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. sp2 Hybridization 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 11 0 Stability of free radicals l l l Ease of formation of free radicals 11 3 Transition state for halogenation 113 Orientation and reactivity 1 14 Reactivity and selectivity 115 Non-rearrangement of free radicals. Isotopic tracers 11 6 Combustion 118 The greenhouse effect 11 9 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 SN2 reaction: mechanism and kinetics 181 The &2 reaction: stereochemistry. Inversion of configuration 182 The SN2 reaction: 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

6 Alcohols and Ethers I !l

6.1 Introduction 213 6.2 Structure of alcohols 214 6.3 Classification of alcohols 21 4 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 SN2 reaction: 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 51 0 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 71 7 Salts of carboxylic acids 71 8 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 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

xvii

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 101 3 Sigmatropic reactions 101 9

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 103 7 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 l 0 73

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 11 04 32.5 Enantiotopic and diastereotopic ligands 1107 32.6 Enantiotopic and diastereotopic faces 11 l 0 32.7 Origin of enantiospecificity 11 12

PART THREE - Biomolecules

33 Lipids Fats and Steroids The organic chemistry of biomolecules 11 19 Lipids 1120 Occurrence and composition of fats 1120 Hydrolysis of fats. Soap. Micelles 1124 Fats as sources of pure acids and alcohols 1125 Detergents 11 26 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 11 32 33.1 1 Steroids 1134

34 Carbohydrates I. Monosaccharides Introduction 11 43 Definition and classification 1144 (+)-Glucose: an aldohexose 1144 (->Fructose: a 2-ketohexose 11 46 Stereoisomers of (+)-glucose. Nomenclature of aldose derivatives 11 46 Oxidation. Effect of alkali 11 49 Osazone formation. Epimers l151 Lengthening the carbon chain of aldoses. The Kiliani-Fischer synthesis 11 52 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 11 60 Optical families. D and L 11 62 Tartaric acid 11 64 Families of aldoses. Absolute configuration 11 66 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 11 85 (+)-Maltose 11 85 (+)-Cellobiose 1188 (+)-Lactose 1 189 (+)-Sucrose 11 91 Polysaccharides 11 92 Starch 1193 Structure of amylose. End group analysis 1193 Structure of amylopectin 11 95 Cyclodextrins 11 98 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 121 1

xxii CONTENTS

Configuration of natural amino acids 1212 Preparation of amino acids 121 3 Reactions of amino acids 121 5 Peptides. Geometry of the peptide linkage 1215 Determination of structure of peptides. Terminal residue analysis. Partial hydrolysis 121 7

,

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

Mechanism of enzyme action. Chymotrypsin 1236 i 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

)solute alcohol, 221 )solute configuration, 155,183,1165,1166- 1168 )solute ether, 240 xtraction of hydrogen, 60,66,566-567,805,838 relative rates, 107 - 109 :cornmodation of charge, 208,209 ztal, 674 (See also Acetals) xtaldehyde, 247,659, t661,670, 11 14 enzymatic reduction of, 1 1 12 - 1 1 13 preparation, 432,435,661 reactions, 673-674,687,800-801,805-808,

830,988, 1102- 1103, 1214 xtaldehyde diethyl acetal, 674 xtaldoxune, 673 :etals, 696 formation of, 680-683, 1 170,1174 reactions, 674, 1 175 - 1 176 :etamide, 754, t755,757,764,77!, 778, 860 Acetarmdobenzenesulfonyl chloride, 863 Acetamidopropenoic acid, 1050, 1 1 13 :etanilide. 546. 858.861 preparation, 848 '

reactions, f520,522,863,947 . . xtate rayon, 1201 :etic acid, 226,258,680,705,713, t715,725-

727,739,754,764,765,768,778,829,859,925 industrial preparation, 7 19 model of. 714 - - - - - - - , reactions, 829 substituted, synthesis of, 925 uses, 764 xtic anhydride (ethanoic anhydride), 754, t755, 757

pr&kation, 763 reactions, 664,764,765,769,859,900 cetoacetic aad, 93 1 cetoacetic ester, 814-815,930,939 preparauon, 8 13 - 8 15 reactions. 927-930 (See also '~th~1 acetoacetate) cetoacetic ester synthesis, 924,927-930 cetoacetvl-S-ACP. 1 133 :etobactir, 719 '

cetolysis, 1039 - 1041 cetone, 258,659, t661,670,673,688 preparation, 432 reactions, 436,687,690-692,704,705,800-

806.816.829.990 substitutkd. svnthesis of. 928 cetone cyanoliydrin, 673

Acetonitrile (ethanenitrile), 258, 725 Acetonylacetone, 930, 1062 Acetophenone (methyl phenyl ketone), 546,557,

581,660, t661 infrared sDectrum. 700 preparation, 664 ' reactions, 672,801,808,835,935

