.--,869 l, l-Dichlorocyclopropanes, 938 Xazonium salts 2,2'-Dichlorodiethyl sulfide, 1037 coupling, 866,868,873-875,878 1,2-Dichloro-l, l dduoroethane, NMR spectrum, preparation, 864,866 617 reactions, 866 DicGi;odifluoromethane, 69 replacement of nitrogen, 866 - 868 1,3-Dichloro-2,3dimethylbutane,435 by -CN, 866-867,870 2,3-Dichloro-2,3dimethylbutane,435 by halides, 866-867,869-870 3,3-Dichloro-2,24imethylbutane,435 by hydrogen, 867-868,871 3,3-Dichloro-1,2-dimethylcyclopropane,476 bv --OH.867 -868.870 trans-2,5-Dichloro- l ,Moxane, 1 184 synbeses using, 87 11873 1,2-Dichloroethane,t169,617, 833 libenzalacetone, 872, 986 l, l -Dichloroethene, 1094 Xbenzyl ketone, 988 1,2-Dichloroethene, 285 )iborane, 222,32 1,347 - 348 geometric isomerism, 280 ,5-Dibromo4aminotoluene, 86 1 Di(2chloroethyl) ether, 9 16 ,2-Dibromobenzene, 496,500 a,cu1-Dichloroglutaricacid, 742 ,3-Dibromobenzene, 496,500 Dichloromethane (methylene chloride), 43,44, ,CDibromobenzene, 496,500 t169,258,442 I-Dibromobenzene, 508,845,970 1,2-Dichloro-2-methylbutane,16 1 -Dibromobenzene, 508, 845 1,2-Dichloro-3-methylbutane,142 -Dibromobenzene, 508, 845,970 2,3-Dichloro-3-methylpentane,92 ,6-Dibromobenzenediazoniumchloride, 969 endo-cis-2,3-Dichloronorbomane,473 ,3-Dibromobutane, 368-372, 1032- 1033 trans-2,3-Dichloronorbomane, 473 dehalogenation, 289 2,3-Dichloropentane, 144- 145, 148 stereochemistry of formation 2,4-Dicbloropentaned1oicac~d, 739 from 2-butenes, 368 - 372 1,2-Dichloropropane, 389 from 3-bromo-2-butanols, 1032- 1034 conformations, 627 - 628 zeso-2,3-Dibromobutane, 371, 373, 375,386 %R signals, 602 E-2,3-Dibromobutane, 371, 1034 1,3-D~chloropropane,447,449 ?,S)-2,3-Dibromobutane, 373 3,4-Dichloro-1,2,3,4-tetramethylcyclobutene,1003 ,4-Dibromo-2-butene,414 Di(pcyanoethyl)amine, 978 4-Dibromo-l-butene, 4 14 Dicyclohexylcarbodiimide (DCC), 1224 !3,3a-Dibromocholestane, 1141 Nfl-Dicyclohexylurea, 1224 2-Dibromocyclohexane, 448 Dicyclopentadiene, 10 18 2-Dibromocyclopentane,464 Dicyclopentadienyliron(ferrocene), 505, 506, 2-Dibromo-1,2diphenylethane,385 1042,1044 l-Dibromoethane, t169 Dieckm~ncondensation, 8 11,8 15 NMR spectrum, 610,612,615 Dielectric constant, 32 2-Dibromoethane, t169 Diels-Alder reaction, 1028 cis and tram isomers, 280 orbital symmetry, 10 13 - 1018 2-Dibromoethene, 280,34 1 retro, 1028 6-Dibromo-2,4-hexadiene,424 stereochemistry, 10 13 - 10 14 6-Dibromo-1,3-hexadiene, 424 Dienes, 409 -4 12 5-Dibromohexanes, 1028 denes, f411 ~,6~bromo-3j3-hydroxycholestane,1 141 stabhtv. 4 11 ibromomethane, t 169 6-Dibromo-2-methylphenol, 906 analysis, 4 12 - 422 2-Dibromo-2-methylpropane, 340 conjugated, 409-4!0,411-422 NMR spectrum, 6 17 1,2- vs. 1,4-addifion, 41 5 -419 S-Dibromo-4-nitroaniline,873 bonds in, 41 1-412 6-Dibromo-4-nitrobenzenWnium hydrogen cycloaddition, 982, 10 13 sulfate, 873 Diels-Alder reaction. 10 13 - 101 8 7-Dibromonorcarane, 174 ease of formation, 4 f4 S-Dibromo-l-pentene, 414 electrocyclic reactions, 1005- 1013 2-Dibromo-l -phenylethane, 6 19 electronic configuration, 996- 1000 2-Dibromopropane, 3 19,339,429 electrophihc addition, 4 14-4 19 5-Dibromopyridine, 1068 orientation, 4 15 -4 19 -n-butylamine, 847, 859 rate vs. equilibrium, 4 16 - 4 19 N-Di-n-butylbenzenesulfonamide,859 molecular orbitals, 996- 1000 -tea-butyl carbonate, 1223, 1224 polymerizauon, 420 3-Di-tert-butylcyclohexane, 490 resonance, 411-412 -n-butyl ether, t238,239 sigmatropic reactions, 10 19 - 1024 5-Dicarbonyl compounds, 820 stability, 410-41 1 carboxylic acids, 742-744,763 heats of hydrogenation, t411 acidity, 744 nomenclature, 409 -41 0 1298 Dienophile 2,4-Dinitrochlorobenzene

Dienes, (cont.) 3,3-Dimethyl-2-butanone (tert-butyl methyl ke- stability, 410-41 1 tone), 705,800,935 structuk, 409-410 2,3-Dimethyl-l-butene, 305,306, 314 Dienophile, 982, 1013 heat of hydrogenation, t326 Diethylamine, 49 1, t82~l 2,3-Dimethyl-2-butene, t285, 305, 306,314 5,5-Bethylbarb~turicac heat of hydrogenation, t326 Diethylene glycol, 484 3,3-Dimethyl-l-butene, 208,282,316, 321, 322, Diethvlenetriamine. 1099 335,347,349,442 Diethi1 ether, 34, 38, t217,237, t238,258, t272, he* of hydrogenation,.t326 442.660 3,3-Dimethyl-2-butyl cahon, rearrangement, 206 absolute ether, 240 3,3-Dimethyl-l-butyne, t429,435 hazards, 240 3,4-Dimethylcyclobutene,1005, 1008 industrial source, 238 -240 5,6-Dimethyl-1,3-cyclohexadiene,1006, 101 1 preparation, 240' 1,2-Dimethylcyclohexane solubility, 218,238 CM@,468-469 3,3-Diethyl-5-isopropyl-4-methyloctane,9 1 conformational analysis, 467-469 o-, m-, and pDifluorobenzene, t945 stability of isomers, 467 - 468 1,2-Difluorotetrachloroethane,NMR spectrum, 629 1,3-Dimethylcyclohexane,444, 445,468 3,3-Difluoro-2,2,3-tnbromopropanenitrile,NMR 1,4-Dimethylcyclohexane,468 spectrum, 629 Dimethylcyclooctatriene, 101 1 Diglyme, 348 l,l-Dimethylcyclopentane, 444 Dihalocarbenes, 477 1,2-Dimethylcyclopentane,t444 Dihydromyrcene, 424 industrial source, 446 cis-9,lO-Dhydronaphthalene,1026 3,5-Dimethylcyclopentane,449 trans-9,lO-Dihydronaphthalene,1025 2,5-Dimethylcyclopentanecarboxylicacid, 489 Dihydrophellandric acid, 9 17 2,s-Dimethyl- l, l-cyclopentanedicarboxylicacid, Dihydropyran (DHP), 788 489 2,3-Dihydro-4H-pyran (DHP), 696 cis- 1,2-Dimethylcyclopentanol,490 Dihydroxyacetone, 1183 1,2-Dimethylcyclopentene,490 Dihydroxybenzenes, 889 (See also Hydroquinone; 1,2-Dimethylcyclopropane

Resorcinol) cis and trans isomers., 465.644 , 3,4-Dihydroxybenzoic acid, 918 preparation, 475 2,4-Dihydroxyphenyl n-pentyl ketone, 901 Dimethyl ether, 36, t238 erythro-2,3-Dihydroxy-3-phenylpropanoicacid, Dimethylethylamine, 830 818 Dimethylformam.de(DMF), 185,255,263 o-, m-; and pDiiodobenzene, t945 as solvent, 926 l,l-Diiodoethane, t 169 N,N-Dimethylformamide, NMR spectrum, 12 16 1,2-Diiodoethane,t169 2,5-Dimethyfiran, 1062 Diiodomethane, t169 2,3-Di-0-methyl-L-galactose,1203 Diisocyanates, 1092 2,3-Di-0-methyl-D-galacturonicacid, 1203 Diisopropyl ether, 233,237, t238,242 2,3-Di-0-methyl-D-glucose,1198 &Diketones. 939 2,4-Di-0-methyl-D-glucuronicacid, 1203 'blcetopipekine, 1248 p,p-Dimethylglutaric acid, 742 Dilactones, 789 2,2-Dimethylheptane, 99 Dimerization, of alkenes, 320,343 - 344 l, l-Dimethyl-2-isopropenylcyclopentane,423 Dimers, 343 3,4-Di-0-methyl-D-mannose,1203 3,4-Dimethoxybenzaldehyde,674 2,3-Di-0-methyl-D-mannuronicacid, 1203 3,4-Dimethoxybenzyl alcohol, 674 2,7-Dimethyl-2,6-octadiene,423 N,N-Dimethylacetamide, 789 3,7-Dimethyl-3-octanol, 778 Dimethylacetoaceticacid, decarboxylation, 93 1 Dimethylolurea, 1092 Dimethylacetylene (2-butyne), 428, t429, 431 2,2-Dimethyl-3-oxobutand,937 Dimethylallyl pyrophosphate, 1137 3,3-Dimethylpentanedioic acid, 742 Diplethylamine, 821, t824, 826, 846 4,4-Dimethyl-l-pentene, 1326 industrial prepara~on,828 Dimethyl-tert-pentylsulfoniumethoxide, 857 reactions, 830,846 Dimethyl-tert-pentylsulfoniumiodide, 857 synthesis, 954, 2,2-Dimethyl-l-propanol,215,727,772 3&Dimethylaminoconanin-6-one, 1140 Dimethyl-n-propylamine, 847 '3&Dimethylaminocon-5-enine, 1140 2,5-Dimethylpyrrole, 1062 5-Dimethylaminonaphthalenesulfonylchloride, 6,9-Dimethylspiro[4.4]nona-l,3diene,1024, 1028 1220 Dimethyl sulfide, 264 Dimeth~lammoniumnitrate, 846 Dimethyl sulfoxide (DMSO), as solvent, 255,263, 2,4-Dimethylaniline, t824 724,926 N,N-Dimethylaniline, 821,829,836 2,5-Dlmethylthiophene, I062 reactions, 846, 849, 865 a$-Dimethylvalenc sad, 7 16 N,N-Dimethylanilimum acetate, 846 2,3-Di-0-methyl-D-xylose,1198 2,4-Dinitroaniline, t824 preparation, 949,954 2,4-Dinitroanisole, 954 Dinitrobenzenes, 954 2,4-Dinitrobenzenediazonium chloride, 874

2;2-Dimethilbutane, 83p ' 3,5-Dinitrobenzoates, see specijic alcohol, deriva- 2,3-Dimethylbutane, 83, 364 tivor 2,3-Dimethyl-2,3-butanediol(pinacol), 705 2,4-l%&obenzoic acid, 7 16 2,2-Dimethylbutanoic acid, 720,722 3,5-Dinitrobenzoic acid, 737, 762 2,3-Dimethyl-2-butanol, 772 3,5-Dinitrobenzoyl chloride, t755 3,3-Dimethyl-l-butanol, 322 preparation, 737 preparation, 349 reactions, 762 3,3-Dimethyl-2-butanol,230, 306 2,6-Dinitro-4-tert-butyl-3-methylanisole,9 15 dehydration, 3 14 2,4-Dinitrochlorobenzene,t945 preparation, 32 1,346 reactions, 829, 898,949,953,954,968 line Electrophilic addition l

4,4'-Dinitrdphenylamine, 823 (E)-9-Dodecen- l -yl acetate, 382 2,4-Dinitrofluorobenzene (DNFB) (2)-9-Dodecen-l-yl acetate, 382 reactions, 970, 1249, 1250 n-Dodecyl alcohol, t2 16 in terminal residue analysis, 12 18 - 12 19 6-Dodecyne, 430 1,5-Dinitronaphthalene, 5 10,547 Doebner reaction, 8 11 1,8-Dinitronaphthalene, 547 L-Do~a.105 1 2,4-Dinitronaphthol, 547 ~ou6le'bonds,see Carbon-carbon double bonds, 2,4-Dinitro- l-naphthylamine, 5 10 Carbonyl oup 2,4-Dinitrophenol, t890,905,954 Double helix, &r DNA, 1244 preparation, 898,949,953 Double irradiabon in NMR spectroscopy, 624-625 N-Dinitrophenyl (DNP), .l2 18, .l249 Double resonance in NMR spectroscopy, 624-625 N-(2,4-Dmtropheny1)amno acld (DNP-AA), 12 19 Dow process, 894,948 2,4-Dinitrophenyl ethyl ether, 949 Dry Ice, 723 2,4-Dinitrophenyl phenyl ether, 970 Drying oils, 1127- 1128 2,4-Dinitrophenyl phosphate, 1137 Duck. D.. 474 2,6-Dinitrotoluene, 509 1.2-Diols (dvwls). 357-358 ' analysiS;-699 '. gene, i553 preparation, 322,357-358,578 Dyes, azo, 875 l ,a-Dioxane, i238 Dypnone, 872 industrial preparation, 478 Dipeptides, 12 15 (See also Peptides) Diphenylacetylene,t553 Diphenylamine, 330, 823, t824 E 1-4-Di~henvl- 1-3-butadiene. 8 12. 10 17 El mechanism, see Elimination reactions E2 mechanism, see Elimination reactions Eclipsed conformation, 79 in E2 elimination, 473 ' preparatibn, 558 ' ' Edman, Pehr, 1219- 1220 1,l-Diphenylethene, t553, 812 Egg albumin, 1234 trans-1,2-Dphenylethene, 386 Elastic fibers, 1097 1,2-Diphenylethenes, 583 Elastomers, 1077, 1094 Diphenyl ether, t238 Electrocyclic reactions, 1005 - 10 13 Diphenyl ketone, see Benzophenone Electromagnetic radiation Diphenylmethane, 546,551,1553,558,575 absorption, 590 -620 Di~henvlmethanol.12 16. 552 related to frequency, 589-590 %5hen$lmethyl biomide, t169 wavelengths in, 589- 590 Diphenylmethyl chloride, t169 Electromagnetic spectrum, 69,589 - 590 1.2-D~phenyl~rownes,377 - 380,399 Electron density, 6 Electronegative elements, 4 Electronegati@ty, 23,850 Electronegab~tysenes, 23,436 1,3-Diphenylpropenone,8 10 Electrogc configuration, 8, t8,996- 1000 1,3-Diphenyl-2-propen-l-one,80 1 Electromc effects Diphosphopyridinenucleotide,see NAD accommodation of charge, 199 Dipolar ions, 862-863 and acidity, 735-736 amino aclds as. 1208- 12 11 In mines, 852-853 phospholipids &, 1130 in aromatic substitution, 536- 544 Dipole-dipole bonds, 259 -260 and basicity, 850-852 Dipoledipole interactions, 28,454, 1180 in carbocations, 196 -203 in macromolecules, 1093- 1095 in carboxylic acids, 728-729 Dipole moments, t24,24-26,295 1 effect of substituent groups, 852-853 Dipoles, 23 in electrophilic addition, 336-339,978-979 Di-n-propylamine, t824 of functional groups, 974 Di-n-propyl ether, t238 in Hofmann degradation, 841 -843 infrared spectrum, 596 infrared absorption shift, 590 Diradicals, 394,475 in nucleophilic addition, 670-671,978 Disacchyides, 1185- 1192 in nucleophilic aromatic substitution, 952-956 defimbon, 1144 in %l reactions, 200-203,961 (See also (+)-Maltose; Sucrose; (+)-Sucrose) in h2reactions, 185- 188,961 Disparlure, 1055 (See also Inductwe effects; Resonance effect) Disped of charge, 406,73 1 Electronic structure, 5,37 Disrotatory motion, 1007- 10 1l. Electronic transibons, 597 Dissociation energy, see Bond mssociation energy Electron-pair acceptor and donor, 34 and insidefront cover Electron paramagnetic resonance, see Electron pDivinylbenzene, 584 spin resonance spectroscopy Divinyl ether, t238 Electron release, 199,540- 542 DMF, 185,255,263,926 Electrons DMSO, 255,263,724,926 odd. 47.64 DNA (deoxyribonucleic acid), 69, 1250 paired, 8 structure, 124 1- 1246 Electron sharing. 4 (See also Bonds) and genetics, 1246 - 1247 Electron spin, c573 DNFB, see 2,4-Dinitrofluorobenzene Electron spin resonance (ESR) suectra, 393,586, DNP (N-dinitrophenyl), 12 18, 1249 Electron @in resonance (ESR) ipectroscopy DNP-AA (N-(2,4-dimtrophenyl)arn1noacid), 12 19 of free radicals, 573 n-Dodecane, t93 m reaction studes, 352 Dodecanoic acid, 7 13,740 Electron transfer, 4 l-Dodecanol, 780 Electrophilic addition, 3 18,332- 333,353,974 (E)-8-Dodecan-l-yl acetate, 382 976.978 (Z)-8-Dodecen-l-yl acetate, 382 to alkenes, 332-345 1300 Electrophilic aromatic substitution Esters

Electrophilic addition, (cont.) Enantiospecificity, 38 1,1112 - 1 11 3 to akenylbenzenes, 579- 580 Enantiotopic faces, 1050, 1101 - 1115 to alkynes, 430-433,434-435 Enantiotopic ligands, 110 1 - 11 15 to a$-unsaturated carbonyl compounds, 974- Enantiotopic protons, 603 976 End group analysis, 1194- 1195 to c&;gated dienes, 414-419 Endothermic reactions, 54 definition, 3 l8 Enediol, 1150 effect of substituent groups, 338,974-975 Energy of activation, see Activation energy hydroboration, 349 Energy changes, 52-55 orientation. 337 Energy content, 66 and readvity, 335-338 Energy factors, 59 oxymercuration, 346 - 347 in reaction rates, 56 reaction mechanism, 332 - 334 Enolate anion, 798 rearrangements, 334-335 Enolic proton chemical shift, t607 (See also.Addition. reactions) Enolization, 804-805 Electrophihc aromahc subshtution, 5 17- 548 Enol-keto equilibrium, 435-436,976,977, 1149- ~rm alkylbenzenes, 562,564 llJV amines and amides, 848,852-853 Enthalpy, 50 couplin of diazonium salts, 873-875 Enthalpy change, 730 effect ofhalogen, 944,948 in macromolecules, 1093- 1096 effect of subfituent groups, 5 19 - 520 Entropy change, 730 Friedel-Crafts acylation, 666, 901 in macromolecules, 1093- 1096 furan, pyrrole, and thiophene, 1062- 1064 Entropy of activation, 67 (See also Activation en- mechanism, 530-535 ergy) naphthalene, 545 -546 "Envelope" conformation, 490 nitrosation of amines, 865 Enzymeaction, 1112-1113, 1114, 1236-1240 orientation, 5 19- 52 1, 522-525 Enzymes, 137, 1054, 1248 phenols, 906 - 907 solubility and shape, 253-254 pyridine, 1068- 1069 (+)-Ephedrine, 137 reaction mechanisms, 525 - 530 Epichlorohydnn, 1099 relative reactivity, 52 1- 522 Epimers, 1152,1153 Electrophilic reagents, 31 8,333 interconversion of, 1154 - 1155 Electrophoresis, 1227 Epoxidation, 322,484 Electropositive elements, 4 Epoxide ring, 48 1 Element effect, 298 - 300,960 Epoxides, 376,384,478 Elimination-addition mechanism, 944,962-967 cleavage, 482 - 487 Elimination reactions, 174,288 -3 15,334 acid-catalyzed, 482,483 -484,9 10 by acetylides, 439 base-catalyzed, 483,485 from alicyclic compounds, 47 1-473 orientation, 485 -487 of alkyl halides, 242 in formation of 1,2-diols, 482,483-484 of alkyl sulfonates, 234 in pinacol rearrangement, 704 in a-halogenated acids, 741 -742 preparation of, 48 1 anti-, 378- 380 protonated, 483,485 j3- and a-, 477 reactions, 482-483 dehydration of alcohols, 3 10- 3 15 with Grignard reagents, 483,485 1,l-, 477 in Williamson synthes~s,9 10 - 9 11 1,2-, 246, 290-293, 308, 477 Equatorial and mal conformations, energy differ- ElcB, 298 ence, 463 E l mechanism, 303 - 307 Equatorial bonds in cyclohexane, 460-463 evidence for, 304-307 Equilibrium, 730-732 orientation, 306- 308 in estedcation, 737 . reactivity m, 304 Equilibrium constant, 730 vs. E2, 308 Ergocalciferol, 1030 E2 mechanism, 293-294,855 Ergosterol, 1030, 1136 absence of hydrogen exchange, 297-298 L-Erythritol, 11 15 absence of rearrangement, 294-295 L-Erythntol-l-phosphate, 11 15 element effect, 298 - 300 Erythro &astereomers, 377, 380 evidence for, 294-306 Erythrose, 380 isotope effects, 295-297 (--)-Erythrose, 789, 116 1 kinetics, 294-295 ESR, see Electron spin resonance spectroscopy orientation and reactivity, 300 - 303 Essential oils, phenols from, 894 stereochemistry, 377 - 380,471 -473 Estedcation vs. El, 308 of alcohols, 226,726 VS.$42,308-310 by acid @oxides, 726,76 1-762,769-770 Hofmann, 854-855 by anhydrides, 764-765,769 orientation of, 4 14 bv carboxvlic acids. 726.737-739.768-770 preparation of alkynes, 429 - 430 bG esters. 771. 7771778' stereochemistry, 377 - 380 rilative reacti*, 738,769 syn-, 378-380 of carboxvlic acids, 726,737- 739,768-770 vs. substitution, 175, 308-310, 833 bond cieavage, 739 . Empirical formula, determination, 74 relative reactivity, 738 Emulsin, 1188 of dicarboxylic acids, 743 - 744 Enarmnes, 935-937 of glucose, l l45 Enantiomerism, prediction of, 133- 134 intramolecular, 770 Enantiomers, 125, 127, 133, 136- 139, 144,381 (See also Esters; Transesterification) and enantiomerism, 130- 134 Esters, 753,755 configurational, 139 alkylation of, 93 1-932 conf&mational, 139 carboxylic acid, 753,768-783 Enantioselective synthesis, 367 - 386 ammonolys~sof, 771, 778 Enantioselectivity, 383, 1049- 105 1 analysis of, 783-785 Estrogen Ethylcyclopentane 1301

Claisen condensation, 772,802,s 13-8 16 alkoxymercuration-demercuation, 24 1 cleavage of, 77 1-774 dehydration of alcohols, 239 conversion, into acids and acid derivatives, from phenols, 240,902 771 -777 ,,. S,- Williamson synthesis, 240,241 -242,902,910 cyclic (lactones), 770, 989 protonated, 242 -243 hydrogenolysis, 77 1, 780 reactions, 242-243,704 hydrolysis, 771 as solvents, 99, 478 acid, 775- 777 sources, industrial, 238 - 240 alkaline, 772-775 spectroscopic analysis, t592,596-597, t607, t786 hydroxy, 832 structure, 237 keto, see&Keto esters Ethide ion, basicity, 438 malonic, 924-927 Ethoxyacetic acid, 745 nomenclature, 754 3-Ethoxy-l-butene, 406 nucleophilic substitution, 755 -760 l-Ethoxy-2-butene, 405 phenolic, 738, 762, 899, 905 2-Ethoxyethanol, 237,482,483 physical properties, 754-755, t755, t769 Ethoxylates, 1126 preparation, 174,226,233,726,737-739, 2-Ethoxyoctane, 242 768-770 Ethyl acetamidomalonate,988 reactions, 770 773 Ethyl acetate, 226,754, t769,802, 81 1,816 wth carbanions, 77 1 arnmonolysis, 771, 778 with Grignard reagents, 772,779 Claisen condensation, 802,s 13- 8 15,s16 reduction, 772,779 Ethyl acetoacetate, 929,98 1 saponilicafion equvgent, 784 preparafion, 802,814 spectroscopic analysis, 692, t607,784-782 reactions, 929,981,988 structure, 753 relative acidity, 8 14- 8 15 transesterification., 771.777 , -778 (See also Acetoacetic ester synthesis) (See alsp Fa?) Ethylacetylene, 428 phosphonc acld, 1128- 1130 Ethyl awlate, 789, 978 hydrolysis, 1129 EfPyl a,dipate sulfonic acid, 1038- 1039 in D~eckmanncondensation. 8 15 preparabon, 233 preparation, 738 Zstrogen, 1136 Ethyl alcohol, 34,36,215, t21 Zstrone, 1136 771. . - , 778. - , 774. . . Zthanal, see Acetaldehyde dehydration, 288 Zthanamide, see Acetamide iodoform test, 244 Zthane, 110,438 preparation, 33 1,347 andiron formulas of, 80 (See also Ethanol) conformational analysis, 79 - Ethyl alkylmalonate, 924 conformafions. 79 - 82 Ethylamine, t824, 829 empirical fom'ula, 75 Ethyl paminobenzoate, 828 physical properties, 754-755, t755, t769 Ethylammonium sulfate, 823 rotational bderin, 82 l-Eihylaziridine, 827 . structure, 78 - 79,2i6 Ethylbenzene, 550-55 I, t553 Zthanedioic acid (oxalic acid), 705, t742 CMR, chemical shift, 634-635 L ,2-Ethanediol (ethylene glycol), t2 16, 1079 reactions, 561,562-563,564,566,567,576,578 polymer with terephthalic acid, 739, 1090-..- Ethyl benzoate, 546, 754, t769, 816 preparation, 223,358,482 in Claisen condensation. 802 Zthanenitrile (acetoniqe), 258,725 hvdrolvsis. 771. 775 Zthanoic acid. see Acebc ac~d pieparkion, 761 Zthanoic anhydride, see Acetic anhydride substituted. 776 3han01, 35, 210,258, 298 tracer studes, 775 biological oxidation of, 1101 - 1106,1114 Ethyl benzoylacetate, 802, 816 deuterated, 1103 Ethyl benzylmalonate, 1213 sources, 2 19,22 1- 222 Ethyl bromide, t169, 187, 188, 197,240,610, 836, substituted, 247 t95 1 uses, 220,22 1- 222 mspectnun, 612,615 (See also Ethyl alcohol) Ethyl bromoacetate, 933 Ztha?~ia,mine(2-aminoethanol), 483, 5 14, 822, Ethyl o-bromobenzoate, 769 113u Ethyl bromomalonate, 1214 Zthanolamine phosphoglyceride, 1130 Ethyl a-bromopropionate, 927 Zthanoyl chloride, see Acetyl chloride Ethyl bromosuccinate, 1072 Zthene, see Ethylene Ethyl n-butylamine, 836 Zther, see Diethyl ether Ethyl n-butyrate, t769 Zthers, 214,237-247 Ethyl carbamate, 78 1 absolute, 240 Ethyl carbonate, 780, 8 16 analysis of, 244-245 Ethyl cation, 191, 197 wl, 909-912 mass-to-charge ratio, 586 of carbohydrates, 1175 - 1176, 1201 Ethyl chloriqe, 98, 104, 110,t169,447,829 of cellulose, l201 confomahons, 627 cleavage by acids, 242 - 243 NMR signals, 602-603,626-627 as nucleo~hilicreaction, 242-243 Ethyl chloroacetate, 12 13 crown, 478148 1 Ethyl chlorocarbonate, 78 1 cyclic, 478 (See also Epoxides) Ethyl cplorohydrin, 482 as Grignard solvent, 99,240,272,948 Ethyl cmnamate, 81 1,872,980 hydrogen bonding, 238 Ethyl crotonate, 976,980,987 industrial source, 238 - 240 Ethyl cyanoacetate, 980,981 nomenclature, 237 reaaons, 927 peroxides in, 240 Ethyl &c anobutyrate, 976 physical properties, 238, t238 ~thylcycLhexane,463,561,578 preparation, 240-242 Ethylcyclopentane, 445 ene Free radicals

3-Ethylcyclopentene, 444 m-Ethyltoluene, 584 Ethyl cyclopentylacetate, 935 o-Ethyltoluene, 584 Ethyldimethylacetic acid, 722 pEthyltoluene, 551, 584 Ethyl 2,2dimethylpropanoate, 772 Ethyl ptoluenesulfonate (ethyl tosylate), 226,234 Ethyl 2,4dimethyl-3-pyrrolecarboxylate,1063 Ethyl tosylate (ethyl ptoluenesulfonate), 234,226 Ethyl 2,340~0-1,4-cyclopentanedicarboxylate,8 16 Ethyl trimethylacetate, 772 Ethyl 1,3dioxo-2-indanecarboxylate,8 16 preparaaon, 726 Ethylene (ethene), 223,282, t285,338,342,358, Ethyl n-valerate, t769 363,364,833,944 Ethynyllithium, 438 adhaon reamons, 328,33 1,337-339,341-342 Eugenol, 582,894,919 cycloaddition reactions, 1014 - 1016 Excited state, of molecules, 997 electronic configuration, 997 Exothermic reaction, 50, 53 -54 heat of hydrogenation, t326 Extinction coefficients, 597 molecular orbitals, 997 polymerization, 1078, 1096 preparation, 288,3 11 structure, 273 -275 from thermal cracking 120 Ethylene bromide, 363 Farnesyl pyrophosphate, 1137 Ethylene bromohydrin, see 2-Bromoethanol Fats, 1119-1142 Ethylene chloride, see 1,2-Dichloroethane biosynthesis of, 932, 1122 Ethylene chlorohydnn, 214,223, 1054 carboxylic acid source, 7 19 Ethylenediamine, 82 1,833 detergents from, 1126 - 1127 Ethylene glycol, see 1,2-Ethanediol hydrolysis of, 1124- 1125 Ethylene oxide industrial uses, 740 detergents from, 1126 occurrence and composition, 1120 - 1124 polymerization, 1086 phospholipids, 1128, 1129 - 113 1 preparation, 482, 1054 soan from. 1124- 1125 reactions, 482-483,687-688,910-911 so& of bure acidsand alcohols, 1125- 1126 Ethyl ethanoate, see Ethyl acetate unsaturated, 1127 Ethyl formate, t769, 816 Fatty acids, 1120, 1134 Ethyl formylacetate, 8 16 biosynthesis of, 1132 - 1134 Ethyl free radical, 112 in fats and oils, t1121 Ethyl fumarate, 1072 unsaturated, 1122 Ethylhexadecanoate, 780 Fehling's reagent, 1144, 1149 2-Ethyl-l-hexanol, 808 Ferguson, Lloyd, 443 Ethyl hydrogen sulfate, 331 Fermentation, carbohydrates, 2 19 Ethyl iodide, t169, 902 Ferr.-ne, 505,506, 1042, 1044 preparation, 170,225,328 Ferther. 784 Ethyl a-isobutylacetoacetate, 928 Fibers (shthetic). 1077- 1078 Ethyl isobutylmalonate, 925 propkities, 1094 Ethyl isobutyrate, 772 Fibrin, 1226 5-Ethyl-5-isopentylbarbituric acid, 938 Fibrinogen, 1226 m-Ethylisopropylbenzene, 55 1 Fibroin, 1225. Ethyl fiketobutyrate, 8 14 Fibrous protems, 1225 Ethyllithium, 98,692 Fischer, Emil, 1112, 1151,1155, 1169,!22 Ethylmagnesium bromide, 99,433 Fischer proof, of (+)-glucose configuraaon, Ethyl malonate (malonic ester), 980, 981,986 1160 preparation, 743 Flagpole hydrogens, 457 reactions, 720,783,925-926,979-98 1 Flash distillation, 38 Ethyl a-methylacrylate, 980 Flavylium chloride, 1075' Ethylmethylamine, 822,829,848 Fluorine, bond formation, 11 Ethyl methyl ketone (butanone), 659, t661,679,836 19F nucleus and NMR spectra, 6 17 Ethyl a-methyl-fiketovalerate, 8 15 Fluorobenzene, t520,867,1945,949 Ethyl methylmalonate, 980, 990 o-Fluorobenzophenone, 758 (R)-2-Ethyl-3-methyl-l-pentene, 164 Fluoroborate ion, 37 Ethyl a-methyl*-n-propylacetoacetate, 929 Fluoromethane, 38 Ethyl methyl-n-propylmalonate, 926 2-Fluoro-2-methylpropane,92 Ethyl pnitrobenzoate, 828 m-, o-,pFluoropheno1, t890 2-Ethyloctanoic acid, 720 m-, o-, pFluorotoluene, 1945 Ethyl oxalate, 816, 987 Formaldehyde, 364, 658, 659, 660, t661, 670, 674, Ethyl oxaloacetate, 8 16 675,683,686,694, 1092 Ethyl oxamate, 88 1 polymerization, 1090- 1092, 1097 Ethyl 3-oxobutanoate, 8 14 Formalin, 660 Ethyl 3-0x0-2-methylpentanoate,815 Formamide, 258, t755 Ethyl palmitate, 780 Formate ion, 674 Ethyl tert-pentyl ether, 204 Formic acid, 261, 397,405, 713,714, t715, t735 Ethyl phenylacetate, t769, 816 bond lengths, 734 Ethyl a-phenylbenzoylacetate, 8 16 Fossil fuels, 1, 94, 120, 220 Ethyl y-phenylbutyrate, 738 Free energy change, 730 - 73 1 Ethyl phenyl ether (phenetole), t238, 546 Free-radical addition, 3 18, 35 1-356 infrared spectrum, 596 to alkenes, 322,351 -356 preparaaon, 240,902 to alkenylbenzenes, 579-580 Ethyl phenylmalonate, 8 16 orientation of, 352-355 Ethyl l-phenyl-2-propyl ether, 183 peroxide-initiated, 35 1- 352 Ethyl propionate, t769, 774-775, 1054 (See also Addition reactions) in Claisen condensation. 8 16 Free-radical halogenation, 562,565-568 Ethyl n-propyl-n-butyl-n-hkxylmethane, 139 Free-radical polymerization Ethyl radical, 112 of alkenes, 356-357 Ethyl stearate, t769 of dienes, 4 19 - 42 1 Free-radical substitution 1 D-Glucosazone

Free radicals from carbohydrates, 2 19 - 22 1 alkyl, 47-49, 106- 109 fossil, 1,94, 120,220 relative stabilities, 11 1 - 112,390- svnthetic. 120 resonance stabhtion, 40 1-402 ~uhi,K., 1004 allyl, 123,389-392 Fullerenes, 3,5 12 - 5 13 electroluc configuration, 999 Fumaric acid. t742.764. t972.973.977. 1046- molecular orbitals, 998 -999 1048,1i15 . . ' ' . relative stabhty, 567 Fumaryl chloride, 987 resonance stabdizafion, 395 - 399 Functional derivatives of carboxylic acids, 753 - ben~yl,123,567:568. 796 (See also Acid chlorides; Acid anhydrides; resonance stabhbon, 568 - 570 Amides; Carbonic acid, functional derivatives chain reaction, 70,7 1 of; Esters; Fats; Imides) combination of, 108 1 Functions! groups, 167,317 definition, 47 electro~uceffects, 974 delocalization of odd electron, 395 - Furan. 478.990. 1057. t1058. 1065. 1074 detection by ESR, 573 reactions,-l062- 1063 triarylmethyl, 580 source, 1060- 1062 diradicals, 394, 1014 structure, 1059- 106 1 disproportionation of, 1081 2-Furanwboxaldehyde, see Furfural electron spin resonance (ESR) spectrum, 573,642 Furanose, 1178 formation Furanosides, 11 78 by abstraction, 47-48 2-Furansulfonic acid, 1064 by addition. 35 1-356 Furfural, t1058, 1062, 1203 fiom alkanes, 47 -49 reactions, 1062 from alkenes, 351 -356,389-392 source, 1062 from alkylbenzenes, 567 Furfury1 alcohol, t1058 in allylic substitution, 389- 392 Furnace oil, 96 by N-bromosucci+mide, 390 Furoic acid, t1058, 1063 from tert-butyl peroxide, 124 2-Furoic acid, 1063 ease of, 113, 39 1,567 Furylacrylic acid, 1074 stabilitv and. 113.353 Fused-ring aromatic compounds, 5 10- 5 13 in haloggnation, 47-49, 106- 109,389-392 Fuse1 03,218 from peroxides, 124,351-356,357 cis-Fusion, 11 35 from tetraethyllead, 76 trans-Fusion, 1135 from tetramethyllead, 76 from toluene, 567 hyperconjugation in, 40 1-402 inhibitors, 49 -50 Gabriel synthesis, 844, 1214 methyl, see Methyl radical Galactaric acid, 116 1 Paneth mirror technique, 76 a-~-Galact~pyran~se,1179 paramagnetism, 573 ~-O-@-D-~~~O~~~~~OS~~)-D-~UWP~O~,1190 racemization and, 16 1- 162,826 (+)-Galactose, 1147, 116 1 rearrangement, lack of, 116 D-(+)-Galactose, 1189 - 1190 resonance stabhtion. 387 - 399.402 D-Galacturonic acid, 118 1 "scavenger" of, 60 Gas oil, 96, t96 stability, 111-112,391,567 Gasoline, 96, 119, 120 ease of formation and, 113,353 ethyl (or leaded), 119 hyperconjugation and, 401 -402 natural, t96 relative, !11 - 112,390-392 Gasoline engine, 118 stereochemistry, 16 1- 162 Gattermann reaction, 879 structure. 64 - 65 Gauche conformation, 85 -86 triarylmethyl, 580 Gelatin, 1234 triphenylmethyl, 570- 574 Genetic code, 1246- 1247 vinyl, 123, 357 (+)-Gentiobiose, l202 (See also individua!free radicals) Geometric isomerism, 275,279-282 Free-radlcal sub*tubon, 46-63,65 prefixes, 283 392,448-449 Geranial, 705 in alkenes, allylic rearrangement, Geraniol, 647,655 Friedel, Charles, 557 Geranyl pyrophosphate, 1137 Friedel-Crafts acylation Globin, 1228 of benzene, 498,s 19 Global warming, 120 of heterocvclic comvounds. 1063 Globular proteins, 1225 of phenol;, 90 1 - structure, 1235 in preparation of ketones, 663-664,666 y-Globulin, 1221, 1234 761,765 Globuhns, 1226 Friedel-Crafts alkylation, 556- 56 1,577 Glucaric acid, 1145, 1149, 1159 of benzene, 498,s 18 (+)-Glucaric acid, 1167 limitations of, 56 1 Glucitol, 1145, 1149 of phenols, 901,907 Gluconic acid, 1145, 1149 reaction mechanism. 528.558-560 D-(-)-Gluconic acid, 1189 - 1190 test for aromatic compou'nds, 580 a-D-Glucopyranose,1 179 Fries rearrangement, 901,905 PD-Glucopyranose, 1178 5-D-Fructofuranosyl a-D-glucopyranoside, &D-(+)-Glucopyranose, 1179 r ~n? l l7L a-D-Glucopyranosyl p-D-hctofuranoside, 1192 :-)-Fructose, structure determination, 1146, 1152, ~-O-(~-D-G~UCO~~OS~~)-P.~UW~~~~~O~, 1155 1186-1188 >~rUctOse,1 183,1191 4-O-(P~-Glucopyranosyl)-~-~u~0pyranose,1189 - =uchsin-aldehyde reagent, 697 1191 =uels, 94-96,218 1304 Glucose Halides