Acetophenoneoxime, 844 Aceto-o-toluiede, 858 Aceto-ptolui&de, 858

preparation, 861 reactions, 86 1,872

Acetoxonium ions, 1040 o-Acetoxybenzoic acid (aspirin), 9 14 2-a-Acetoxycholestane-3-one, NMR spectrum, 623 2-Acetoxycyclohexyl tosylate, 1039, 1040 (+)-trans-2-Acetoxycyclohexyl tosylate, 1040

NMR spectrum, 820 preparabon, 8 16

Acetylalanine, 1050 Acetylation

of amines, 858 of cellulose, 1201

Acetyl chloride, 754, t755,757 preparation, 726

Acetylcholine, 882 Acetyl COA, 1132-1133, 1139 Acetyl CoA carboxylase, 1 133 Acetylene, 43, t429

as acid, 436-438 analysis, t607 industrial source, 43,429 reactions, 38,432-433,435,438, 1181 structure, 276,425 -427

2-Acetylfuran, 1063 Acetylides, 429-430,433,438 Acetyl-S-ACP, 1 1 33 Acetylsalicylic acid (aspirin), 9 14 Acetylurea, 783 Aad anhydrides, 753,763-766

addition to aldehydes, 81 1 conversion

into acids and derivatives, 764 into amides, 764

cyclic anhydrides, 765 physical properties, 754-755, t755 preparation, 763 reactions, 764-766,769,783,811 structure, 753

Acid-base catalysis, 1239- 1240 Acid-base properties, used for separation, 7 18 - 7 19 Acid catalysis, 175,229-233, 771

Acid chlorides Alcohols

Acid chlorides, 753,760-763 aromatic vs. aliphatic, 762 carboxylic acid

spectroscop~c analysis, 784-785, t786 structure, 753

conversion of into acids and derivatives, 760,761,762,769 into amides, 76 1, 857- 860 into esters, 761, 769

Friedel-Crafts acylation, 663,666-667,761 with organocopper compounds, 664,668 -

669.762 - - - a

ketone formation, 663,761 -762 with orpnocopper compounds, 762

nucleophllic substitution, 760 physical properties, t755 ~reuaration. 760 - fiom carboxylic acids, 665,726,737 reactiqns, 760-762,783 redumon, 662 - 663 spectroscopic analysis, 784-785, t786 structure, 753 ~.ulfonic acid, 857

Aadity, 33-35 alcohols, 227 - 229 alkynes, 436-438 amides. 766. 859 carboxylic a'ci&, 718,725,732-736 dicarboxylic acids, t742,742 - 744 hydrocarbons, 436-438, 1071 - 1072 g-hydrogen, 797-799,8 14-815,924,930, 1070 ~mides, 768 8-keto esters, 8 13 -81 5.930 malonic ester, 924 . phenols, 843,874-875,903-905 phosphates, 1 128 - 1 129 and rate of reaction, 680, 874, 1238 relative series of, 34, 35, 38,228,437, 575, 729,

1146 sulfonamides, 860 sulfomc ac~ds, 233,860

Acidity constants, 729 amjdes, 768 amno aads, 1208 - 12 1 1 ammonia, 768 benzamide, 768 carboxylic acids, 729, t735 dicarboxylic acids, t742 imides, 768 phenols, 843, t890 phthalimide, 768 substituted benzoic acids, t735 sulfonamides, 860

Acids cleavage of ethers by, 242-243 Lewis, definition, 34 Lowry-Brransted, definition, 33 and molecular structure, 35 (See also Acidity; Amino acids, Carboxylic

acids, Fatty acids; Sulfonic acids) Aconitic acid, 988 ACP, 1 133 Acrilan, 1094 Acrolein, e72, 973

preparabon, 974 reactions, 683,975,983

Acrylic acid, 713,750, 1972,973 hydration, 975

Acryloid, 973 Acrylonitde, 1972,973

industrial preparation, 973 reactions, 978, 988, 1080, 1083

ACTH, 1216, 1226 Activating groups, 52 1 - 522,537 - 540 Activation energy, 5 1 -52, t l l l, 324

and reamon rate, 56 and the transition state, 67-69,579

Acylabon, 666 of amines, 858

by benzyl chlorocarbonate, 1222 Friedel-Crafts, see Friedel-Crafts acylation

Acyl azides. 839 Acjll carrier protein (ACP), 1133 Acyl compounds

nomenclature, 753 -754 nucleophilic substitution, 755 - 760 structure, 753

Acyl group, 728,753 compared wth allcyl group, 759 -760 compared with phosphate group, 1129 compared with sulfonyl group, 860 nucleophilic substitution, 666, 755-760

Acylium ions, 666,905 Adamantane, 445 Addition polymerization, 1079 Addition reactions

1,4-, 414-419 vs. 1,2-addition, 417-419

of aldehydes and ketones, 671 -684 of alkenes, 317-365 of alkenylbenzenes, 577 of alkynes, 430-433,435 of conjugated dienes, 414-41 7 of cycloallcanes, 448 of cyclopropane, 449 - 450 defimhon, 3 18 of halogens to alkenes, mechanism, 368-372 stereochemistry, 372- 377 syn- and anti-, 368-372, 1047- 1048 to a$-unsaturated carbonyl compounds, 974-