Glucose, 220, t1149 Glyceraldehyde, 683 D-Glucose, 1172 configuration, 143, 1162- 1163 a-ands, 1172 relationship to glucose, 1166 - 1167 (+)-Glucose, 146, 1155, 1171 relationship to tartaric acid, 1164- 1165 D-(+)-Glucose (+)-Glyceraldehyde, 1163 acetylation, 1145 D-Glyceraldehyde, 1162, 1183 as aldohexose, 1144- 1146 ~Glyceraldehyde,1162, 1212 a-and forms, 1168, 1174, 1176 R-Glyceraldehyde, 789 inamyopectinstructure,B 1195-1198 R-(+)-Glyceraldehyde, 679,703, 1153 in amylose structure, 1193- 1196 D-(-)-Glyceric acid, 1163 anomers, 1170 Glycerides, 1120, 1125 configuration, 1170 hydrolysis, 1124 conformations, 1169,1178 - 1180 G1 cerol, 214, t216,272, 11 15 s@c rotahons, 1168 gom glycerides, 772 biological importance, 1143 - 1144 polymers from, 1090 in cellobiose structure, 1188 - 1189 Glycerol-l-phosphate, 11 15 in cellulose structure, 1143, 1200 Glycine, 863, t1206,1209, 1220 configuration, 1159, 1166 isoelectric point, 121 1 Fischer proof, 1155 - 1160 preparation, 829 conformation, 1178 - 1180 reactions, 1223, 1224 cyclic structure, 1168- 1172 Glycine hydrochloride, 1213 configuration, 1169 Glycogen, 1132, 1143, 1198 conformahon, 1178 - 1180 Glycols, see 1,2-Diols methylation, 1169, 1174- 1176 Glycosides, 1170 ring size, 1176-1178 Glycylalanine, synthesis, 1221 - 1222, 1224 in dextrans, 1198 Glycylalanylphenylalanine, 12 15 enantiomeric forms, 1166 Glycylglycine, 1215 epimers, 1152 Glyptal, 1090 formation Gomber& Moses, 570 from arabinose, 1157 Gossyplure, 706 in photosynthesis, 1143 Graduate student, naive, 704, 8 19,989 y-glucoside of, 1178 Graft copolymer, 1084 glucoside formation, 1168 - 1170 (See also Glu- Grain alcohol, see Ethanol, Ethyl alcohol cosides) Grains, as alcohol source, 2 18 as hemiacetal, 11 68 - 11 70 Gramicidin S, 48 1, 1250 inlactose structure, 1189-1191 Graphite, structure, 5 12 in maltose structure, 1185 - 1188 Greenhouse effect, 3,119 - 120 methylation, 1169,1174- 1176 Greenhouse gases, 43,2 19 molecular models, 1148 Griess, Peter, 5 16, 115 1 mutarotation, 11 68 - 11 70 Grignard reagent, 99- 101,240,483,668,870 nomenclature, of derivatives, tl149 in alcohol synthesis, 222,223,675,685-692 openchain structure, in mutarotation, 1170 choice of, 272,690,695-696 osazone, see Glucosazone decomposition, 695 oxidation, 1145,1158, 1167 preparation, 99- 100, 124, 174,685,688-692, in body, 1143 948 reactions, 1145 reactions reduction, 1145 with acids, 100- 101, 228 ring size determination, 1176- 1178 with aldehydes and ketones, 124,675,685- in starch structure, 1143, 1193 692,692-693 stereoisomers, 1146- 1149 with esters, 771,778 structure, 1145 - 1146 with water, 100- 101 ' in sucrose structure, 1191 - 1192 vs. organocopper compounds, 668 ~-(+)-Glucose,1 166 Grignard synthesis, 722 L-(-)-Glucose, 1166 of alcohols, 222,223,675,685-692 Glucose phenylhydrazone, 1145 of alkanes. 100 - 101 D-Glucose-l-phosphate, 1183 of carboxjhic acids, 72 1- 724 Glucosides, 117 1 limitations, 695 -698 as acetals, 1169, 1170, 1175 products of, 686 -688 configuration, 117 1 Grignard, Victor, 99 conformation, 117 1 Ground state, of molecules, 997 formation, 1168 - 1170 Guaiacol, 9 13 hydrplysis, 1175 Guanidine, 783,784 acld. 1169 Guanine, in nucleic acids, 1241- 1245 base: stability toward, 1170 Guanine-cytosine,-hydrogen bonding in, 1245 enzvmabc. 1173 Gulose, 1147 meth 1, see ethyl a-D-glucoside, Methyl (+)-Gulose, 1159, 1167 jD-@ucoside (-)-Gulose, 1159- 1160, 1162, 1167 methylabon, 1174- 1176 Guncotton, 1201 oxidation by periodic acid, 1173 - 1174 Gutta percha, 1095 Glucosone, 115 1 Guvacine, 1076 Glucuronic acid, t1149 DGlucuronic acid, 118 1, 1203 Glutamic acid, 137,930,1220 (+)-Glu-c aad, t1206 H I+Kilutamne. t1206 Halfchair conformation, 458 Halidejon, 176 Glutamyl~steiny&lycine,12 17, 1220 relahve reamvity, 27 1,272 Glutaric aad, t742 solvation, 257,263 Glutathione, 1217, 1220 Halides, see Alkyl halides, Aryl halides a-Halo acids Hohann orientation a-Halo acids, 727,973 n-Heptyl iodide, t 169 amination of, 1213-1214 l-Hepfyne, t429 Haloalkanes, 9 1 Heredity, 1246- 1247 Haloalkenes, 283 Heterocyclic compounds, 443,478-487, 1057- l-Halo-2-butene, t 169 1076 Haloethane, t169 five-membered rings, 1059- 1066 Halofonn reaction, 671,676,757,819 reactions, 1059- 1060, 1062 - 1064 a-Halogenated carboxylicacids, reactions, 741 - 742 saturated, 1065- 1066 Halogenation structure, 1059- 1061 addition to alkenes, 3 19,339- 342 source, 1060 - 1062 addition to allcynes, 432,434-435 physical constants, t1058 of aliphatic acids, 74 1- 742 six-membered rings, 1066- 1073 of alkanes, 103, 104- 118 uses, 1058 of alkylbenzenes, 565 -566 Heterocyclic rings, 478 -48 1 alternative mechanisms, 6 1-63 Heterolysis, 22, 166, 189, 196 of amides, 938-939 in acetylene, 427 aromatic, 518,529,946-948 Heterotopic faces, 111 1 of benzene, 498,529 Heterotopic ligane, 11 10 of ketones, 800,802-804 Hexa-0-acetylgluatol, 1145 of methane, 44-55 1,2,3,4,5,6-Hexachlorocyclohexane,644 order of reactivity, 44-45, 59-63 Hexachloroethane, 356 of phenols, 906 Hexacyclopropylethane, 584 of pyridine, 1068 (1 OE, 122)- 10,12-Hexadecadien- l-01,382 of pyf~ple,bran, and thiophene, 1062- 1063 n-Hexadecane, f93 trans~aonstate for, 113 - 114 Hexadecanoic acid, 1123 Halogen dance, base-catalyzed, 944,970 l-Hexadecanol, 780 Halogens cis- and trans-9-Hexadecenoic acid, 1123 addition to alkenes, 339-342 n-Hexadecyl alcohol, t2 16 addition to allcyn.es, 432,434-435 3,3,4,4,5,5-Hexadeuteriocyclohexanol,NMR speo addition mechamsm, 340 - 342 trum, 624 effect on aadlty, 735 -736 1,5-Hexadiene, t411 effect on electrophilic aromatic substitution, 2,4-Hexadiene, 315,415, 1005, 1008 542-544 1,4-Hexadieu-3-01,423 homolytic bond dissociation energies, 21 3,5-Hexadlen-2-01,423 order of reactivity, 42-45, 103 Hexamethylbenzene, t553 Halohydrins, 342 Hexamethylenediamine,.830,844,880,1090 orientation in, 342-343 Hexamethylphosphorotnarmde(HMPT), 255,263 preparation, 320,342 Hexanamide, 830 3-Halo-3-methyl-2-butanone, 931 n-Hexane, 90,f93,637 3alonium ions, 340,343,372,376,487 Hexanedioic acid, see Adipic acid I-Halopropene, t169 2,5-Hexanedione, 930, 1062 I-Halopropyne, t169 Hexanes, isomeric, 90 lammett, Louis P., 732 l-Hexanol (n-hexyl alcohol), t216,238 lammett equation, 732 2-Hexanol, 346 lammett U-p relationship, 732 2-Hexanone, t66 1 lanack, Michael, 408 3-Hexanone, t66 1 lardeners, 1099 Hexaphenylethane, 570 lardening of oils, 1127 1,3,5-Hexat~iene,424, 1005 lassner, Alfred, 384 electronic configuration, 1010 leat of activation, see Activation energy molecular orbitals, 1010 Ieat of combustion Hexatrienes, 1008- 1009 of benzene, 498 -499 l-Hexene, t285,347,720 of cycloallcanes, 450-45 1, t45 1 2-Hexene, 359 of methane, 43 3-Hexene, 359,431,639 Ieat of hydrogenation, 323-327, t326, t411,411 Hexestrol, 916 of alkenes, 323- 327, t326 n-Hexyl alcohol, t216,238 of benzene, 498 -499 n-Hexylbenzene, 667 definition, 324 n-Hexyl bromide, t169 of dienes, t4 11,499 n-Hexyl chloride, 89, t169 Teat of reaction, definition of, 50 - 5 1 Hexylenes, 282 Tell-Volhard-Zelinsky reaction, 727,728,741 - n-Hexyl iodide, t169 742, 1213 4-n-Hexylresorcinol, 677 Ieme, 1059, 1228 l-Hexyne, t429,429 Iemiacetals, 68 1,896, 1169 CMR, 635-636 Ienjketal., 896 2-Hexyne, t429 Iemmefitene, t553 3-Hexyne, t429,431 Iemoglobin, 1221, 1226, 1228, 1234, 1235 Highest occupied molecular orbital (HOMO), 1007 -Heptadecane, t93, 1122 Hindered rotation, 275,278 [eptaldehyde, 1661,835 Hine, Jack, 909 [eptanal, 835 Hinsberg test, 876 -Heptane, f93, 118,238 Hippuric acid (N-benzoylglycine), 880, 1215 [eptanedioic acid, 1075 Histamine, 1076 [eptanoic acid, 1145 Histidine, 1209, 1238, 1240 -Heptene, t285, t326 (-)-Histidine, t 1206 -Heptyl alcohol, t216 HMFT (hexamethylphosphorotriamide), 255,263 -Heptylamine, 835 Hohann, Roald, 1004, 1029 -Heptyl bromide, 98, t169 Hofmann degradation, 767,830,831,836,838-843 -Heptyl chloride, t169 Hofmann elimination, 849,854-855 !eptylenes, 282 Hofmann orientation, 302,855 1306 Hofmann rearrangement m 4-1Hydroxy- 1,3-benzenedisulfonic acid

Hofmann rearrangement, 838- 843 of esters, 77 1 stereochemistry at mi 840 heat of, see Heat of hydrogenation timing of steps, 840 - Gting heterogeneous, 324 HOMO (Gghest occupied molecular orbital), 1007 homogeneous, 324, 1042- 1046 Homocychc compounds, 443 -478, 1057 (See also stereochemistry, 384, 1046 - 105 1 Cyclic aliphatic compounds, Cycloalkanes) of &o compounds, 828 Homologous senes, 86 - 87 of oils, 1127 Homologs, 87 quantitative, 42 1 Homolysis, 22,47, 165,427 Hydrogen atoms, 110 Homopolymers, 1083 ease of abstraction, 110- 11 1,391 Homotopic faces, 11 1 1 Hydrogen bonds, 32,217-218,255,454,640, 1235 Homotopic ligands, 11 10 in alcohols, 2 17 - 2 18 Hordmene. 9 18 in armdes, 755 Hormone! in amines, 823 juvenile boilingpoint and, 217-218,891 Hbst-gues m carboxyhc aads, 7 17 House, Ht :rbert, l01 - ' in ethers, 238 Hiickel, Erich, 504, 1001 formation, 10 Hiickel4n + 2 rule, 504-507,1000- 1004 and infrared absorption shift, 592 Hudson, C:.S., 1173 in macromolecules, 1093- 1096 Hughes, E.D., 179, 183,293,294,303, and molecular shape, 29 1034 in nitrophenols, 89 1- 892 Hyalophora cecropia, 1139 in phenols, 890 Hybrid bonds, see Bonds and physical properties, 890 - 89 1 Hybridization of atomic orbitals Hydrogen bromide, 327 sp, 12,426,427 addition to alkenes, 330,35 1- 352 (See also Orbitals) Hydrogen chloride, 31,38,43,76,327 Hydration addition to alkenes, 333,335 of alkenes, 320,332 Hydrogen-chlorine bond, 63 of alkynes, 4!2,435-436 Hydrogen exchange, 297-298,807,969 Hydratropic aad, 750 Hydrogen fluoride, 24,30,38 Hydrazine, 673 dipole moment, t24 Hydrazones, 673 molecular orbitals, 994 Hvdride ion. 345 Hydrogen hahdes ~i+deshift, 206 addition to alkenes, 3 19,327- 329 Hydndotetracarbonylwbalt, 1052 addition to alkynes, 432 Hydriodic acid, 9 11 heterolytic bond dissociation energies, t22 used for identification, 245 homolytic bond dissociation energies, t2 1 HydroboraQon reactivity, 224,242 mechanism of, 349 - 350 reaction with alcohols, 229 - 233 orientation of, 348 - 349 Hydrogen iodide, 76,327,544 Hydroboration-oxidation, 222,321,347-348,898 addition to alkenes, 334-335 Hydrocarbons, 39 Hydrogen isotope effects, 295-297,532-535,964, acidity, 107 1 -969. -.> ----1099 aromatic, 287 Hydrogen migration, 206, 1020- 1024 combustion, 42-43, 118 Hydrogenolysis, of esters, 77 1,780 homolytic bond dissociation energies, 2 1 Hydrogen sulfide, 3 1 NMR and CMR spectra of, 639 Hydrolysis unsaturated, 273 alkahne, relative rates, 776 (See also.Allc?nes;pllcenes; Alkynes; Arenes; of alkyl hydrogen sulfates, 33 1- 332 Cychc ahphaQc compounds) of amides, 767 Hydrocracking, 120 in biochemical processes, 1236- 1238 Hydrodealkylation, industrial, 556 of carboxamides vs. sulfonamides, 864 Hydrogen of carboxylates, 729 abundance, t588 of carboxylic acid derivatives, 759,764,772 allylic, 124, 390 of esters, 77 1 CU, 235,683,814-815, 1102 of fats, 1124- 1125 ionization of, 797 of glycerides, 1124 p, 29 1,300,303 of (+)-maltose, 1187 benzylic, 124,566 of methyl glucosides, 1174- 1176 bond formation, 10 and neighboring group effects, 1038 classification, 92 of nitriles, 724 diastereotopic, 1109 paaial, 1217- 1221 different kinds of, 393 of phosphates, 1129 - 1130 enantiotopic, 1107- 1109 of substituted amides, 859 equivalent, 393 of urea, 783 flagpole, 457 Hydronium ion, 176 hydride character, 35 1 Hydroperoxides, 894 isotope effects, 295-297,532-535,964,969, aliphatic, 898 l099 rearrangement of, 895 migration, 206, 1020- 1024 3-Hydroperoxycyclohexene, 844,9 17 relative reactivity, 103, 110 Hydrophiliq, definition, 253, 1124 vinylic 124,390. Hydrophobic, defimhon, 253,1124 (See aho Deuterium; Protons; Tritium) Hydroquinone,.330,889,984,985 Hydrogenation Hydroxamic acid, 842,844 of alkenes, 319,323-327 Hydroxide ion, 176 of alkynes, 430-431,433 o-Hydroxybenzaldehyde,see Salicylaldehyde of alkylbenzenes, 56 1 p-Hydroxybenzaldehyde, t66 1 of aromatic hydrocarbons, 447 4-Hydroxy- 1,3-benzenedisulfonicacid, 547 o-Hydroxybenzoic acid (salicylic acid) Ionization