984 (See also Electrophilic addition; Free-radical ad-

dition; Nucleophilic addition) Adenine, 1 182,1229, 1241 - 1243

-thymine, hydrogen bonding in, 1245 Adenosine. 1183.1241 ~denosinitriphdsphate (ATP), 1 128 Adenylic acid, 1 182 Adipaldehyde, 844,9 17 Adipic acid (hexanedioic acid), 489,742, t742,

763,880, 1090 estenficabon. 738 preparation, 927

Adi~onitrile. 830 (-)--Adrenalhe, 137,9 17 Adrenocorticotropic honnone (ACTH), Agar, 1203 AIBN, 1082 Alanine, 144, 1209, 1223

preparation, 1050,,833, 1213 Strecker synthesis, 12 14

(+)-Alanine. t l206 hbumin, l226 Alcohol dehydrogenase, 1102 A ~ c o ~ o ~ s , 2 13 -247

as acids and bases, 227-229 addition to aldehydes and ketones, 674,680-683 aldehydes from, 226,235-237,662 akyl halides from, 170, 17 1 akyl sulfonates from, 234 analysis of, 243 - 244

iodoform test, 244 Lucas test 244 periodic akd oxidation, 699 spectroscopic, 594-595

carbocations from, 559 carboxylif: acids from, 226,235-237 cl-ficabon, 214-215 dehydration

to alkenes, 225,288,289,306,310,313-315 to ethers, 552

detergents from, 1 126 estefication, 226,239, 726, 737-739,769-770 ethyl, see Ethanol, Ethyl alcohol Grignard synthesis of, 685-692 heterolytic bond dissociation energies, t22 hydrogen bonding, 217-218 industrial source, 21 8-221, 1089

; Alkanes

:tones from, 236-237 S%, 221 omenclature, 2 15 - 2 18 rder of reactivity of, 3 13, 306 xidation, 226,235-237,694,699, 1101 - 1106 hysical properties, 2 15 - 2 18, t2 16 reparation, 222-223 aldol condensation, 808 - 809 Grignard synthesis, 222,685 -692,779 hydroboration-oxidation, 222,321,347- 348 hydrolysis of halides, 222 oxymercuration-demercuration, 222,32 1,

346-347 reduction of carboxylic acids, 727,740 reduction of esters, 779 reduction of fats, 1125- 1126

rotonated, 176 actions, 224-227 as acids, 225,228 with active metals, 225 with hydrogen halides, 170,224,229-233 with phosphorus trihalides, 170, 17 1,225

:activity, 224-227,,726,769 wth hydrogen hahdes, 224,230

:solution, 160,766 ~lubiity in water, 217-218, 238,1253 S solutes, 2 17,252 -253 S solvents, 217,255,256-257 xctroscopic analysis, t592,594-595,1607, t786 mcture of, 2 14 se in synthesis, 692-694 oholyis f acid anhydrides, 765 f acid chlorides, 761 festers, 77 1 -772,778-779 aric acids, t1149, 1150 ehydes, 235,237,359,440,657-712, 1102-

1103 ddition of alcohols, 674,680-683 of aldehydes and ketones, 805 - 8 1 1 of ammonia derivatives, 673,679-680,697 of carbanions, 675 of cyanide, 673,678-679 of derivatives of ammonia, 673,679-680,697 of Grignard reagent, 124,222,675,686-687

Idol condensabon. 800-801.805 -807 .-.- ~ ~

related reactions.' 8 10-8 1 1 ' li$hatic, preparation, 662,665 nalysis, 671,673,675-677,679,697-698 romatic, prepqtion, 662,665 :annizzaro reamon, 674,683 -684 crossed, 674,683-684

lemmensen reduction, 672,677 xmation, 762 hoevenagel reaction, 927,s 10 - 8 1 1 omenclatyre, 658 -660 ucleopbhc addbon, 669 -671,673 -675 xidation. 671.676-677.697

henolic, 663 hysical ,properties, 660-661, t661 reparabon, 66 l-663,665 oxidation of alcohols, 235-237,662 oxidation of methylbenzenes, 662,665 ozonolysis, 358-360 reduction of acid chlorides, 662-663 Reimer-Tiemann reaction, 663,902,908 -909

xctions, 669-675,686-687,704 summary, 800- 802

eduction, 677-678 to alcohols, 672,677-678 to hydrocarbons, 672,677

eductive amination, 829-830,832,834-835 pectroscopic analysis, t592, t607,700-701,2786 tructure. 657-658 &t for, 697 lnsaturated

oxidation of. 676

preparation, 808 reduction, 808 -809 a,D-unsaturated, 978 (See also a,jhUnsatu-

rated carbonyl compounds) vs. ketones, 657,697 Witti reaction, 801, 811-813 ~ o l k ~ i s h n e r reduction, 672,677