Hydroxybenzoic acid (salicylic acid), t715,748, of ethers, 596- 597 ona of hydrocarbons, 592 - 594 ~igx~benzoicacid, 889,t7 15 of phenols, 912-913 Hvdroxvbutanal. vrevaration. 800.806 Ingold, Sir Christopher, 134, 140, 179, 183, 191, Hjldroxjrbutyralddhyde, preparation, 806 199,293,294,303, 1034 .P-Hydr~xybut~l-S-ACP,1133 Inhibitors, 49- 50,7 1,330 Hydroxy-2'-chlorodiethyl sulfide, 1037 in chlonnation of methane, 49 Hydroxy-2,2dimethylpropanoicacid, 987 definition, 49, 1082; 1083 Hydroxyesters, 932 Imtiators, for polymembon, 357, 1085 ydroxylamine, 673,679,705,977 Inorganic compounds, 1 ydroxylamine hydrochloride, 679 Insecticide, 5 16 (N-Hydroxy1amino)-3-phenylpropanoicacid, 977 Insertion reactions ydroxylation of alkenes, 1045 of alkenes. 223.322.357 of methylene, 476 anti, 483-484 ' ' Insulin, 76, 1220, 1226, 1234 formation of 1,2-diols, 357 - 358 structure of, 1249- l250 with permanganate, 358,372,384 Interionic forces, 1235 with peroxy acids, 357,372 of liquids, 3 1 with peroxyformic acid, 358,384 of solids. 27

-X.-. .- - and solubility, 3 1 'ydroxyl group, 725 Intermolecular forces, 28 -33 proton chemical shift, t607 in liauids. 30 -)-Hydroxylysine, t 1207 .Hydroxy-2-methylpentanal, 806 in solids, 28 .Hydroxy-4-methyl-2-pentanone, 800,806,807 and solubility, 250-258 .Hydroxymethylphenol, 109 1 Intermolecular reacC1ons. and intramolecular reac- .Hydroxy-a-methylvaleraldehyde,806 tions, 296 .Hydroxynaphthalene, 547 Intramolecular fonres, 20-2 1 .Hydroxyphenyl ethyl ketone, 905 Intramolecular nucleophilic substitution, 841, .Hydroxyphenyl ethyl ketone, 905 1035 (See also Rearrangement) -)-Hydroxyproline, t1207, 1234 Intramolecular reactions. 448 -Hydroxypropionic acid, see Lactic acid competition with int&no~cularreactions, 296 .Hydroxypropionic aad, 975 Inversion .Hydroxypropjophenone, 905 of ammonia, 19 .Hydroxypropiophenone, 905 of configuration, 182- 185,375,826,1023 IY*~, 1% of radicals, 65 [ygnmc aad, 1066 of sucrose, 119 1 lyperconjugation, 200,401 -402,413 Inversional isomers in alkenes, 4 13 of sucrose, 119 1 Iypnotic, 221 (See also Stereoisomerism) [ypochlorous acid, 529 Invertase, 119 1 Iypohalites, 237,676, 698, 783 Invert sugar, 119 1 [ypohalous acid, 342 Iodine, 59 [ypophosphorous acid, 87 1 as tracer, 118 Iodine azide, 384,487 0-Iodoaniline, 509 Iodobenzene, 508, t520,867, r945 2-Iodobutane, 329 -Icosane, t93 l-Iodo-2-butene, t169 I-D-Idopyranose,1 180 2-Iodocyclohexyl brosylate, 1041 -)+dose, 1162 2-Iodo-2,3dimethylbutane,208,335 &on test, 745 3-Iodo-2,2dimethylbutane,208 midazole, 1057, 1238 Iodoethane, t169 ring, 1238 Iodoform, 671,800 mides, 767 - 768 boiling point, t171 mine-enamine tautomerism, 935 Iodoform test, 698 mines, 834-835,935 2-Iodohexane, 1145 mimum ions, 937 2-Iodo-2-methylbutane, 168,329 ndanone. 8 18 1-1odo-l -methylcyclopentane, 448 ndigo, 76 l-Iodo-2-methylpropane, 92 ndole, t1058, 1064 2-Iodooctane, 183 nduced dipoles, 29 2-Iodopentane, 329 nductive effects, 200,406, 670 3-Iodopentane, 329 in aromatic substitution, 537 m-Iodophenol, t890 definition, 200 o-Iodophenol, t890 of halogens, 542,944 pIodopheno1, t890 of substitutent groups on acids, 735-736 2-Iodopropane, 3 19 (See also Electronic effects; Resonance effect) 3-Iodopropene, t169 nfrar=+bsorption bands, for organic groups, 590, 3-Iodopropyne, t 169 LJ7L m-IodotoIuene, t945 nfrared absorption shift, 590, 592 0-Iodotoluene, t945 nfrared radiation, 119 . pIodotoluene, 943,845,970 nfrared spectra, 585,590-592,592-594 Ion-dipole bonds, 25 1,258- 26 1 analysis, 121, 122,590-592 Ionic bonds, see Bonds ofalcohols, 217,594,912-913 Ionic character, 400,967 of aldehydes and ketone, 70q- 70 1 Ionic polymerization, 1084- 1086 of amines and subshtuted amdes, 877 - Ionic solutes, 3 1,254-258 of carboxylic acids, 745 -746 Ionization, see Acidity, Acidity constants, Basicity, of carboxylic acid derivatives, 784-785 Basicity constants 1308 Ionizing power Kekult structures

Ionizing power, 260 Isopentane, 87,90, t93,95 Ion pair, 30, 196,254-258,265,270 Isopentenyl pyrophosphate, 1128, 1136, 1137, 1140 loose, 257-258,270 Isopentyl acetate, t769 tight, 257,270 Isopentyl alcohol, see 3-Methyl-l-butanol Ions, solvated, 249,255 Isopentyl chloride, 90 Isoalkane, 90 Isophthalic acid, 564, t715, t742 Isobutane, t84,91, t93, 103, 116,345,364 Isoprene, t4 11,420-42 1 Isobutyl alcohol, 215, t216, 349,694,721,769 polymerization, 420,420- 42 1, 1088 Isobutvlamune. t824 Isoprene rule, 4 12 infdspekum, 878 Isopropyl alcohol (2-propanol), 21 N-Isobutylaniline, 830 225,233,316,320,331,691 B-Isobutyl-BBN, 934 Isopropylamine, t824, 830 Isobutylbenzene, 55 1, t553 Isopropylbenzene(cumene), t553, Jsobutjll benzoate, 769 Isopropyl bromide, 124, t169, 187 Isobutyl bromide, 124, t169, 190, 330, 925,928 242,308,310,319,330,353 Isobutyl chloride (l-chloro-2-methylpropane), 10 dehvdrohalo~enahon.290 -29 1 104, 108, 168, t169, 560 infiked spehm. 591 Isobutylene, 277, t277, 282, t285, 31 1, 321, 323, NMR spectrum, 6 18 364.559.724. 1099 Isopropyl cation, 19 1 ionization pqtential from bromide, 197 heat of hyclrdgenation, t326 Isopropyl chlonde, 89, 104,134,168, t169,335,388 NMR signals, 602, 6 17 NMR signals, 602 reactio~q.336,338, 340,343, 345, Isopropylcyclohexane, 463 Isobutyl idde,!l69 Isopropyl ether, see Diisopropyl ether Isobutylmagnesium bromide, 687,69 Isopropyl fluoride, 645 Isobutylmalonic ester, 926 ~Isopropylglutaricacid, 705 Isobutyl methyl ketone, t661 Isopropyl hydrogen sulfate, 320, 331 Isobutyl radical, 116, 117 Isopropyl iodide, t169,3 19, 328 Isobutpldehyde, 830 Isopropylmagnesiumchloride, 100 Isobutync aad, 247, 72 1 4-Isopropyl- l -methylcyclohexane, 940 Isobutyryl chloride, 664 Isopropyl methyl ketone, 660 Ismproaldehyde, 659 Isopropyl n-propyl ether, 240 Isocaproic acid, 925 Isopropyl radical, hyperconjugation, 402 Isocrotonic acid, 872 Isopropylsuccinic acid, 705 Isocyanates, 839 Isopropyltoluenes (cymenes), t553, 1200 reactions, 839,844, 1092 Isopropyltrimethylammoniumion, 316 Isodurene, t553 Isoquinoline, 1057, t1058 Isoelectric point Isotactic polypropylene, 1089 in amino acids, 121-1- 1212 Isotope effects, 295 -297 in ~roteins.1226 - 1228 in electrophilic substitution, 532 - 535 in elimination reactions, 297 Isoeugenol, 582,894 in free-radical chlorination, 295 Isohexane (3-methylpentane), 90, 9 1, t93 in nucleophilic aromatic substitution, 964,969 Isohexyl chlonde, 90 in polymerization, 1099 Isolability, 149,28 1 primary, 295 Isolated double bonds, 410 Isotopes, heavy, abundance of, t588 Isoleucine, 219, 927, 1238 Isotopic exchange, 183,297-298, 313,774,777, (+)-Iso!eucine, t 1207 807,969 Isomensm, 36- 37 Isotopic peaks, in mass spectra, 588, t589 alicyclic compounds, 463 -467 Isotopic tracers, 118 alkanes, 88 in addition, 364 alkenes. 277-280 in aldol condensation, 807 alkyl groups, 89 -90 in biological oxidation-reduction, 1103- 1106, alkynes, 427 1113, 1114 butanes, 83 - 85, t82 in elimination, 298, 313, 380 butylenes, t277,277-2?8,280 in halogenation of alkanes, 116 - 118 cis-trans, see Geometric isomerism in hydrolysis of esters, 774,775,777,778 concept of, 36 in nucleophilic substitution, 183,963 hexanes, 87 in rearrangements, 839,896, 1056 o~tical.133 (-)-Isotrehalose, 1202 sibstitu!ed benzenes, 495 -497 Isovalent hyperconjugation, 413 IsomenzaQon Isovaleric acid, 727 catalytic, 96 IUPAC system of nomenclature, 90-92, 168, 215, industrial, 555-556 282,428,659,716,754 (See also individual Isomer number, 84,126- 128 farnilzes) benzene and, 495 tetrahedral carbon and, 126- 128 Isomers cis and trans, 463-467,470 J configuratioral, definition, 149, 28 1 Johnson, W.S., 623 conformational, 149 - 150,28 1 Juvenile hormones, 1139 definition, 36 mirror-image, see Enantiomers stereo-, see Stereoisomers torsional, 28 1 Isoniadd, 1068 Kekulk, August, 2,494 Isoecoti+c a4d, see 4-Wdinecarboxylic acid benzene structure, 401,494-497,500,503 IsomcoQmc aad hydrazlde, 1068 68, 574,903,950, "Isooctane", see 2,2,4-Trimethylpentane Kelvin, Lord Light

Kelvin, Lord, 134 Ketoses Kendrew, J.C., 1235 definition, l l44 a-Keratin, 1225 effect of alkali, 1150 proposed helm structure, 1233- 1234 oxidation, 1149 Kerosine, 96, t96, 124 Kharasch, M.S., 102, 161,330, 351 Ketals, 681 Kiliani, Hemrich, 1152 --Ketene. 474. 763 Kiliani-Fischer synthesis, 1152- 1153, 1162 Keto a&ds, from tetra-O-methyl-D-glucose,1 177 Kimball, G.E., 374,.1034 a-Keto acids, preparation, 930 Kinetic energy htnbuhon. 56 PKeto acids, decarboxylation, 930-931 Kinetics -- 8-Keto esters, formation of, 8 13 - 8 15 definition, 177 - 178 a-Ketobutyric acid, preparation, 930 of dehydrohalogenation, 293 Keto-enol tautomerism, 435-436,804-805,977 in the E2 mechanism, 295 acjd and base catalysis, 820 first-order, 178- 179, 188,293 and-catalyzed aldol condensation, 8 18 second-order. 178 - 179.-2 ---182 bromination, 804-805 ~jeldahlmethddj 513-5 14 in carbohy.drate% 1149 - 1150 Kloosterziel, H., 1024 electropluhc conjugate adduon, 976 Knocking, in gasoline engine, 118

nucleo hi!.ic conjugate addition, 977 Knoevenanel reaction. 927.8' 10-81 1 (See alo Imine-enamlne tautomerism) Knoop, FGnz, 1134 . FKeto esters, 802,813 ; 8 16 (See also.Acetoacetic Kolbe reaction, 5 19,902,908 ester synthesis; Clsusen wndensauon; Ethyl Komer, Wilhelm, 509 acetoacetate) Korner method of absolute orientation, 509 a-Ketoglutaric acid, 11 15 Kossel, Walther, 4 2-Ketohexose, (-)-fructose as, 1146 Krebs, H.A., 11 14 2-Ketohexoside, 1178 Ketones, 359,440,657-712,692,797-814, 1103 addition of alcohols, 674,680-683 of ammonia derivatives, 673,679-680 ~,preh,1162-1164, 1166 of carbeons, 675 I, preh, 11 63 of cyamde, 673,678-679 Labeling experiments, 117 - 118 (See also Isotope of Grignard reagents, 685-688 effects; Isotopic tracers) aldol condensation. 805 - 809 (R)-Lactaldehyde, 11 15 aliphatic, 665 . Lactams, 840, 1248 alkylation, 93 1-932 Lactic acid, 135, 138,716,770 analysis, 697-698 enantiomers, 132 aromatic, 665 (+)-Lactic acid, 159, 1163 Clemmensen reduction, 667,672,677 D-(-)-Lactic acid, 1163 crossed Claisen condensation, 8 16 L-(+)-Lactic acid, 1163, 1164

enamine~p~---p- formation.~ 935-937-. Lactide, 770 enolization, 804 - 805 Lactobacillus bulgaricus, 1189 in Grignard synthesis, 685 - 692 Lactobionic acid, 1189, 1190 halogenation, 675,800 p-Lactoglobulin, 1248 aad-catalyzed, 804- 805 Lactones, 770 base-promoted, 802-804 FLactones, 989 industrial source, 661 Lactonic acid, 789 nomenclature, 658 - 660 Lactosazone, 1189- 1190 nucleophilic addition, 669-675, 800-801 (+)-Lactose,1185, 1189-1191 oxidahon. 67 1.675 -677 properties, 1189 source, 1189 structure, 1189 A acetoacetic ester synthesis, 664,927-930 Ladenburg, Albert, 5 15 from acid chlorides. 664.665.668.762.,, benzene structure, 5 15 via enamines, 935-.937 Lanosterol, 1136, 1137 Friedel-Crafts acylation, 663-664,666-667, Lapworth, A., 803 765 Lard, t1121 ~ries'&man~ement,901,905 Lauric acid, 7 13, t7 15,725,740 organoborane synthesis, 933 -935 Lauryl alcohol, 780, 1126 wng organocopper compounds, 664,665, Lauryl hydrogen sulfate, 1 126 668-669,762 LCAO (linear combination of atomic orbitals) oxidation of secondary alcohols, 226,236, method, 993-994 237,663,665 Lea:;! grryps, 172- 173, 175, 177, ozonolvsis. 358-360 pinacoi rebgement, 705 reactions, 669-675 wrth Gngnard reagents, 685 - 692 reduction, 556-557 to alcohols, 672 synthesis, 12 14 to hydrocarbons, 672,677-678 (-)-Leucine, t 1207 reductwe amination, 672,834-835 Levorotatory, definition, 129 spectroscopic analysis, 692, 700-701, t786 Levulinic acid. 705 structure. 657-658 unsaturated, preparation, 973 Lewis, G:N., 4 Witti reaction, 801 81 1-812 acid and base definition, 34 - 36 ~olkKishnerreduction, 667,672,677 Lewis acids, 528,557,559,561 (See also a,&Unsaturated carbonyl compounds) Life, origin of, 4 1 7-Ketonorbornene, 988 Ligands, 1042 - 1045 Ketopentoses, dehuon, 1144 Light, detection of, 285 1310 Ligroin (light naphtha) Methanethiol

Ligroin (light naphtha), 96, t96 from amylose, 1193 Limonene, 492 reactions, 1186 - 1188, 1204 Linalool, 647 structure, 1185-1188 Lindlar's catalyst, 433 Mandelic acid, 144,673,750, 751 Linear combination of atomic orbitals (LCAO), Mandelomtnle, 673 993-994 ManganeHW), 236 Linear free energy relationships, 732 Mannan, 1203 Linear polymers, 1088- 1089, 1096 Mannaric acid, t1149 Linoleic and, t7 15, 11 22 Mannitol, t1149 Linolemc aad, t7 15, 1122 Mannonic acid, t1149 Linseed oc,. 1100, 1128 &D-Mannopyranose, 1179 composltIon, t1121 Mannose, 1149 Lipids, 1120, 1137, 1138 (See also Fats; Steroids: (+&Mannose. 1147.1 155 Terpenes) itructure &termihation, 1151- 1152,1157-1 160 Lipophilic, definition, 253, 1124 Mannuronic acid, t1149,1203 Lithium acetylacetonate, 38 Markovnikov, Wadimir, 328 - 329 Lithium acetylides, 429,437,438 Markovnikov's rule, 329, 336-337, 342,346,349, Lithium aluminum hydride, 349,351,677 959 in reduction of acids, 728,740 ~ar&&, 41 Lithium apide, 437,1085 Mass spectra, 586- 589 L~thiumdpllcylcopper, 101 Mass spectrometry, 122,586 Lithium halkylcuprate, 668 Mass spectrometers, 586 Lithium diarylcuprate, 668 Mass-tocharge ratio, 586,588 Lithium di-tert-butylcopper, 122 Maximum overlap, principle of, 10 Lithium di-n-butylcuprate, 664 Maximum rotation, 156 Lithium diethylcopper, 98 Mayo, Frank R., 330,35 1 Lithium diisopentylcuprate, 669 Meerwein, Hans, 19 1,204,306 Lithium dimethylcopper, 102 Melander,. W, 532 Lithium dimethylcuprate, 668 (+)-Melezitose, 1202 Lithium di(ppitrophenyl)cuprate, 669 Melibiose, 1202 Lithium hvdnde. 35 1 Mellitic acid, 745 Lithium ishpropylacetylide, 433 Melting point, 27-28 Lithium methylacetylide, 433 and crystal structure, 27 -28 Lithium n-pentylacetylide, 430 ionic vs. non-ionic compounds, 27 - 28 Longuet-Higgins, H.C., 1004 and molecular symmetry, 553-554 Lossen rearrangement, 844 pMenthane, 492,492,940 Lowest unoccupied molecular orbital (LUMO), 2-Menthene. 473.491 .1015-1016. . - .. . . Lowry-Bronsfed, acid and base definition, 33 Lubricat~ngofi, t96 Menthone, 940 Lucas, Howard, J., 386, 1032, 1034 (-)-Menhone, 663 Lucas reagent, 244 Menthyl chloride, 473,49 1 Lucas test, 230,244 Mercuric acetate, 222,321,346 Lucite, 973, 1081, 1096 Mercuric trifluoroacetate, 24 1 LUMO (lowest unoccupied molecular orbital), Mercurinium ions, 347 1015-1016 Memfield, R. Bruce, 1225 Lycopene, 488 Mesitoic acid, 724, 738,739 Lycra, 1097 Mesitylene, 535,546, t553, 584,724,765, (+)-Lysine, t1207 1174 (-)-Lyxose, 116 1 &R spectrum, 606,608,643 Mesityl oxide, see 4-Methyl-3-penten-2-one Meso compounds, 147 Meso structures, 146 - 147 Mesotartaric acid, 750, 1161, 1165, 1166 Macromolecules, 1077- 1100 Messenger RNA, 1247 definition, 1077 Mesyl group, 234 structure and properties, 1093- 1096 Metabolite antagonism, 864 "Magic" acid, 102 Meta-directing groups, 520-525,954 (See also Magnesium-halogen bonds, 100 Orientation) Magnesium perchlorate (Dehydrite), 73 Metal acetylides, 430 Magnehc moments reactions, 433,438-439 in free radicals, 573 Metal hydride, 678 (Seealso individual compounds) of nuclei, 600 - 60 1 Methacrylmde, 789 Magnetogyric ratio, 600 Methacrylic acid, 673,789, t972,973 Malaprade, L., 1150 Methallyl chloride, 364,645 Malicacid, 144, 159, 160, 751, 1115 Methanal, see Formaldehyde Maleic aphydride, t755, t972, 973, 983 Methane, 39-76, 119 Malic aad 144, 159, 160, 1115,751 bond formation, 15- 17 Malonic akd, 742, t742 bromination, 44-45 118 decarboxylation, 930 - 93 1 chlorination, 43 -44,48 -49 Malonic ester, see Ethyl malonate heat of combustion,-42 Malonic ester synthesis, 924-927 phys* properties, 28, 31,32, Malonyl CoA, 1133 reachons, 42 -49 Malonyl-S-ACP, 1133 halogenation, 42,44-46 Malonvlurea. 783 oxidation, 42-43 ~altask,1 187 source, 4 1- 42 Maltobionic acid, 1187 - 1188 structure, 17,20,40, 126 - 128 (+)-Malto~,1185-1188, 1195 Methanesulfonic acid, 234 Methanethiol, 35 Methanoic acid m Methyl cis-9-octadecenoate