Alditols, t 1 149 Aldohexoses

anomers, 1 170, 1 173 configurations, 1155-1160, 1173-1174 conformations, 1 178 - 1 180 conversion to epimers, 1 1 54 - 1 1 55 cvclicstructure. 1168-1172 definition of, 1 i44 denvatives, nomenclature, t1149 (+)-glucose as, 1 144- 1 146 Kiliani-Fischer synthesis, 1 152 - 1 154 ring size, 1 176 Ruff degradation, 1154 (See also Aldoses; D<+)-Glucose)

Aldol preparation, 805 reactions, 807-809

Aldol condensation, 800- 801,805 -807,973 acid-catalyzed, 8 18 crossed, 809- 8 10 related reactions, 8 10 - 8 1 1 use in synthesis, 808 -809

Aldonic acids, t1149, 1150, 1154- 1155 Aldopentoses

configurations, 1156- 1158, 1160- 1162 in Kiliani-Fischer synthesis, 1 153 from Ruff degradation, 1 154

Aldoses carbon-chain lengthening, 1 152 - 1 154 carbon-chain shortening, 1 154 configurations, 115 1 - 1152, 1160- 1162 cyclicstructure, 1168-1172 definition, l l44 derivatives, nomenclature, 1 146- 1 149, t1149 effect of alkali, 1 150 epimers, conversion into, 1 154- 11 55 families, 1166- 1 168 Kiliani-Fischer,synthesis, 1 152- 1154 osazone fornabon. 1 15 1 - 1 152 oxidation, 1149- 1'150 Ruff degradation, 1 154 (See also Aldohexoses; D<+)-Glucose)

Alenic acid, 1203 Ahcyclic hydrocarbons, see Cyclic aliphatic corn-

pounds, Cycloalkanes Aliphatic compounds, see Alkanes, Alkenes, Al-

W? defimaon. 493

Aliphatic cyclic hydrocarbons, see Cyclic aliphatic compounds

Aliphatic hydrocarbon, see Alkanes, Alkenes, Al- kynes, Cyclic aliphatic compounds, Dienes

Aliphatic hydroperoxides, 898 Alizarin, 1202 Alkaloids, 75,159,164,918,1059,1066,1073,

1140 piperidine ring in, 1073 pyridine ring in, 1073 pyrrolidine rin in, 1066 in resolution of racemic acids, 159

Alkanes, 39,77- 124 addition to alkenes, 321,344-345 analysis, 122, t592, 593-594, t607 bond dissociation energies, 22 1, t22, 1 1 1 - 1 12 chlorination of, 104 - 1 18 classification by structure, 77 combustion, 103, 1 18 - 1 19 common names, 90 general formula, 87 halogenation, 104- 1 18, 160- 162

mechanism of, 106-107, 116-118

1282 Alkenes B-*l-9.

Alkanes, (cont.) orientation in, 107- 109 relative reactivities, 109 - 1 1 1

homologous series, 86 - 87 industrial source, 94 - 96, 1 19

vs. laboratory preparation, 96 - 97 isomeric structures, 83 - 87 isomerism, 89 - 90 IUPAC names, 90 - 92 methylene insertion into, 476 nomenclature, 87- 92, t88 physical properties, 92-94, t93, 122 preparahon. 97 - 102 - by coupling of alkyl halides with organometal-

lic compounds. 98 - 99. 10 1 - 102 - .- by hydrogeliation of alkenk, 98 by hydrolysis of Grignard reagent, 98,99- 101 by redudon of alkyl halides, 98,99 - 10 1 by Wurtz rea&on, 102

~ ~ n f i ~ a t i o n . 332 ~Y~OIYSS, 96,-io3,1 20 - 12 1 reactions, summary, 103 reactivity, 103 solubility, 94 spectroscopic analysis, 122, t592, 593-594, t607 structure, determination of, 121 - 122 uses, 96

Alkenes, 246,273-316,409-410 addition reactions, 3 19 - 32 1

of alkanes, 32 1,344-345 anti-Markovnikov, 3 19,32 1,330 of bromine azide, 384,487 of carbenes, 476-478 character, 302,307 dimerization, 320,343 -344 electrophilc, 3 18,332 - 344 free-radical, 390 of halogens, 319,339-342,372-376 halohydrin formation, 320,342,384 of halogens, 313,339-342,372-376 halohydrin formation, 320,342,384 hydration, 218,320,332 hydroboration-oxidation, 222,321,347-348 hydrogenation, 3 19,323 - 327 of hydrogen bromide, 319,329,351 -352 of hydrogen chloride, 327-329,329 of hydrogen halides, 3 19,327 - 329 of hydrogen iodide, 3 19,328-329 hydroxylation, 223,323,357-358,484 of iodine .zide, 384,487 MarkoMlkov, 319,321,327-329,336-337,

351.-352 mechamsm

electrophilic, 332 - 342 free-radical, 322, 351 -356, 1081 - 1083 hydroxylation, 484

of methylene, 474-476 orientaaon in, 327-329,335-338 oxymercuration-demercuration, 222, 32 1,

346 - 347 peroxide effect, 330,351 -352 po lymdt ion , 356-357, 1081 - 1083, 1084-

1089 stereochemistry

halogen azides, 384 halogens, 372-377 halohydrin formation, 384 hydroboration, 222, 321, 348 -349 hydroxylation, 484 oxymercuration, 346-347

of sulfUric acid, 320,331 -332 of water, 320, 332

alkylation, 32 1,344 - 345 alkyl halides from, 17 1 analysis, 360- 362 carbocations from, 559 cleavage reactions, 323 dimerization of, 320,343-344 ease of formation of, 301 free-radical halogenation, 388-390

free-radical substitution, 390 geometric isomerism in, 278- 280 halogenation, 323,388-392 higher, 282 hydration, 218,320,332 hydrogenation, 3 19,323 -327

heats of, t326 hydroxylation, 223,323,357-358,484

stereochemistry, 484 hyperconjugation, 41 3 industrial source, 119,287, 1089 nomenclature, 282-283 ozonolysis, 323, 358-360 physical properties, 283-285, t285 polymerization, see Polymerization . preparation, 246,288-290,310-315

dehalogenation of vicinal dihalides, 289 385 dehydration of alcohols, 288,289,3 1013 15 dehydrohalogenation of alkyl halides, 288,

289,290-293 Hofmann elimination, 854-855 reduction of alkynes, 289,43 1,433 -434 Wittig reaction, 8 1 1 - 8 13

readons, 3 17 - 365 relative reactivity toward acids, 338 resonance in. 413 spectroscopic analysis, t592 599,592- stability, 301,326-327.41j structure, 273-283 '

substitution reactions, 323,388 -390 substitution vs. addition, 388 - 390 (See also Alkenylbenzenes; Dienes)

Alkenvlbenzenes conjugated, 579- 580 preparation, 576 -578 reactions. 578 - 580 ring-halogenated, 578 (See also Arenes)

Alkoxides, 227,228,241 Alkoxymercuration-demercuration, 24 1 Alkyd resins, 1090 Alkyl acetates, rates of reaction, 776 Alkylacetoacetic esters, 927 Alkyl aryl ethers, 240

cleavaee. 242 -243 Williamson synthesis, 902

Alkylation of alkanes, 120 of alkenes, 321,344- 345 of amines, 836-837,847,854-855 of carbonyl and acyl compounds, 923 -940 of esters and ketones, 93 1-932

B-Alkyl-9-BBN, 934 Alkylbenzene derivatives, synthesis of, 689-690 Alkylbenzenes, 55 1

analysis, 564,580: 58 1 electropec subsatution, 564 halogenahon, 562,565-568 hydro enation, 56 1 idendcation of, 564 industrial source, 555-556 oxidation, 562, 563-564 physical properties, 552-555, t553 preparation, 556

Clemmensen reduction of ketones, 556-557, 677

~riedei&ft.s alkylation, 556- 56 1,564 WoH-Kishner reduction of ketones, 556-

557,677 reactions, 550

hydrogenation, 56 1 oxidation, 562,563-564,721 ring vs. side chain, 565-568 substitution in the ring, 562 substitution in the side chain, 562,565-568

side-chain halogenation of, 566- 568 spectroscopic analysis, 592- 594, t607,606 -607 structure and nomenclature, 551 -552 (See also Arenes)

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~um halide, 99 yl free radicals, 47 - 49, 106 - 109 Akylmalonic esters, 924 ase of formation, 1 13 Alkyl phosphates, 1 137 lyperconjugation, 401 -402 Alkyl shift, 206,934

, elative stabiilities, 1 1 1 - 1 12 Alkyl sulfonates, 860 tereochemistry, 160- 162 in l ,2-elimination, 308 tructure, 64-65 formation of, 233-235 71 groups, 309

A G l 3 1 halides, 234-235

~omenclature, 88 - 90 ates, 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 : l a ss i f~~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 z%$ii%ect of solvent, 260

terminal, 437,440 AUcynylbenzenes, 550,580 (See also Arenes)

hydrolysis, 178- 179 Allene, 410, t411,411,423 alcohol synthesis, 222-223 o p t i d y active, 423 glycol synthesis, 222-223 Allinger, N.L., 468,490

NMR and CMR spectra of, 640 Allitol, 1 162 nomenclature, 168 (+)-Nose, 1 162 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, 101 1 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~tal p~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)barbituric acid, 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

1284 a-helix W Ammonium salt

l a

AUyl radical, (cont.) symmetry, 393 -394

a-helix, 1230, 1232- 1234 (+)-Altraric acid, 1 162 (+)-+OX,, l l62 Alumlnum so prop oxide, 225 Amanita rnuscaria, 164 Amanita rubescens, 164 Amides, 727, 753

analysis, NMR, 786, 877 carboxylic acid, 727,728,740,766-767

acidty, 766, 859 analvsis. 784 ~ o f m & n degradation, 836,838-843 hydrolysis, 767 nomenclature, 754 nucleopbilic substitution, 755 - 760 physical properties, 754-755, t755 preparation, 727, 740,76 1, 766,77 1,778 reactions, 766-767,838-843 spectroscop~c analysis, 784-785, t786 structure, 753 vs. sulfonamides, 857-860