dethanoic acid, 7 13 3-Methyl-2-buten-2-y1 group, 409 dethanol, 31, 32,43,88,215, t216,255,256,674, 3-Methyl-2-buten-2-y1 triflate, 409 683,726,739, 1125 3-Methyl-2-buten-2-y1 trifluoroethyl ether, 409 and methyl bromide, 172, 178, 181 3-Methyl-2-butyl tosylate, 305 -)-Methionme, t1207 Methyl n-butyl ketone, 688,690 tethoxyacelic acid, 745 3-Methyl-l-butyne, 1429 -Methoxy-4-acetoxyphenylalanine, 105 1 2-Methyl-3-butyn-2-01,692 -Methoxy-4-allylphenol (eugenol), 582,894,919 a-Methylbutyric acid, see 2-Methylbutanoic acid Iethoxyaniline (anisidine), t824,965 -967 a-Methylcaproic acid, 1146 -Methoxybenzaldehyde (anisaldehyde), t66 1,683 Methyl cation eMethoxybenzoic acid, t7 15 ionization potential from bromide, 197 -Methoxybenzo$ acid, t7 !5. structure, 193 -Methoxybenzo~cacld (amsic acid), t7 15,912,9 18 Methyl chloride (chloromethane), t24,43,46,74, -Methoxvbenzvl alcohol, 683 88, t169,283, 564 -~ethoxjrhexabe,237 a-Methylcinnamicacid, 677 dethoxymethyl chlonde, 407 Methylcyclohexane, t444,446 -Methoxy-4-methyl-2-pentanone, 975 conformation, 46 1-463 -(pMethoxyphenyl)propene, 583 1,3-diaxial interactions, 46 1,462 (ethyl acetate, 757, t769 industrial source, 446 infrared spectrum, 786 3-Methylcyclohexene, 49 1 preparation, 764 Methylcyclopentane, 322, t444 dethylacetylene, 276 industrial source, 446 dethyl acrylate, t972, 973 1-Methylcyclopentanol, 346 dethyl alcohol, see Methanol 2-Methylcyclopentanol,490, 703 dethylamine, 821, t824,826, 828, 836, 846, 977 trans-2-Methyl-l-cyclopentanol, 322 -(n-Methylammo)heptane,822 l-Methylcyclopentene, 322, 347, 448, 490 -(n-Methy1amino)-4-methyl-2-pentanone,977 3-Methylcyclopentene, 703 dethylaniline, see m-, o-, and pToluidine Methylcyclopropane, 602 tJ-Methylaniline, 546,821,836 5-Methyl- 1,3-dihydroxybenzene, 9 15 infrared spectrum, 878 N-Methyl-2,4-dinitroaniline,829 preparation, 859 Methyl dodecanoate, 780 -reactionwith nitrous acid, 865 Methylene, 473-476,763 ~Methylanisole,724, 905, 912 Methylene bromide, 45 dethyl a-L-arabinoside, 1178 Methylene chloride (dichloromethane), 43,44, dethyl aryl ethers, 9 11 t169, 258,442 ~Methylbenzaldehyde,898 Methylenecyclohexane, 801 tJ-Methvlbenzanilide, 859 Methylene group, 43 dethyl&nzene, see Toluene Methylenetriphenylphosphorane, 801,812 dethyl benzoate, 726, 739 N-Methyl-N-ethylaniline, 822 v-Methylbenzyl alcohol, 727 N-Methyl-N-ethylbenzamide, 848 cMethylbenzy1 bromide, 576 Methylethyl-n-butylamine, 837 cMethylbenzy1 hydroperoxide, 898 N-Methyl-N-ethylbutyramide,858 v-Methylbenzyl tosylate, 576 N-Methyl-Nethyl-ptoluenesulfonamide, 848 ~Methylbenzyltosylate, 576 Methyl fluoride, 38 dethyl bromide, 45,88, 102, t169, 178, 187, 190, N-Methylformamide, 258 243,262,837,926 Methyl free radical, 48, 64-65, 76, 112 and methanol, 172, 178, 181 Methyl p-D-fructofuranoside, 1178 :-Methyl-l-bromobutane, 225 Methyl a-D-fructoside, 1178 :-Methyl-1,3-butadiene, see Isoprene Methyl /?-D-glucopyranoside, 117 1, 1178 . !-Methylbutanoicacid (a-rnethylbutyric acid), Methyl a-D-glucos~de 716,721 formation, 1169- 1173 chirality, 155 reactions, 1171, 1173 preparation, 226 structure and properties, 1169 - 1173 !-Methyl-l-butanol, 135, 136, 138, 215, 225,226, Methyl &D-glucoside 313.560.721 formation, 1169 - 1173 enantiomek, 132 reactions, 1174, 1176 from fermentation, 159 structure and properties, 1169 - 1173 from fuse1 oil, 129, 130, 156 Methyl group, 88 ~re~arationof, 687 2-Methyl-3-heptanone, 664 ieadons, 154 2-Methyl-2-hexanol, 687,688,690 specific rotation, 130, 156 3-Methyl-2-hexanone, 929 I-Methyl- l-butanol (isopentyl alcohol), t2 16, 560, 5-Methyl-2-hexanone, synthesis, 928,934 694 2-Methyl-4-hydroxyacetophenone, 901 synthesis, 694 4-Methyl-2-hydroxyacetophenone, 901 !-Methyl-2-butanol, see tea-Pentyl alcohol Methyl iodide, 88, t169, 91 1 L-Methyl-2-butanol, 2 15,560 Methylisopropylacetylene,428 preparation, 349 Methylisourea, 784 L-Methyl-2-butanone, 660 Methyl ketones, 671,676 L-Methyl-2-butenal, 8 19 Methyl laurate, 780 !-Methyl-l-butene, 305,306, 313, 347 Methylhthium, 102 heat of hydrogenation, t326 Methylmagnes!um bro.mide, 688,690 preparation, 301,857 Methylmagnes~umiede, 99,772 3-Methyl-l-butene, t285, 305, t326, 335 a-Methylm~dehcacld, 804 synthesis, 693-694 Methyl mesltyl ketone, 765 !-Methyl-2-butene, t285, 305,306, t326, 334, 336, Methyl methacrylate, 872, 973 349,720 polymerization, 1081, 1083, 1085, 1096 preparation, 300,313,693,857 4'-Methyl-3-nitrobenzophenone, 66 !-Methyl-2-butenoic acid, 679, 987 Methyl pnitrophenyl ketone, 668 I-Methyl-2-butenoic acid, 67 1 Methyl cis-9-octadecenoate, 773, 1137 7

Neomenthyl chloride

3-Methyloctane, 102 Molecular weight Methyl oleate, 773, 1137 of cellulose, 1200 Methyl orange, 75,875 end-group analysis, 1193- Methyl 4oxo-7-'pethy1octanoate, 669 by mass spectrometry, 75, y-Methylpamomc acid, 8 18 of pepudes, 12 18 2-Methylpentanal, 659 of polysaccharides, 1195 3-Methylpentanal, 659 Molecule of the Year, 446 4Methylpentanal, 659 Molecules 2-Methvl~entane.91.638 flat, 15 3-~eth$fpentie'(isdhe&e), 90,9 1,193 linear, 13 2-Methylpentanoic acid (a-methylvaleric acid), 926 polarity of, 23 -26 4-Methvloentanoic acid (isoca~roicacid). 925 Molozonides, 359 Monomer, 356, 1078 Monosaccharides, 1143 - 1184 1 1 50, analvsis.+---, --1149 ------1152 classipcation, 1144 2-Methyl-l-peniene, 307 defimtion, 1144 2-Methyl-2-pentene, 307, 359 effect of alkali, 1149- 1150 (&3-Methyl-2-pentene, 1055 reactions, 1149-1150, 1175 4-Methyl-2-pentene, 282, 307 (See also Aldohexoses; Aldoses; ~-(+)-Glucose: . . 4-Methyl-3-penten-2-one (mesityl oxide), 67 1,800, etc.) - -7 1972.973 Morphine, 159 reactions, 975,977,982 Morpholine, 937 Methyl n-pentyl ether, 238 Ms. 234 2-Methyl-3-pentyl tosylate, 307 MUCGacid, 116 1 4-Methyl-2-pentyne, 428 Mulliken, R.S., 402 Methyl phenyl ether, see Anisole Muscalure, 442 Methyl phenyl ketone, see Acetophenone Muscarine, 164 2-Methyl-3-phenylpentane, 55 1 Musk (synthetic), 91 5 2-Methyl-l-phenyl-2-propanol,690 Mustard gas, 1037 2-Methyl-3-phenylpropenoic acid, 676 Mutarotation Methylpropane, see Isobutane of ~-(f)-gl~cose,1170 2-Methyl-l-propanol, see Isobutyl alcohol of (S)-maltose, 1187 2-Methyl-2-propanol, see tert-Butyl alcohol Mutations, 1247 2-Methylpropene, see Isobutylene (-)-Mycarose, 1 184 2-Methylpropenoic acid, see Methacrylic acid Myoglobin, 1235 Methyl-n-propylamine, 847 Myosin, 1225 Methyl n-propyl ketone, 659 Myrcene, 424 Methyl-n-propylmalonic ester, 926 Myristic acid, t715 N-Methylpyridinium iodide, 1072 Methyl rahcal, 48,64-65,76, 112 Methyl salicylate, 9 14 NAD (nicotinamide adenine dinucleotide) 114, 1229 1175, 3, 1105-1106 !-1106 Metd;lptolyl ether @methylanisole) 724,905,912 tinamide adenine dinucleotidr Methyltriphenylphosphonium bromide. 8 12 a-Methylvaleddehyde, 659 &Methylvaleraldehyde, 659 Naphthalene? 510-513,s41, s y-Methylvaleraldehyde, 659 electroph&c substituQon in, 34s - a-Methylvaleric acid, 926 industrial source. 555 -556 Methylvinylmethanol, t216 nomenclature, 5 l0 Methyl vinyl ketone, reactions, 981 structure, 511-512 Methyl &D-xyloside, 1178 test for, 580 Mevalonic aad. 1139. 1140 Naphthalenesulfonic acids, 547 Meyers, A.I., 932 ' l-Naphthol, 547 MIBK (Isobutyl methyl ketone), t66 1 2-Naphthol, 5 10,889 Micelles, 1124 - 1125 &Naphthol, 510, 876, 889 Michael addition, 979-982 1,4NaphthoqUinone, 986 Michael condensation, 927 Natta, Giulio, 1087, 1089 Micrococcus ureae. 783 Natural gas, 41,94 Microscopic revekibility principle, Natural rubber, 420-421,422, 1095 Middey, T.C., Jr.. 119 NBS (AJ-bromosuccinimide),323,390, Mi - tob aptitude, 842, 896-897 Neighboring group effects, 386,103 1- ME,Stapley, 42 by acetoxy group, 1039- 1040 "Mixed acq, 525 anchirnenc assistance, 1037 - 104 1 Modena, G~orgo,408 by bromine, 1032- 1035, 1037 Moffitt. W.A.. 453 bv carbon. 1037 ~olecularbiology, 1235- 1236 in enzyme action, 1240 Molecular forrpula, determination, 72,75 intramo~ecdarnucleo~hilic attack, 1035-1037 Molecular orbltals,.9,99! - 1030 by nitrogen. 1037 - bonding and anbbonhng orbitals, 994-996 by oxygen, i037 LCAO method, 993-994 reaction rate, 1037 - 1041 orbital symmetry and chemical reactions, 1004- stereochemistry, 1032- 1035 1024 by sulfur, 1037, 1038 theo&%9 1 -992 Neohexane. 364 wave equations, 992-994 Neopentane W N-terminal residue

hydrogenation, 828 Neopentyl alcohol, 230,231,316,560,720,727,772 importance, 869,-870,878,946-947 Neopentyl bromde, 188,305 mfrarg absorphon frequencies, t592 Neopentyl cation redudon, 828,830,832 mass-tocharge ratio, 586 removal of nitro group, 871 rearrangement, 204- 205 m-Nitrodiphenylmethane,547 Neopentyl chloride, 110, 171 pNitrodiphenylmethane, 584 Neopentyl ethyl ether, 204 o-Nitroethylbenzene, 550 Neopentyl hahdes, 203 pNitroethylbemene, 550 Neoprene, 420, 1080 Nitrogen - (+)-Neotrehalose, 1202 armno, Van Slyke determination, 12 15 Ned, 705 analysis, 513-514 Nerol, 492,647 electrondeficient, 838-839 Nerolidol. 939 electronic configuration, t8 Ne~onic.acid,1 137 lSNas tracer. 118 Neutralization equivalent, 744 - 745 Nitrogen-hydrogen bond, 18 Newman, M.S., 8 1 Nitrogen tntluoride, t24,25 Newman projections, 81,463 Nitro group, 396 Niacin, see 3-Pyridinecarboxylic acid m-Nitromandelic acid, 678 Nicol prisms, 128 Nitromethane, 384,396 Nicotinamde adenine dinucleotide, see NAD l-Nitronaphthalene, 547 reduced,.see NADH Nitro~llumIon, 525-526 Nicotinarmde adenine dinucleotide phosphate, see Nitronium salts, 526 NADP m-Nitrophenol, t890 reduced, see NADPH ~ntermolecularh drogen bonding, S90,89 1- 892 Nicotine, 1059, 1073 o-Nitrophenol, t89( 902 (-)-Nicotine, 1075 chelation, 89 1 N~cotinicacid see 3-Pyridinecarboxylic acid preparation, 900,906 - 907 Nitration pNitrophenol, 769, t890 of benzene, 497,5 18 intermolecular hydrogen bonding, 890,89 1- 892 orientation of in substituted benzenes, t521 preparation, 900 of phenols, 900,906 - 907 Nitrophenols of pyridine, 1068 idtared bands, t892 of pyrrole, furan and thiophene, 1064 models of, 892 reaction mecha&m, 525 - 527,532- 533 pNitropheny1 acetate, preparation, 769,900 Nitriles o-Nitropheny! meeyl ether, 902 hydrolysis, 678-679,722,724,870 3-Nitrophthahc aad, 750 infrared absorption frequencies, t592 l-Nitropropane, 828 nomenclature, 725 3-Nitropyridine, 1068 preparation, 678-679,723,724,870 4-Nitropyridine n-oxide, 1073 reduction, 830,83 1 Nitroquinolines, 1069 Nitnle synthesis Nitrosation, 5 19,864 of carboxylic acids, 722,723,724-725 of phenols, 901,907 o-Nitroacetanilide, 546,832 pNitroso-N,Ndmeth laniline, 822,954 pNitroacetanilide, 546,86 1 preparation, 849,8d;. pNitroacetophenone, 668 N-Nitroso-N-methylahe, 865 m-Nitroene, t824 4-Nitroso-2-methylphenol, 90 1 o-N~trodne,t824 Nitrosinium ion, 865 p-Nitroaniline, t824, 828,873 pNitrosophenol,907 - preparation, 861 PNitrostyrene, 986 o-Nitroanisole, 902 o-Nitrotoluene, 509,871 m-Nitrobenzaldehyde, 695,678 preparation, 562 pNitrobenzaldehyde, 659,683 pNitrotoluene, 563,662,721, 832, 870, 871, 872 preparation, 662,663 preparation, 562 Nitrobenzene, 508, t520,667,827,872,947 pNitrotriphenylmethy1 hydroperoxide, 897 orientahon of electrophilicsubst~tut~on, 539 -.540 N~troqaad preparation, 497 reaeons yith amines, 849,864-866 rate comparison, 536- 537 readon wth urea, 783 pNitrobemenediazonium ion, 880 NMR, see Nuclear magnetic resonancespectroscopy m-Nitrobenzoic acid, 509,667, t715,750 Nodal plane, 992 Nodes, wave, 992 o-%L'obeGo$ acid, t7 15 Nomenclature, see specificfamilies 0-Nitrobenzoic acid. 563.713,. . t715.721.750 Nonadn, 48 1 relative acidity, 73 l n-Nonadecane, t93 Nitrobemo~caads, 524 - 525 n-Nonane, t93,98,102 m-Nitrobemophenone, 666 - 667 Non-bonding orbitals, 996 l-Nonene, 1285 -m-Nitrobemoyl chloride, 667 Non-ionic solutes, 252-254 pNitrobenzoy1 chloride, 663,668, t755 Non-stereoslective addition, 476 mNitrobenzv1 alcohol. 683 l-Nonyne, t429 >NiGObenZyl benzoaie, 564 Noradrenaline, 9 15 pNitrobenzy1 bromide, 552,902 Norbornane, 445 pNjtrobenzy1 isophthalate, 564 Norbornene, 32 1 pN~trobenzylphthalate, 564 exo-Norbornene, 1023 ~Nitrobenzylterephthalate, 564 exo-Norborneol, 32 1 pNitrobenzyl ptolyl ether, 902 Norcarane, 174,489 pNitrobiphenyl,547 Nortricyclene, 445 o-Nitrocinnamic acid, 750 Novocaine, 882 Nitro compounds N-terminal residue, 12 19 1314 Nuclear magnetic resonancX spectra n-Octyl bromide