Hofmann degradation, 767,831,836,838-843 physical properties, 754-755, t755 substituted, 847 -848,857-859

analysis, 877 hydrolysis, 859 nomenclature, 858 preparation, 847-848,857-859 spectroscopic analysis, 877-878

Amidol, 9 15 Amination

ofa-halo acids, 1213-1214 pyridine, 1070 reuctive, 829,831,834-835,836, 1214

Ammes, 821 -844,845 - 888 aci&ty, 860 acylaaon, 847, 858 alkylation, 836,847,854-855 analysis, 876-878 aromatic

acetylation, 848, 859, 861 basicity, 850 conversion intopiazonium salts, 864- 865, coupling with &azonium salts, 873-875 mtrosaaon. 849.864 ring substitdon. 848.860-862 sulfonation, 8621863

-

baslclty, 823, t824, 845, 849-853, t850 effect of substituents, 853

classiiication, 821 -823 conversion into amides, 847,857-860, 1222 derivatives, 877 Hinsberg test, 876- 877 Hofmann elimination, 849,854-857 industrial source. 828 nitrosation, 849,'864 nomenclature, 822- 823 optical activity, 825 physical properties, t824, 823-824 preparation, 828-837

Curtius reaction, 839 from halides, 829, 831,832-834, 836 Hofmann degradation of amides, 767,830,

831,836,838-843 Lossen reaction, 844 reduction of nitriles, 830,83 1 reduction of nitro compounds, 828,831,832 reductive amination, 829-830,83 1,834-

835,836 of secondaxy and tertiary, 836-837

protection of amino group, 861 quaternary ammonium salts, 854-855 reactions, 845 - 888

with carbonyl compounds, 935-937 with nitrous acid, 849,864-866 with sulfonyl chlondes, 847,857-859,876 summary, 845 - 849

salts, 823,823-825,845 spectroscopic analysis, t592, t607, 877-878 stereochemistry, 826- 827 S-ture, 82!,.850-852

eArnmoacetamhde, 832 Aminoacetic acid, see Glycine pAminoacetophenone, 695 Amino acid residue

C-terminal, 1216, 1218, 1220 N-terminal, 1216, 1218-1219 terminal residue analysis, 12 18 - 12 19

Amino acids, 741, 1049- 1051, 1205- 1250, 1247 a+dic, 1208 acldity constants, 12 10 basic, 1208 configuration, 12 12 as &polar Ions, 1208 - 12 1 1 essential, 1206, t1206 - 1207 isoelectric point, 12 1 1 - 12 12 natural, t1206 - 1207, 12 12 physical ,properties, 1208 - 12 1 1 preparaaon, 12 13 - 12 15 reactions, 1215 structure, 1206- 1208 synthetic, 1214

1-Aminoalkanes, synthesis, 828 m-Aminoanisole. 965 p~minobenzene sulfonamide, see Sulfanilic acid pAminobenzenesulfonanilide, 879 pAminobenzenesulfonic acid, see Sulfanilic acid Aminobenzoic acids, 5 15 m-Aminobenzoic acid, t7 15

formation, 970 c-Aminobenzoic acid, see Anthranilic acid pAminobenzoic acid, t715, t824, 863, 1210

as essential metabolite, 864 y-Aminobutyric acid, 822 2-Aminoethanol (ethanolamine), 483, 514,822,

1130 a-Aminoglutaric acid, 930 Amino group, protection of, 1248 l-Aminoheptane, 835 a-Aminoisocaproic acid, 927 2-Amino-4-methoxybiphenyl, 949 l-Amino-2-methyl- l-phenylpropane, 143 2-Amino-2-methyl- l-propanol, 932 a-Amino-jLmethylvaleric acid (isoleucine), 2 19,

927. 1238 6-~mino-2-naphthalenesulfonic acid, 5 10 2-Aminopentane, 835 . m-Aminophenol, t890 c-Aminophenol, physical constants, t890 pAminophenol,t890 2-Amino-l-phenylpropane, 843 a-Aminopropionic acid, see Alanine FAminopropionitrile, 978 2-Aminopyridine, 1069, 1070 3-Aminopyridine, 1069 4-Aminopyridine, 969, 1070 Aminosuccinic acid, see Aspartic acid Aminotoluene, see Toluidine Ammonia, 17- 19,258,825,828,846

aa&ty, 437 constant, 768,860

basicity, 33 compared with amines, 85 1 constant, 850

bonding in, 18- 19,20,24-25 derivatives. addition to aldehydes and ketones,

679-680 dipole moment, t24,24-25 . . i n k i o n , 19 unshared pair of electrons,

Ammonium acetate, 764 Ammonium carbamate, 782 Ammonium chloride, 258 Ammonium formate, 7 17 Ammonium ion, 827,85 1 Ammonium salt. 265

Ammonium succina

immonium succinamate, 764 immonolysis

of acid chlorides, 76 1 of anhydrides, 764 direct, 1213- 1214 of esters, 77 1, 778 of halides, 829,831,832-834,836

imphipathic, definition, 1 124 implitude, of wave, 992 imyl alcohol, 2 18 rctive-Amyl alcohol, t2 16 imylopectin, 1 193

structure, 1 195 - 1 198 imylose, 1 193- 1 196

reactions, 1 193 - 1 196 structure, 1 193 - 1 196

imytal, 938 inalysis

Carius method, 74,5 14 chromatographic, 12 17 combustion, 72-73 conformational, see Conformational analysis dansyl method, 1220 by derivatives, 149- 150 determination of structure, 121 - 122,585-586 Dumas method, 513-514 elemental, qualitative, 72 -73 elemental, quantitative, 73 - 74 Kjeldahl method, 5 13 - 5 14 mass spectrometric, 122,586-589 neutralization equivalent, 744-745 by periodic acid, 699 saponification equivalent, 784 Schoniger oxidation, 72 sodium fusion, 72 spectroscopic, 121,585-655,700-701,877-

878 (See also individual types and individ- ual families)

carboxylic acid derivatives, 784-785 structure, determination of, 121 - 122,585-586 ultraviolet, 597-598 Van Slyke method, amino nitrogen, 1215 x-ray, 122

for configuration, 140 (See also individual families and individual ele-

. . inchimeric assistance, 841,1035,1037 - 1041 indiron formula, of ethane, 80 indrogen, 1 136 indrost-9(11)-ene, 1141 inet. F.A.L.. 624 inethole, 894 ingle strain, 450-455

orbital picture, 453-454 (See also Baeyer stmn theory; Bond angle)

inhydrides, t755 acld, see Acid anhydrides carboxylic acid, structure, 753 physical properties, 754-755, t755

iniline, 508, 821,822, t824, 825, 830, 836, 839 industrial preparation, 827 -828 preparation, 953,962,963 protection of amino group, 861 reactions, 540-542,846,848,858,862,863,867 resonance, 540 - 542

inilinium chloride (aniline hydrochloride), 823, 827 846 --., - - -

ini!+um hydrogen sulfate, 546, 547, 862 inhnmm ion, 85 1 inionic polymerization, 1085 inisaldehyde, t661,683 inis~q a%d, t7 15, 9 12, 9 18 n-All~sidme, t824,965 -967 ~Anisidine, t824 ~Anisidine, t824 inisole (methyl phenyl ether), t238,546, 547,724,

874,909,911, 1204 innulenes, 5 16,644, 1000 inomeric effect, 1 180

mate Aryl halides

Anomers, l l70 Antarafacial reaction, 101 6 Anthocyanins, 1075 Anthracene, 5 10,580 Anthpnlic acid (o-Aminobenzoic acid) t735,970,

lLlU ~ h v s i d constants. t7 15

an'ti-addition, 370-372,373,374,376,392-393, 1047- 1048

Antiaromatic, 1003 Antibiotics, 863, 1247 Antibonding oybitals, 994-996 anti conformabon, 85

n-butane, 463 in E2 elimination, 47 1 -473

Apoenzymes, 1229 Aprotic solvents, 254-258,926 Arabans, 1203 (+)-Arabinose, 1 155 (-Mrabinose. 1156- 1158. 1161 i-~rabinose, 1203 Aralkyl halide, 552 Arecaidine, 1076 Arenes, 549-584

analysis, 580-581 industrial source, 555 -556 nomenclature, 55 1-552 physical properties, 552- 555, t553 preparation, 556-561,576-578 reactions, 561 -568,578-580

addition, 579 -580 hydrogenation, 562,578 oxidabon, 562,563-564,578 ring substitution, 562,565-566 side-chain substitution, 562, 566-568

structure, 55 1 - 552 (See also Alkenylbenzenes; AUcylbenzenes; Al-

kytylbenzenes) (+)-Argume, t1206 Amett, Edward, 202 Aromatic character, 1000- 1004 Aromatic compounds

aliphatic, 549- 584 definition. 493 heterocyclic, see Heterocyclic compounds polynuclear, 5 10 - 5 13 sources, 446-447,555-556

Aromatic hydrocarbons aliphatic, 549- 584 physical properties, 552-555, t553 (See also Arenes; Polynuclear aromatic com-

~ounds) Aromiticity, 493 - 516

of annulenes, 5 16,644, 1000 electronic configuration and, 1000- 1004 experimental cnteria of, 494,504,604-608,

1000- 1001 geometry and, 504,506, 1000 Hiickel rule and, 504-508, 1000- 1004 NMR and, 504,605, 1000 requirements for, 504 - 508, 1000 - 1004

Aromatic properties, 493 -494,504 - 508 (See also Aromatiaty)

Aromatic proton, MMR chemical shift, t607 Aromatic ring, 549

spectra, t592, 593 Aromatic sextet, 504-507,511, 1001- 1003, 1060,

l067 Aryl bromides, see Aryl halides Aryl carbamates, see Urethanes Aryl chlorides, see Aryl halides