Nuclear magnetic resonance spectra, vs. addition, 756 com~licated,623 -625 vs. allcyl substi!ution, 759-760 Nuclear magnetic resonance (NMR) Nucleophilic ad&aon 192,585,600-629 acid-catalyzed, 67 1 absor&onfrequency, 600 to aldehydes and ketones, 671 -684 of alcohols, 640 in aldol condensation, 800 - 80 1,s13 of aldehydes, 70 1 in Cannizzaro reaction, 683-684 of amides, 786,877 to carbonyl compounds, 800 - 80 1 of amines, 877 to a$-unsaturated carbonyl compounds, 974, carbon- 13 (CMR), 629 - 639 976-978 of carboxygc acid derivatives, 785 vs. acyl substitution, 756 of carboxyhc aclds, 747 in Wittig reactions, 8 11 - 8 12 chemical shifts. 604-608. t607 (See also Addition reactions) 6 scale, 605 ' Nucleophilic aliphatic (alkyl) substitution, 166, of 1", 2", and 3" hydrogens, 604-607 175-181 reference mint, 605 alcohols. 229.232.239 7 scale, 605 in alkylation of esters, 802,924-930 conformational analysis and, 625 - 629 alkyl halides and organometallicorga$omet&c cornpun&,co&pun&, coupling constant, 6 14,620 101 - 102,172- 175,802 conformations and, 620 +kyl sulfonates, 233-234 decoupling spins in, 624 - 625 m ammonolys~sof halides, 832-834 deuterium labeling, 625 in cleavage of ethers, 242 - 243 double resonance method, 624-625 electronic effects, 961 of esters. 786 energy cwe, 956 field strength, 600 - 60 1 and epoxides, 485-487 of fluorine, 617,629 a-halogenated acids, 741 -742 of hydrocarbons, 623 -624,639 kinetics, 178 inversion of molecules and, 626 mechanisms, 179- 181,955-956 magnetic moment in, 600 in Michael addition, 979-982 molecular changes and, 625 -629 vs. acyl substitution, 759-760 of monosaccharides, 1184 Nucleophilic aromatic substitution, 944,952-967 peak area and proton counting in, 609 bimolecul~displacement, 952- 956 of 2,4-pentanedione, 820 mechamsm, 955-956,959-961 of phenols, 9 13 orientation, 957-958 of l -phenyl- 1,3-butanedione, 820 reactivity, 952-955,956-957 proton exchange, 626 elimination-addition (benzyne), 949,962-967 protons in, 600 energy curve, 956 aromatic, 606, t607 in pyridine, l069 - 107 1 chemical shifts, 604-608 Nucleophilic assistance, to solvolysis, 269 -271 counting of, and peak area, 609 Nucleoph&c power, 176,257,269 deshielded, 604 Nucleophdx reagents, 172 &astereotop~c,603 Nucleophilic substitution enantiotopic, 603 !n allylic substrates, 404-406,407 eqgvalent, 60 1- 604,625 -629 m benzyhc substrates, 575 -576 nelghbonng, 6 16 in vinylic substrates, 407 -409 non-eqmvalent, 605,6 16 Nucleophihc sulfonyl substituaon, 859 shielded, 604 Nucleoprote~ns,1241 - 1246 side-chain, 607 - 609 Nucleosides. 1241 rotations about single bonds in, 626-629 signals in, 60 1- 604 intensities, 601,609 number of, 60 1- 604 positions of, 601,604-608 splitting of, 601,610-619 spin (of nuclei) in, 600 spin-spin coupling, 6 10- 620 Oblivon, 8 18 structural information from, 602-603 Octa-o-acetylcellobiose, 1200 temperature effects, 629 Octacarbonyldicobalt, 1052 theory, 600- 60 1 9,12-Octadecadienoic acid, 1100 Nuclear spin, 600 n-Octadecane, t93 Nucleic aci*, 1077, 1128, 1182, 1241- 1246 c@-9-Octadecenoicacid (Oleic acid), 7 13, t7 15,1122 denaturaaon, 1226 cz3-9-Octadecen-1-01.773 genetic code, 1246 - 1247 n-Octadecyl alcohol,'t216 heredity and, 1246 - 1247 1,4,5,8,11,12,13,14-Wydro-9,lO-anthraquin- primary structure, 1241 - 1242 one, 983 secondary structure, 1242 - 1245 A'~9-Octalone,98 1 Nucleophiles, 172- 173, 175 - 178 Octa-o-methyl-D-maltobionic acid, 1187 - 1188 ad&uon effect, 34 1 n-Octane, t93 concentration of, 2 10 mass spectrum, 587 nature of, 2 10 Octane number, 118 Nucleophilic acyl substitution, 758 2-Octanol, 242 acid-catalyzed, 758 (+)-2-Octanol, 182 in acid chlorides, 76 1-762 (-)-2-Octanol, 182 acylation of organocopper compounds, 668 - 2,4,6-Octatriene, 1006, 101 1 in carboxylic acid derivatives, 755 -760 l-Octene, t285,322,355,392 in Claisen condensation.,, 802.8 13 - 8 15 CMR spectrum, 634-635 in esters, 770- 771 infrared spectrum, 59 1 in Friedel-Crafts acylation, 666 - 667 n-Octyl alcohol, t2 16 in hydrolysis of amides, 767, 859 n-Octyl bromide, t169 n-Octyl chloride m 1,3-Pentadiene

I-Octyl chloride, t169 Oxalic acid (eeanedioic acid), 705, t742 z-Octyl iodide, 102, t169 Oxaloacehc acid, 11 14, 1139 .-Octyne, t429 Oxazole, 1057 l-Octyne, t429 2-Oxazoline, 932, 1058 Idor - Oxidation acid chlorides, 755 of alcohols, 226,235-237,662,663,665, amines, 823 of aldehydes and ketones, 675 - 677 carboxylic aci+, 717 of alkenes, 359-360 and configurabon, 137 of alkvlbenzenes. 563-564 esters, 755 if amines, 823 ' Yi of wintemeen,- 9 14 biological, 1103 - 1106 3ils of ethanol, 1101 - 1106 definition, l l20 of carbohydrates, 1149 - 1150 drying,. l l27 in determination of structure, 699 hardemng of, 1127 of 1,2-diols, 699 hydrogenation of, 1127 of methane, 42-43 31+, George, 192,347,376,526,535 of methylbenzenes, 662,665 31eic acld, 713, t715, 1122 Onmes, 673,679,697 3leomargarine, 1127 Oxirane ring, 48 1 31eyl alcohol, 773 Oxonium ions, 34,906 3ligosaccharides, 1198 0x0 Drocess. 218. 1052- 1053 Olive oil, t1121 oxygen, 178 . Olivetol, 9 !5. electron-deficient, 895 - 896 Optical act~nty,128 - 130 as tracer, 118 in armnes, 825 transuort of by hemoglobin, 1235 in amino acids, 1049 - 1051 Oxygen exchange and ckahty, 1.39, 154- 155 in hydrolysis of esten, 774-775,778 and configurat~on,140-141, 1173-1174 in rearrangement studies, 896 and enantiomerism, 133 Oxygen-hydrogen bond, 20 in naturally occumng substances, 159 0xym~;curation-demercuration, 222,32 1, Optical families, 1162- 1164 54 1 Optical isomers, see Stereoisomerism Oxytocin, 1216- 1217 Optical purity, 156,194 Ozone. 70. 119.359 Orbitals. 6.992 ozone'layer . atomic, 6-7 deplebon of, 3,69-71, 120 bond, 9,10 formation of, 70 geometry of, 15,275 Ozonides, 359 hybrid, 11 - 19,276 Ozonolysis molecular, 9,99 1- 1030 of alkenes, 358-360 overlap of, 9 - 10 of dienes, 422 size and hybridization, 276 2,34:%75,426 6=427,501--503 S, 6-7,275 a, 10, 11, 13,78,274-275,426,501 Paints. 1127 sp 11-13,426 eg,1100 S$, 13-15,67-69,274-275,502 Pal1111bc acld, t7 15 S$, 15-19,453 biosynthesis, 1134 (See also Molecular orbitals) Palm kernel oil, t 112 1 Orbital symmetry, 1004- 1024 Palm oil, t1121 Orcmol, 9 15 Pamaquine, 1075 Organoborane compounds, 933-935 Pan, S.C., 1203 Organocopper compounds, 102 Paneth, Fritz, 76 in preparation of ketones, 664,668-669 (+)-Panose, 1203 reactivity, 668 Pantothenic acid, 882 Organolithiumcompounds, 102,685,696,966-967 Papaverine, 75 Organometallic compounds, 100,437,686 Paraffin-based petroleum, 96 adhhon of carbenes, 477 -478 ParafEns, see Alkanes coupling with alkyl halides, 10 1- 102 Paraflin wax, 96 Gripard reagent, 99, 100 Paraformaldehyde, 660,661 use in synthesis, 923 Paraldehyde, 66 1 Organosodium compounds, 102 Paramagnetism, 573 Orientation, 538 - 540. Para red, 875 of free-radd adhbon, 352-355 Pasteur, Lams, 130, 138, 1164 of halogenation, 107 - 109 Pauli, Wolfgang, Jr., 8 in hydroboration, 348 - 349 Pauli exclusion principle, 8,398 reactivity and, 114- 115,300-303,307,335- Pauling, Linus, 10, 1230 338,337,391,536-540,579 Peanut oi, t1121, 1137 Saytzeff S rule, 3 14 Pectic acid, 1203 in substitution, 520-521,522-524,545 -546 Pectin, 1203 and synthesis, 524- 525 Pedersen, Charles J., 479,916-917 Orlon, see Polyacrylonitrile Pendant groups, 1080 Ornithine, 1250 Penicillin G, 863, 1059 Ortho effect, 736, 853 Penicilliurn glaucum, 137 Ortho,para-directinggroups, 519-525, 542, 848, D-Penta-o-acetylglucopyranose,1 184 860,900,905,948 (See also Orientation) Penta-o-acetylglucose, 1145 Osazones, 115 1- 1152 D-Penta-o-acetylmannopyranose, 1184 Osmium tetroxide, 484 n-Pentadecane, 83 Osones, l l5 1 1,3-Pentadiene, t411,442, 1017 1316 14-Pentadiene Phenylacetyl chloride

1,4Pentadiene,.410,t411 source of aromatic compounds, 555 Pentadienyl cabon, 101 1 source of carboxvlic acids. 720 Pentaeryhitol uses, 96 physical constants, c216 Petroleum coke, t96 synthesis, 8 18 Petroleum ether, 86 Pentamethylbenzene, t553 Petroleum jelly, 96 Pentamethylsalicin, 1182 Phases - n-Pentane, 87, t272,599 of orbitals, 992-994 CMR, chemical shift, 636,637 of waves, 992 nomenclature, 90 Phase-transfer catalysis, 265 physical constants, t93, t217,442,660 (+)-Phellandral, 9 17 2,4Pentanedione, 798 (-)-Phellandral, 9 17 NMR spectrum, 820 (-)-PheUandric acid, 9 17 preparation, 8 16 Phenamn, 9 16 Pentanenitrile (valeronitrile), 212, 722, 724, Phenanthrene. 5 10 725 test for, 580 ~ent&es,90 - 92 Phenetole, see Ethyl phenyl ether isomers of, 87,95 Phenol, 889, t890 Pentanoic acid (valeric acid), t7 15,716, 722, 750, industrial source, 555-556,894 1175 reactions, 240,447, t520,531, 540-541, 899- 902.905-911,------relative acidity, 899 , , use, 893 reductive amination, 835 (See also Phenols) 3-Pentanone, 226,659, t661 2,4-Phenoldisulfonicacid, 907 l-Pentene, t285, 306, t326, 360,599,855 Phenol-formaldehyde resins, 109 1 2-Pentene, t285,306, ~326,326,329,442,855 PhenoGc an&, 908 isomers of. t285. t326.327 Phenohc esters, 738 Pentosan, l062 ' Phenolic ethers Pentose. 1062 preparation, 902 n-pent$ acetate, t769 spectroscopic analysis, 596, t607, n-Pentyl alcohol, t2 16,224 913 tert-Pentyl alcohol (2-methyl-2-butanol), 2 15,t2 16, Phenolic ketones, 905,907 -314 - ., 7211. - - Phenols, 2 14,889-922 n-Pentylamine, 830 acidity, 843, 874-875, t890, 903- 1009 tert-Pentylbenzene, 560 effect of substituents, 904 n-Pentyl bromide, 99,1169 aldehydes from, 902,908-909 tert-Pentyl bromide, 306,3 10 analysis, 843,912-913 tert-Pentyl cation, 205 carbonation, 902,908 n-Pentyl chloride, 89, t169,430,224 coupling with diazonium salts, 868,873-875 tert-Pentyl chloride (2chloro-2-methylbutane), 722 electrophili~substitution, 900 - 902,906 - 907 preparation, 230,336 fiom essephal oils, 894 Pentylenes (amylenes), 282 estenficahon, 738, 899,905 n-Pentyl iodide, t 169 ether formation, 902 tert-Pentyl iodide, see 2-Iodo-2-methylbutane formation, during diyotization, 870 n-Pentyl phenyl ketone, 663,667 Friedel-Crafts acylahon, 90 1 2-Pentyl tosylate, 306 Friedel-Crafts alkylation, 90 1 2-Pentyltrimethylammonium ion, 855 Fries rearrangement, 901,905 2-Pentylurethane, 783 halogenation, 901,906 l-Pentyne, t429,442 hydrogen bonding, 89 1- 892 2-Pentyne, ~429,438 industrial source, 893- 894 3-Pentyn-2-01,692 ionization, 843 4-Pentyn-1,2,3-triol, 118 1 Kolbe reaction, 902 Peptide chains, 1226, 1230 nitrosation, 90 1 Peptides, 12 15; 1225, 1240 in polymerization, 1090- 1092 molecular weights, 12 18 preparabon, 895 -899 peptide linkage, 12 15 - 1217 from diazonium salts, 868, 870,898 geometry of, 12 16 reactions, 240,868 structure determination. 12 17 - 1221 with di~onium,salts, 873- 875 synthesis, 1221- 1225 with femc chlonde, 9 12 solid-phase, 1225 with forpaldehyde, 1090- 1092 Periodic acid, 237,359- 360 A Reimer-Tiemann reaction, 902,908 analys~sof carbohydrates, 1150 ring substitution, 906-908 analysis of 1,2-diols, 699 salts. 843 Peridc Table, inside back cover speckoscopic analysis, t592,t786, 9 Perkin condensahon, 8 10-8 11,973 sulfonation, 900 Permanganate test, 694 Williamson synthesis, 902, 910 Peroxide effect. 330- 33 1 (See also Hydroquinone) mechanism. '35 1- 352 o-Phenolsulfonjc acid, 900, 906 Peroxides, 330 pPhenolsulfomc acid, 900, 906, 907 analysis for, in ethers, 238. Phenoxyacehc and, 902 effect on orientation, 579- 2-Phenoxvethanol. 9 10 removal from ethers, 240 ~henoxid;ion, 843; 903,904,910 Peroxy acids, 357-358 Phenylacetaldehyde, 659, t661 Peroxybenzoic acid, 322,48 1 Phenylacetamide, 727 Peroxyformic acid, 358,484 N-Phenylacetamide, see Acetanilide Perutz, M.F., 1235 Phenyl acetate, c769 Petroleum, 1,219,220 Phenylacetic acid, 713, t715,722,727 constituents, 94, t96 Phenylacetomtrile, 830 source of alcohols, 218 Phenylacetyl chlonde, 727 Phenylacetylene Polyamides

Phenylacetylene, 55 1, t553 Phenyl n-propyl ketone, 672 Phenylalanine, 1209 2-Phenylpyxidne, 1070 (-)-Phenylalanine, t 1207, 12 13 Phenylthiohydantoins, 12 19 Phenylalkanes, 55 1 Phenyltrimethylammoniumiodide, 829 p(Phenylazo)phenol, 868 Pheromones, 382,442,491,819, 1055 2-(Phenylazo)pyrrole, 1063 Phillips, Henry, 180 N-Phenylbenzenesulfonamide, 848 Phloroglucinol, 9 16 Phenyl benzoate, 547 Phosgene (carbonyl chloride), 780,78 1-782,789, preparation, 762,899 1222 l-Phenyl-I,3-butadiene, 583, 801 manufacture, 78 1 l-Phenyl- 1,3-butanedione, 820 reactions, 782 2-Phenyl-2-butene, 55 1 Phosphate esters, 1128 - 1130 4-Phenyl-3-buten-2-one, 801,810,973 Phosphatidic acid, 1128 3-Phenyl-2-butyl tosylate, 1055 Phosphatidyl choline, 1130 y-Phenylbutyic acid, 7 16,738 Phosphatidyl ethanolamine, 1130 Phenyl carbitol, 484 Phosphoglycerides, 1128 - 1130 l-Phenyl-l-chloroethane, 552,577 Phospholipids, 882, 1128,1129 - 1130 2-Phenyl-l-chloroethane, 552 in cell membranes, 1 130 - 113 1 l-Phenyl-2-chloropropane, 577 Phosphonium salts, 8 12 l-Phenylcyclopentene, 473 Phosphoric acid, 1128, .l 129 2-Phenylcyclopentyl tosylate, 473 Phosphorus pentachlonde, 737 l-Phenyl-3,4-dibromo-l-butene,583 Phosphorus trichloride, 737 m-Phenylenediamine, t824 Phosphorus trihalides, 225,692 o-Phenylenediamine, t824 Phosphorus ylides, 8 12 pphenylenediamine, 5 14, t824,828, 1099 Photolysis, 69 Phenylethanal, 659 Photosynthesis, 220, 1143, 1182 l-Phenylethanol, see a-Phenylethyl alcohol Phthalamic, acid, 768 2-Phenylethanol, see&Phenylethyl alcohol Phthalic acld, 564, t715, t742 a-Phenylethyl alcohol (l-phenylethanol), 170, 194, lndustnal source, 720 t216, 552, 557, 577 Phthalic anhydride, t755 preparation, 672,689 in polymerization, 1090,1091 /3-Phenylethylalcohol, t2 16,552 preparation, 763 preparation, 688 reactions, 765,768 a-Phenvlethvlarmne, f824 Phthalimde, t755,844 acidity constant, 768 preparation, 768 Phthalimidomalonic ester method, 1214 . preparation, 830 Phytol, 1122 a-Phenylethyl bromide (l-bromo-1-phenylethane), Picolines, t1058, 1067- 1068 t169. 857 Picolinic acid, t1058 pG~tion,170,550,566 x-complexes, 506 -507, 1045, 1051 B-Phenylethyl bromide, t169,296-297,857 Picric acid{2,4,5-trinitrophenol), 547, cu-Phenyle%yl chloride, 159, t169, 194,552,567 preparabon, 899,907,953 preparaaon, 563 Picrvl chlonde. t945.953-954 /3-Phenylethyl chloride, t169,552,557,567 Pimklic acid, h75 ' preparation, 563 Pinacol(2,3-dimethyl-2,3-butanediol),705 Phenylethylene, see Styrene Pinacol rearrangement, 705 a-Phenylethyl hydroperoxide, 896 Piperic acid, 9 18 . p-Phenylethyl iodide, t 169 Pipendine, 837,982,988, Phenylglyoxal, 684 in alkalojds, 1073 Phenyl group, 296 preparaaon, 9 18, 1073 Phenylhydrazine, 673 -674,679,680 Piperine, 9 18 in carbohydrate studies, 115 1 Piperonal t66 1, 9 19 Phenylhydrazine hydrochloride, 679 - 680 Piueronvlic acid. 9 18 Phenylhydrazones, 673-674,679 &er, $.S.? 468 Phenyl isothiocyanate, 12 19 Plane-polarized light, 128 Phenyllithium, 1070 Plasticizers, 1126 reactions, 949,966 Plastics Phenylmagnesium bromide, 688,689,704 industry, 420 -Phenvlmalonic ester. 748. 816 preparabon, 1077 2 -p~-- l-~hen~l-3-meth~l-2-bu&l,691 structure. 1096 5-Phenyl-2,4-pentadienal,8 10 uses, 1077 - 1078 3-Phenylpropanoic acid, 716 (See also Polymers) 1-Phenyl-2-propanol, 183,577 Plemglas, 973, 1081, 1096 l-Phenyl-2-propanone,660 PMR, 600,629 3-Phenylpropenal, 677 Polar effect, 185- 186, 199 (See also Electronic ef- 3-Phenyl-2-propenal, 801,8 10,973 fects) l-Phenylpropene Polar factors cis and trans isomers, 583 in free-radical addition, 354 preparation, 577 in Hofmann orientabon, 855- 857 2-Phenvlurouene. 584 Polarimeter. 128- 129 Polarity , of bonds, 23 , . . , .. . -, ., . of molecules, 23 -26 propen-1-01 (cinnamyl alcohol), t216, Polaroid, 128 Pnlli~tinn------a-~h;:*~l~ropionaldehyde,840 from automobile emission, 119 (+)-a-Phenylpropionamide, 159,840 from plastics, 1077 Phenyl propionate, 905 Polyacrylonitrile (Orlon), 357, 973, 1080, 1094 Phenyl n-propyl ether, 242,9 10 Polyamides, 1090 1318 Polybutdiene Proteins

Polybutadiene, 41 9 Probability factor, 59 copolymers, 1096 and reaction rates, 55 - 56 Polychloroprene, 420 Prochiral center, 1107, 11 1 1 Polycyclic compounds, 445 -446 Progesterone, 1141- 1142 Polyester resin, 1097 (-)-Proline, t 1207 Polyesters, 1090 synthesis, 1248 Polyethylene, preparation, 356, 1088 Proline residue, 1234 Polyhalomethanes, 7 1 1,2-Propadiene, t4 11 cis-Polyisoprene, 420 -42 1, 1089, 1095 Propanal, see Propionaldehyde Polyme.rization, 356-357, 1077- 1100 Propane, 83-85, t93,319,397,449 addibon, 1079 rotational barrier in, 83 of alkenes, 356-357,419 Propanedioic acid, see Malonic acid anionic, 1084- 1085 1,2-Propanediol, t216, 322,485,491 "back-biting", 1083 preparation, 322,358, 11 15 cationic, 1084- 1085 (+)- 1,2-Propanediol, 1163 chain-reaction, 1078 1,3-Propapepiol, t2 16 condensation, 1079 Propanemtnle, 247 definition, 356 1,2,3-Propanetriol, see Glycerol of dienes, 4 19 -42 1 2-Propanol, see Isopropyl alcohol free-radical vinyl, 1080- 1083 Propanone, see Acetone of alkenes, 356-357 Propargyl chloride, t169 of dienes, 4 19 -42 1 Propenal, see Acrolein stepreamon, 1078- 1079 Propene, see Propylene stereochemical control, 1088 Propenenit.de, see Acrylonit.de transfer constant. 1082 Propenoic acid, see Acrylic acid vinyl, 1080 2-Propen-l-ol,2 14,283 Polymers, 356,419-421, 1077- 1100 Properties, and structure, 1- 38 branched, 1096 Prophos, 1051 crystallinity, 1088- 1096 /l-Propiolactone, 1098 formation, 356,419-421 Propiolic acid, 988 linear, 1096 Prppionaldehyde, 226,323,659, t661 living, 1084- 1086 in aldol condensahon, 806 surface-active, 1097 Propionamide, t755 Poly(methy1 methacrylate), 973, 108 1, 1096, Propionic acid, 660, t715,717,750, 833, 973, Polynuclear aromatic compounds, 5 10- 5 12 infrared spectrum, 745 - 746 Polvnucleotide chains. 1241 Propionyl chloride, 2755 ~ol~(oxyprop~lene)glycols, 485 Propiophenone, t66 1 Polypeptides, 12 15 (See also Peptides) n-Propyl acetate, t769 Polypropylene, 1088- 1089 n-Propyl alcohol, 170, t216,226,229,316,348 Polysaccharides, 1077- 1078, 1 192- 1201 n-Propylamne. t824. 847 definition, 1144 preparation, 828 ' Polystyrene, 108 1, 1082 n-Propylbenzene, 551, t553,559,584 copolymers, 1083- 1084 NMR spectrum, 6 18 properties, 1096 n-Propyl bromide, 124, t169, 170, 188,240,31 Polystyrene(co-methyl methacrylate), 1083 330,353,388,926 Polyurethane foam rubber, 485 n-Propyl chloride, 89,104, t169, t217,229,t272, Polyurethanes, 1092 NMR sienals. 602 Poly(viny1 acetate), 1093 n-~ro~~ldi'heth~lamine,847 Poly(vinyl chloride) n-Propy13,5dinitrobenzoate,762 preparation, 356, 1080 Propylene, 276,280,282,284, t285, 316, t326, properties, 1094, 1096 337-339,397 Poly(vinylidene chloride), 1094 CMR and NMR analysis; 637-638 Ponnamperuma, Cynl, 159 polymerization, 1088, 1097 Porphin, 1228 preparation, 290-291 Porphyrin system, 106 1 reactions, 319-320,322,323,335,338,342, Potassium permanganate, 358 349,358,364,388 Potassium tert-butoxide, 476,703 structure. 276 preparation, 225 Propylene bromide (1,2dibromopropane),3 19, Potassium 2,3dibromopropanoate, 7 17 339.429 Potassium (~j3-dibromopropionate,717 Pro~vlenechloride. 389 Potassium d-tert-butylphenoxlde, 934 ProGlene chlorohydrin (l-chloro-2-propanol), Potassium isopropoxide, 227 23 1,320,342,487 Potassium phthalimide, 1213,1214 Propylene oxide, 485,491 Potassium triphenylmethide, 970 Propyl groups, 90 Potential energy changes n-Propyl iodide, t169 in 1,2- vs. 1,4-addibon, 418 n-Propylmagnesium chloride, 100 in chlorination of allcanes, 107 n-Propylmalonic ester, 925 and conformation, 82,85,458 n-Propylmethylamine, 847 in halogenation of methane, 52,53,61,66, n-Propyl m-tolyl ketone, 664, 667 in hydrogenation of alkenes, 325 n-Propyltrimethylammonium iodide, 847 in simple dissociation, 55 Pro~yne,t429.436.437 Power sources, 2 preparation; 429. Pre-cholecalciferol, 1030 Propyn-l-yllithium, 437 5a-Pregnane-3a-ol-20-one, Propyn- l -ylmagnesium bromide, 437,692 Prehnitene, t553 Pro-R.7 ----1 108 Prelog, V., 134, 140 pro-~,1108 Primeverose. 1202 Prosthetic groups, 286, 1228- 1229 Prismanes, 51 5 Protecting groups, 696,861, 1222, 1224 Probability, and orbitals, 6 Proteins, 1132, 1205 - 1206, 1225 - 1235 Protein sequenator Rearrangement

Pyrro!el 516, 548, 837, 880, 1057, t1058 p-,' 1234 ba~~aty,1060 - 1062, 1064 classification and function, 1225 - 1226 reactiops, 1062- 1063, 1064,1074 conformational analysis, 1229 reactinty, 1064 conjugated, 1228 - 1229 Source, 1060- 1062 denaturation, 1225 - 1226 structure, 548, 1059-1061, 1065 DNA and synthesis, 69, 1246- 1247 2-Pyrrolecarboxaldehyde, 1064 fibrous, 1225 Pyrro!kjine, 837,880, t1058 globular, 1225 - 1226, 1234 basicity, 1065 isoelectric point, 1226 peptide chains, 1226 reactions, 937 side chains, 1226 structure, 1057, 1065, 1066 . ' structure, 1226 hnhne. 1074 'rotein sequenator, 12 19 'rotic solvents, 254-258 'rotium, 117,969 'rotocatechuic acid, 9 18 htodesulfonation, 530 3otonated alcohol, 176 Q 'rotonated epoxide, 9 10 - 9 11 Qualitative elemental analysis, 72 - 73 %otonatedether, 242 -243 Quantitative elemental analysis, 5 13- 5 14 ?rotonation, of aromatic compounds, 5 19, Quantum mechanics, 4,5,991 530 Quat, 265 Proton counting, 609 Quaternary ammonium hydroxide, 854 Proton exchange, 640 Quaternary ammonium salts, 258,265,834,849, Proton magnetic resonance (PMR), 600,629 854-855, 1072 Protonolvsis. 934 (-)-Quinine, 159, 160 Protons ih nuclear magnetic resonance Quinoline, 1057, t1058,1069 alignment, 600-60 1 Quinones, 984-985 chemical shifts for, characteristic, t607 counting, 609 equivalence, 601 - 604,605 -606,625 - 629 and psitlon of WRsignals, 604-608 shleldmg and desbeldmg, 604 R, prefix, for configuration, 140- 141, 1108, 1163 spin-spin coupling, 6 10-620 R, symbol for alkyl group, 97 vicinal. 620 Racemic mdcation vinylic; 620 definition, 138 Pseudocumene, t553 formation, 15 1 Pseudotropine, 1076 Racemization, 368 D-Psicose, 1162 through free-radical formation. 161 Puckered rings, 452 partid, 194 Purine, 837, 1057 resolution, 138, 153, 158- 160 Purity, of syntheac products, 871 in,%l reactions, 194, 196 Putremne..- . - 844.986 Ra&abon, biolo@callyharmful, 70 PVC, see Pd~~(;in~lchloride) Radical-anion, 1085- 1086 Pyran, 1177 Radical character, 115 Pyranose ring, 1178 Radicals, see Free radicals Pyranosides, 1178 Radioactive labeling, see Isotopic tracers *ale, l057 (+)-Ra5nose, 1202 Pyridine, 385,837, 1057, t1058, 1064, 1073 Rancidity, of fats, 1127 in alkaloids, 1073 Rappaport, Zvi, 408 as base, 762 Rate constant, 178 basicity, 1071 - 1073. Rate-determining step, 188,297 electrophibc aromahc substitution, 1068- 1069 Rate equation, 57 nitration. 1068 Rates of reaction, 55-59, 166- 167, 177, nucleopf;ilic aromatic substitution, 1069- 1071, 1041 I n77 and activation energy, 56 and molecular structure, 114 reduction, 1073 and probability factor, 55 -56 source, 1067- 1068 relative, 58-59 structure, 502-503, 1066- 1067, 1073 and temperature, 58 sulfonation, 1068 Rayon, 1201 Pyridineacetic acids, 1076 Reactant state, 579 Pyridinecarboxylic acids, 1069, 1074 Reaction constant, 732 2-Pv~idinecarboxvlicacid, 1067- 1068.1074. 1076 Reaction mechanisms, 45 3-P$dinewboxj4ic acid.(niacin, nicotinic acid), Reaction progress, 52- 55 t1058, 1067- 1068, 1074 Reaction rate, see Rates of reaction decarboxylation, 1076 Reactions 4-Pyridinecarboxylic acid (isonicotinic acid), intermolecular. 448

-1067- - . -1068. - - - 7 --1074 - physical constants, t1058 preparation, 1068 Pyridine methiodide, 1072 Pyridine N-oxide., 10/2- 1073 3-Pvridinesulfomc aad 1068 andselectivity, 115-116 F'yridinium chlorochromate, 237,662 Rearrangement Pyrimidine, 837,1057 of carbocations, 203 - 208 Pyrolysis, of alkanes, 120- 121 in dehydration of alcohols, 3 14 in electrophilic addition, 334-335 1320 Reducing sugars Skewphos

Rearrangement, (cont.) Roberts, John D., 395,626,963 in Friedel-Crafts alkylation, 559 Rosanoff, M.A.? 1166 in Hofmann degradation, 838 - 843 Rotational barner of hydroperoxides, 895- 898 in carbon-carbon single bonds, 79 - 83 Lossen, 844 in ethane, 82 in SN1reactions, 204-208,405-406 in Drouane. 83 Reducing sugars, 1144 (~iedso.&bon-carbon bonds) ondabon rate, 1182 Rotaaonal isomers, see Conformational isomers Reduction Rubber, 419 -421 biologcal, 1103 - 1106 preparation, 420 (See also Hydrogenaaon and specijic compouj~d structure, 420, 1095- 1096 orfamily) vulcanization, 420, 1096 Reductive amination, 831,834-835, 1214 (See also Natural rubber, cis-Polyisoprene) Reeves, R.E., 1179 Ruberythnc acid, 1202 Reface, 1111 Ruffdegradation, 1154 Reformatsky reaction, 939 Russell. Glen. 117 Reforming, see Catalyhc reforming "~uss&ndoll"molecule, 5 12 Regioselective reactions, 327 - 329,346 Re~mer-Tiemannsynthesis, 5 19,902,908- 909 Relaave reactivity, 45 Replication, 1246 S Repulsive forces, 20 S, prefm for configuration, 140- 141, 1108, 1163 Reserpine, 1059, 1073 Saccharic acid, see Glucaric acid Resins Sacrificial hyperconjugation, 413 structure, 1096 Safrole, 894, 919 synthesis, 1090- 1092 Salicin, 1182 Resolution, of racemic modification, 138, 153, Salicylaldehyde, 546,659, t661,1182 ..-158-160 -.. preparation, 902,908 Resonance, 387-424 Salicylic acid, t7 15,748 alkenes, 4 13 preparation, 908 allyl radical, 395 - 399 Saligenin, 1182 aromatic amines, 85 1 Salmine, 12 18 aryl and vinyl halides, 950-952 Sandmeyer reaction, 866,879 benzyl cation, 574 Sanger, Frederick, 12 18, 1220- 122 1, 1249- 1250 beql radical, 568-570 Saponification, 1124- 1125, 1138 carbanions with a-ionization, 798 Saponification equivalent, 784 carboxybc acids, 733 Saran, 357,1080, 1094 chloromtrobenzenes, 957- 959 Sarett, Lewis, 984 conjugated dienes, 4 11 -4 12 Saytzeff,Alexander, 301 definition, 394 Saytzeff orientation, 301,306 - 307 electron withdrawal by, 958-959 Saytzeff's rule, 301,307,314 hybrid, 394,526 SBR (styrene-butadiene rubber), 1096 phenols, 904 SchX test, 697 theory of, 394 Schlesinger, H.L, 349 use of, 399-401 Schleyer, Paul, 202,270 Resonance effect, 200,406 Sch8niger oxidation, 72,211 Resonance energy Schotten-Baumann reaction, 762,770,858-859, alkyl free radicals, 40 1 1072 allyl radical, 397-399 Schr&linger, Envin, 5 benzene. 498 - 500 Seagram, Joseph E., 1203 beGi&-c;?,568 -570 Second. 939 conjugated denes, 41 1 Secon& structure, of proteins, 1229- definition. 394 Selectivity, 105 pyrrole, &n, and thiophene, 1059- 1060 and reactivity, 115 - 116 triphenylmethyl radical, 570-574 Semicarbazjde, 673,679,680,705,990 Resonance stabhtion Se*carbazide hydrochloride, 679 aromatic Fnes, 851 -852,860-861 Semcarbazones, 673,679,697,990 bewl rad~cal,568-570 Sequence rules, for configuration, 140- carboxylic acids, 733 Serine, in chymotrypsin, 1237- 1238 phenols, 904 (-)-Serine, t1207 urea, 781-782 Sex attractants, 382, 706, 1029 Resonance structure, 500 Sex hormones, 1136 Resorcinol, 677,889,901 Sex pheromones, 442,819, 1055 Respiration, 11 14 Sheehan, John C., 1248 Retinal, 286-287 1,2-SW, 206-207,839, 895, 1041 Retinol, 286 stereochemisty, 840 Reversible reactions, 730-732 Sickle4 anemia 1227. 1247 Rhodopsin, 286 Sifa~,llll ' ' Ribitol, 1160 a orbitals, see Orbitals, Molecular or1 Ribonucleic acids, see RNA Sigmatropic reamons, 10 19- 1024 (-)-Ribose, 1160, 1162 Silk fibroin, proposed structure, 1231 D-Ribose, 1241 Silver ammonia ion, 676 Ring closure, 452 (See also Cyclization) Silver mirror test, 671, 676 Ring-opening reactions, 449 Silver nitrate, 2 11 RNA (ribonucleic acids), 1241- 1243, 1250 Simmons. H.E.. 477-478 and geneucs, 1246- 1247 ~immons'-smithreaction. 477-478 messenger, 1246 Singlet methylene, 474-476 structure, 1241 - 1242, 1245 Skell, P.S., 475 transport, 1247 Skew conformations, 79 Roberts, L, 374, 1034 Skewphos, 1051 Smalley, Richard E. Steric repulsion

Smalley, Richard E., 5 12 Solvolysis, 268-271, 1039 Smith, R.D., 477-478 nucleophilic ass~tanceto, 269 - 27 1 &l reactions, 232,409 Solvomercuration, 347 mechamsm and lanetics, 188 - 189 Sorbic acid, B72 migration, 841, 1035 Sorbitol (gucitol), 1145, 1149 reactivity, 200-203,404-406 D-Sorbose, 1162, 1183 rearrangement, 204-208,405 -406 Soybean oil, t 112 1 role of solvent, 258-26 1 Space-network pol&ers, 1090, 109 1 stereochemistry, 194- 196,368 structure, 1096 - . theory, 19 1 Spandex, 1094, 1097 vs. &2 reactions, 180,208-210,576 Specific rotation, 129 - 130 &2 reactions, 232 Spectra, analysis of, 642 cleavage of epoxides, 485-487 S~ectrometers.585 migrahon, 841, 1035 ~&ctroscopicmethods, 585 - 586 mechanism and kinetics, 181,955-956 Spectroscopy, and structure, 585 - 586 phase-transfer catalysis, 264-266 Suermaceti. 1137 reactivity, 185- 186,407 Skrmine, 986 role of solvent, 26 1- 264 Spin-spin coupling, in NMR,610-620 stereochemistry, 182- 184,367 Squalene, 1136 - 1137 steric factors, 187 - 188 Standing (stationary) waves, 992 vs. &l reactions, 180,208-210,576 Stang, Peter, 408 Soaps Stannic chloride, 35 cleansing power and solubility, 1124- 1125 Starch, 219,220, 1143- 1144, 1192-1193 manufacture, 1124 - 1125 , Stark, Charles M., 265 Sodioacetoacefic ester, 8 14,927 Steam cracking, 120 - 12 1 Sodiomalonic ester. l2 13 Stearamide, l755762 Sodium, 229 Stearic acid, t715,726,762 Sodium acetate, 680,939 Stearoyl chloride, 726, t755,762 Sodium acetylide Stepreaction polymerization, 357,1078- 1079, formation, 436 1089- 1092 reactions, 438 Stereochemical control, 234-235, 1088 Sodium &oxides, 227,241 -242 Stereochemistry, 125- 164, 175,367-386, 1106 Sodium amide, 1070 in addition of halogens, 368- 376 Sodium azide, 839 m Unehydrolysis of esters, 772-775 Sodium benzenesulfonate, 894, 1200 and chlonnation. 160- 162.368 Sodium benzoate, 717,725,771,859 control of ~olymerization,1088 Sodium borohydride, 346,349,35 1 definition,-125 Sodium a-bromopropionate, 1034 in Diels-Alder reaction, 10 13 - 10 18 Sodium tert-butoxide, 241 of electrocyclic reactions, 1005- 10 13 Sodium butyrate, 767 of elimination reactions, 377-380,471- Sodium chloride, 27,30 of epoxide cleavage, 483-484 Sodium chloroacetate, 743 of fatty acids, 1122 Sodium cyanoacetate, 743 of(+)-~~UCOS,1146-1149,1155-1160 Sodium cyanohydridoborate, 834 of Hofmann elimination. 855 Sodium 2,4-di111trophenoxide, 899 of homogeneous hydrogenation Sodium ethoxide, 225,227,309,483,814,815 diastereoselectinty, 1046- 1049 Sodium formate, 683,749 enantioselectivity, 1049- 1052 bond lengths, 397,734 of hydroboration, 348-349 Sodium hslon, 72,211 of neighboring group effects, 1032- 1035 Sodium hydroxide, 684 of nitro en compounds, 825 - 827 Sodium 0-hydroxybenzoate, 902 optical families D and L, 1162-1 164 Sodium isopropoxide, 240 sequence rules, 14 1- 144 Sodium lactate, 1034 of &l reactions, 194- 196,368 Sodium laurate, 725 of &2 ieactions, 182 - 184,367 Sodium lauryl sulfate, 1126 of stero~ds,1134- 1136 Sodium mandelate, 684 of (+)-sucrose, 119 1- 1192 Sodium methoxide, 684 Stereoisomerism Sodium o-nitrobenzenesulfonate, 954 cyclic compounds, 464 -47 1 Sodium pnitrobenzoate, 683 definition, 125,149- 150 Sodium periodate, 359-360 diastereomers, 144- 146 Sodium phenoxide enantiomers, 130 - 138 formation, 899 geometric (cis, trans) isomers, 279 reactions, 894,902 mterconvertibility, 149 Sodium ecylate, 902,908 meso structures, 146 - 147 Sodium tnchlorocetate, 938 reactions, 150 Soft soap, l l24 Stereoselective reactions, 367-386,433-434 Sofid-phase peptide synthesis, 1225 addition, 475 Solubility definition, 369 and interionic forces, 3 1 reduction of alkynes, 433 and intermolecular forces, 250-258 vs. stereospecific reactions, 382-383 and structure, 3 1- 33 Stereospecific reactions, 367- 386 Solutes, see Ionic solutes, Non-ionic solutes definition, 370,38 1 Solvating power, 254 vs. stereoselectivereactions, 382 - 383 Solvation. 228 Steric factors. 354.454 Solvents in butane, 86 . alcohols as, 217,255,256-257 in este&ication, 738 - 739 aprotic and protic, 26 1-264 in Hofmann orientation, 857 effect on rafe of reaction, 258-264 in &2 reactions, 187- 188 and reactinty, 175 Steric hindrance, 185- 188,209,231,738 role of, 210,249-272 Steric repuls~on,86 1322 Steric strain 1,3,5,5-Tetramethyl-l,3cyclohexadiene

Steric strain, 86,454 Symmetry, orbital, 994 Steroids, 421,984, 1030, Symmetry-allowed reactions, 1004 1140, 1141- 1142 Symphona, 175,383, 1031- 1056, 1088 Sterols. 1134 definition, 1032 stigmkterol, 1141 - 1142 syn-addlbon, 368 -370, 1047- 1048 cis-Stilbene, t553, 583 Syndiotactic polypropylene, 1088- 1089 trans-Stilbene, t553, 583 Synthesis Stork, Gilbert, 936 procedure, 247 Strecker synthesis, 12 14 working backwards, 690 Structural theory, 3 Synthetic fkels, 120 Structure, 1- 38 Szwarc, Michael, 1086 atomic, 6 molecular, 6 Strychnine, 159, 1073 (-)-Strychnine, 160 Styrene (phenylethylene, vinylbenzene), 298, 551, t553. 557.578 D-Tagatose, 1162 commercial'preparation, 577 (+)-Talose, 116 1 polymerization, 108 1- 1084, 1085- 1086, 1096 Tamelen, E.E., van, 1030 Styrene-butadiene rubber (SBR), 1096 Tanret, C., 1169 Suberic acid, 750 Tarbell, D.S., 989 Substitution nucleophilic bimolecular reactions, Tartaric acid, 154,918 see &2 reactions configuration, 140, 1164- 1166 Substitution nucleophilic unimolecular reactions. optical activity, 130, 154- 155 see G1reactiois (+)-Tartaric aad, 1164- 1166 Substitution reactions, see Free-radical substitu- (-)-Tartaricacid, 1161,1167 tion, In$molecular nucleophilic substitution, w(-)-T*c acid, 1 165 &l reamons, &2 rea&ons L-l+bTartanc aad. 1165 Substrate. 173 Tauiomerism ' alcohols as. 177 enol-keto, 435 -436 nature of, 209 imine-enarnine, 935 reactivity of, 179-181. 185. 188 Tautomers, 436 . Succinamk acid, 764 Teflon, 357 Succinic acid, l i 15,742, t742 Terebic acid, 94 1 Succinic anhydride, 1755,763,764 TerephthaIic acid (1,4-benzenedicarboxylic acid), Succinimde, 390, t755 546, 563, 564, t715, t742, 1079, 1099 Succinoylsulfathiazole, 864 Terminal residue analysis, 12 18 - 1221 1 Sucrose. 218. 1144.7 --146 - Terpenes, 421,424,488,492,647,705,915,917, inve&on of. l 19 1 919,.939:940,941, 1120, 1128 (+)-sucrose, 1185; iiw-1192 Temnyhc aad. 94 1 Sugar cane, as alcohol source, 2 18 Sulfa drugs, 863-864 y-Te6inene; 42 1 Sulfamerazine, 864 a-Terpineol, 492,9 19,941 Sulfa@-imide, t824,.863 -864 Terpin hydrate, 492 anhbactenal a&vlty, 863 - 864 Terramycin, 863 preparation, 863 Tervlene.,-- , -l094 N-substituted, 864 Testosterone, 1136 Sulfanilic aad, 547, t824 D-Tetra-0-acetyIribopyranose,1 184 preparation, 862 D-Tetra-0-acetylxylopyranose,1 184 properties, 862, 1210, 1212 1,2,4,5-Tetrabromopentane,4 14 Sulfhydryl group, 1132, 1227 2,2,3,3-Tetrachlorobutane, 644 Sulfolane, 258 Tetrachloroethylene,t169,356 Tetrachloromethane, see Carbon tetrachloride sblvent, 258,1066 Tetracosanoic acid, 1137 Sulfonamides, 857,863 Tetracyclone, 988,990 hydrplysis?859 n-Tetradecane, t93 relabve aadlty, 860 n-Tetradecyl alcohol, t2 16 Sulfonation Tetraethyllead, 76, 119 of aromatic amines, 862 - 863 1,2,3,6-Tetrahydrobenzaldehyde,983 ofbenzene, 498,518,527,534 A'-3,4-tram-Tetrahydrocannabinol, 9 15 of phenols, 900 Tetrahydrofuran. t238.258.478. t1058 of pyridine, 1068 of pyrrole, furan, and thiophene, 1062- 1063 is solvent, 346, 1066 reaction mechanism, 527,534-535 5,8,9,10-Tetrahydro-1,4-naphthoquinone,983 Sulfonic acids, 233,529,744 cis-1,2,3,6-Tetrahydrophthalicanhydride, 983 akyl esters of, 177,233-234 Tetrahydropyranyl esters, 788, 1058 Sulfonium ions, 857, 1037 Tetrahydropyranyl (THP) ethers, 696,704, Sulfonyl chlorides, 857 1058 Sulfw, analysis for, 5 14 Tetr;thy$othiophene Sulfur dioxide, 258 ondabon, 1066 SMcacid, 770 preparation, 1065 reaction with alkenes, 320,33 1-332,333 Tetraiodoethylene,t169 Sulfur trioxide, 1063 Tetraiodomethane, t 169 Superacid, 192 B-Tetralone, 937 Superconductors, 5 13 Tetramethylammonium chloride, 258 Superimposability, 127, 149 Tetramethylammonium hydroxide, t824 Suprafaci&reactions, 10 16 Tetramethylammonium ion, 264,827. Surface-a&ve polymer, 1098 2,2,4,4-Tetramethyl-1,3-cyclobutan~one,990 Symmetrical ethers, 237 1,3,5,5-Tetramethyl- 1,3-cyclohexad~ene,490 1,1,3,5-Tetramethylcyclohexane,468 m-Toluic acid, 17 15, 716, 727 Tetramethylenediamne, t824 c-Toluic acid, t7 15 Tetramethylene sulfone, see Sulfolane infrared spectrum, 746 Tetramethylethylene, 282, 990 preparation, 722 1,3,4,6-Tetra-0-methyl-D-fructose,1202 pToluic acid, 546, t7 15 2,3,4,6-Tetra-0-methyl- galactose, 1202 preparation, 870 2,3,5,6-Tetra-0-methyl-D-gluconicacid, 1186, Toluic acids, 7 16 1187-1188 m-Toluidine, 1824 o-Toluidine, 750,1824 reactions, 859,867,868, 871 pToluidine, 822, t824,832 protection of amino group, 86 1 oxidation of. i 177 reactions, 870,871,872 reactions, 1176- 1177 c-Tolumtnle, 722, 867 a-2,3,4,6-Tetra-0-methyl-D-glucose,1175 - 1178 pTolunitrile, 725, 870 /l-2,3,4,6-Tetra-O-methyl-~-glucose,1 175, 1176 2,4-Tolylene diisocyanate, !092 3 7 11,15-Tetramethylhexadecanoic acid, 1122 a-(p-~Tolyloxy)isobutyricacld, 9 19 cis-?(R), 11 (R)-3,7,11,15-Tetramethyl-2-hexadecen- Tors~onalenergy, 82 , - --- Torsional strain, 79-83,454 ~et-ethyllead, 76 Tosylates, 234 2,3,4,6-Tetra-0-methyl-D-mannose,1203 Tosyl chloride (ptoluenesulfonyl chloridt Tetramethylsilane, 605 234,703,900 Tetraphenylethylene,t553 Tosyl group, 234 4,5,6,7-Tetraphenylindene,990 Tracers, see Isotopic tracers Tetraphenylmethane, 570 Transcription 1246 rf, 234 ~ransesterifidtion, 77 1,777-778 rhallium acetate, 529 Transfer constant, 1082 rhermoplastic polymers, 1096 Transition metal complexes, 1042- 1046 rhermosetting polymers, 1096 catalysis by, 1031- 1056 rhiamine, 1059 Transition state? 65-67,579 l'hiazole, 1057 for halogenahon, 113 - 114 rbiele, Johannes, 504 reactivity and development of, 67-69 rhioglycolic acid, 355 Transport proteins, 113 1 rhiois, 1132 Transport RNA, 1247 rhionyl chloride, 726,737 (+)-Trehalose, 1202 rhiophene, 1057, t1058 Triacylglycerols, 1120, 1134 reactions, 1062- 1064, 1074 Trialkylborane, 934, 898 source, 1060- 1062 Trialkylborane, 898, 934 structure, 1059- 1061 2,4,6-Trikomoaniline, 509, 547, 822 rhiourea, 784 preparahon, 848 THP ethers, 696,704, 1058 3,4,5-Tribromoaniline, 873 .-Threitol, 11 15 1,2,3-Tnbromobenzene, 873 ,-Threitol- l-phosphate, 11 15 1.2.4-Tribromobenzene. 509 rhreo diastereomers, 377,380 keonine, 12 12 3,4,5-~ribrornobe&enediazoniumchloride, 873 -)-Threonine. t1207 1,1,2-Tribromoethane,NMR spectrum, 6 10,612, :hreose, 380 ' h15 -)-Threose, 789, 116 1,1167 ~ribi~moethylene,t169 'hymine, 1243, 1245, 1246- 1247 Tribromomethane (bromoform), 45, t169

'hymol, 894,9 16 3.4.5-Tribromonitrobenzene.- . - .. . -. -. 873 'hyroglobulin, 1226 l; (3-~ribromononane, 355 ' - 'ollens' reagent, 676,697,705, 1144, 1149 2,4,6-Tribromoghenol, preparation, 900,906 'ollens' test. 671. 676 Tricarballylic ac~d,989 2-~olualdeh~de,'t661 Trichloroacetic acid. oreoaration,727,74 1 -Tolualdehyde, 1661 -Tolualdehyde, 659,1661 'oluene, 508, 551,1553, 562, 568-570,667, 720, Trichloroethylene, t169 8'31 Trichloromethane, see Chloroform brimination, 1521 l, l, l-Trichloro-2-methyl-2-propanol, 909 industrial source, 446,555-556 l, l, l -Trichlorononane, 355 nitration, t520,t521 Tricyclo[2.2.1.OZ6]heptane (nortricyclene), 445 NMR spectrum, 606,608 Tricyclopropylmethanol,646 orientation of electrophilic substitution, 538 -540 n-Tridecane, t93 vrevaration. 557 Tridentate, definition, 1042- 1043 ktd compdson, 536-537 1,3,5-Triethoxybenzehe, 9 16 reactions, 171,519,525,562,565-566,567, Triethylaluminum-titanium trichloride, 1087 690? 870,871 Triethylamine, t824 sulfonahon, t521 Triethylboron, 347 vs. benzene, 555 Triethylene glycol, 484 .Toluenediazoniumbromide, 87 1 Triflate. 246.408 -409 ,Toluenediazoniumbromide, 87 1 Trifluoroacetic acid, 26 1 ,Toluenediazoniumchloride. 867.947 2,2,2-Trifluoroethanol, 26 1 ~oluenediazoniumchloride: 870' Trifluoromethanesulfonate. 246,408 Toluenediazonium hydrogeh sulfate, 867 Trifluoromethanesulfonicacid, 234 Toluenesulfonates, 234 Trifluoromethanesulfonyl group, 408 Toluenesulfonic acid, 5 19,562 Trifyl group, 234,408 - - - Toluenesulfonic acid; 234; 5 14,519,562 1,3,5-Trihydroxybenzene (phloroglucinol), 916 Toluenesulfonyl chloride (tosyl chloride), 226, l, l, l -Triiodo-3,3-dimethyl-2-butanone,800 234,703,900 Triiodomethane, t169 1324 1,3,5-Tnmethoxybenzene 8 Vinyl chloride

1,3,5-Trimethoxybenzene, 9 16 ~

NMR signals, 602 Westheimer, Frank H., 1104, 1113 polymerization, 356,1080 Wheland, G.W., 395 reactions, 329,544,944 Whitmore, Frank, 192,206 relative reactivity, 338, 949-950 WiUcinson, Sir Geofiey, 1044, 1053 resonance, 95 1 Wilkinson's catalyst, 1044, 1053 Vinyl free radical, 123 Williamson, ILL., 623 Vinyl group, 283 Williamson synthesis, 241 -242,309, Vinyl halides, t169,408 stereochemistry of, 24 1-242 reactivity, 949 - 950 Winstein, Saul, 270, 386, 468, 1032. vs. aryl halides, 944 Wittig, Geofg, 8 11 Vinyl-halogen bond, 408 Wittigreackon, 801,811-813 Vinylic cations, 408 Wobier, Friedrich, 3 Vinylic hydrogen, 124,390 WoH-Kishner reduction, 556,667,672,677 Vinylic spectroscopic analysis, t607 Woodward, R.B., 984, 1004, 1029 Vinylic substrates, nucleophilic substitution in, W~odward~HoBnannrules, t10 10, t 10 17 407-409 Wurtz rea&on, 102 Vinylidene chloride, 1094 Vinyl monomer, 1080 Vinyl radical, 123 Viscose, 1201 Viscosity, of macromolecules, 1093 Xanthates, 120 1 Vision, organic chemistry of, 285-287 X-ray analysis Vitamin A, 286,488,599 for configuration, 140 Vitamin A,, 412 for proteln structure, 1229 Vitamin B,, 1059 Xylans, 1198, 1203 Vitamin D, precursor, 11 36 Xylaric acid, 116 1 Vitamin D2,1030 m-Xylene, 551, t553,554,564, 570,583-584 Vitamjn D,, 1030 o-Xylene, 551, t553, 554,562, 564, 570, 583-584, Vitamns, 1229 720 Vulcanization, of rubber, 420, 1096 Vycra, 1094 Vycron, 1094 NMR spectrum, 606,608 Xylenes, 551, 554,555 (+>Xylose, 1161, 1167

Walden, Paul, 184 Water, 19-20,24-25, 31, 176 addition to alkenes, 333, 334 bond formation, 19 - 20 ' dipole moment, t24 as solvent. 3 1 z Watson, J.D., 1242- 1246 Zerewitinoff active hydrogen determination, 124 Wave amplitude, 992 Zervas, Leonidas, 1222 Wave equations, 5,992-994 Ziegler, Karl, 1087 Wave functions, 5, 992 Ziegler-Natta polymerization, 1088- 1089, 1096 Wave mechmcs, 6 Z~ncacetate, 725 Wavenumbers, 590 Zwitterions, 862 (See also Dipolar ions)