"rdr%gn of, 909-9 1 1 reactions of, 9 1 1 - 9 12

AryI fluorides, in nucleophilic aromatic substitu- tion, 960 (See also Aryl halides)

Aryl halides, 552,943-970 ammonolysis, 831, 950,953 analysis, 967

1286 Aryl iodides Benzene

Aryl halides, (cont.) bond lengths, 8 5 1 charactenstic proton chemical shifts. 2607 and

inside.fioht cover dipole moments, 851,95 1 electrophilic substitution, 522,2522,542-544 Grignard reagent, 695,948 h y d r ~ l y ~ i ~ , 898- 899,949-950,952-953 low reactivitv. 948 -950

structure and. 950-952 nomenclature, 508 -509 nucleophilic substitution, 949,952-967

bimolecular displacement, 949,952 -967 elimination-addition, 949,962-967

orientation, t520,542-544 physicalproperties, 944-946,845, 851 preparabon, 946 - 948

from diazonium salts, 867,869-870,947 by halogenation, 529,551,947

nitration, 2520 reactions. 704.948 - 949 reactivi$, 542 structure, 943 -944,950-952 vs. alkyl halides, 910,943-944, 948 vinyl halides, slrmlanty to, 949-950

Aryl iodides, see Aryl halides Arylmagnesium chlorides, 685, 1066 Aryl methyl ether, 909 Aryloxyacetic acids, 9 12 Ascarite. 73 ~ s p a r d n e , 137 (-)-Asparagine, t 1206 Aspartic and, 977, 1214, 1247 (+)-Aspartic acid, 21206 Aspergillus niger, 1203 Asphalt, 8 6 Aspirin, 9 14 Associated liquids, 30, 2 17 -2 18 Atactic polypropylene, 1088 - 1089 Atomic orbitals, see Orbitals Atomic structure. 6 Atomic weights, see inside back cover ATP (adenosine triphosphate), 1 128 Atropa belladona, 750, 1075 Atropge, 750, 1075 Atropisomers, 150 Attractive forces, 20- 2 1 Aureomycin, 863 Axial bonds in cyclohexane, 460-465 Azeotropes, 221,681,738 Azobenzene. 844 Azo compounds, 849,868,878,873-875 Azo dyes, 875 Azoisobutyronitrile, 1082

Bacillus macerans, 1 1 98 Back-bonding, 1042 Bacterial enzymes, 7 19 Baeyer, Adolph von, 450 Baever strain theory, 450-453 (See also - .

-strain) Baeyer test, 36 1 Bakelite, 109 1 Barbital, 938 Barbiturates, 783 Barbituric acid, 783 Bartlett, P.D., 989 Base-catalyzed halogen dance, 944,970 Base-~romoted 1.2-elimination. 246 ~ a s e i

Lewis definition, 34 Lowry-Brvnsted definition, 33 and molecular structure, 35

Basicity, 33-35, 175-178 alcohols, 228

S Angle

alkenes, 3 18 alkoxidk ions, 228 amines, 823, t824,849-853 benzene ring, 5 18 carbanions, 436 -438 carboxylate ions, 729 piperidine, 1073 pyridine, 1067, 1071 - 1073 pyrrole, 1059- 1064 relative, 34,228, 437, 729, 1071 - 1072

Basiqty constants, 849 -853 amines, t824,849, t850 amino acids, 1208 - 12 1 1 ammonia, 849 pyridine, 1073 pyrrole, 1060- 1061

Basketane, 445 9-BBN (9-borabicyclo[3.3. llnonane), 809, 8 18,

934-935 Beckmann r k g e m e n t , 88 1, 1098 Beef insulin, 1249 Beef tallow, tl l21 Bender, Myron, 775 Benedict's reagent, 1 144, 1 149 B e d group, 80 1 Benzalacetpne, 872,973,985

preparabon, 801 Bedacetophenone (chalcone), 872

preparation, 801 reactions, 976, 979

B e d bromide, 2169 Benzal-pbromoacetophenone, 982 B e d chloride. t169

preparation, 562, 566 Benzaldehyde, 659, t661,673,674,681,704,835

reactions, t520,680, 801, 810, 811, 812, 990 Beddehyde diethyl acetal, 68 1 Benzaldehyde phenylhydrazone, 674, 1 15 1 Beddoxime, 844 B e d group, 801 Benzgnide, 754, t755,767,839

aa&tv constant. 768 infrarkd spectrum, 785 preparation, 76 1

Benzanilide, 858 preparation, 858, 1098

Benzedrine, 843 Benzene, 296, 399,447,493-516,643

aromatic properties, 493-494,497-498,500, 502- 504 ..

bond angles in, 50 1 - 503 ' bond dissociation energy, 502 bromination, 498, 524 carbon-carbon bonds in, 499-500 chlorination, 498,529 derivatives, nomenclature, 508 - 509 "Dewar" formula, 1029 disubstitution products, 495 - 496 electronic configuration, 1000 electrophilic substi!ution, 497:498,504 (See

also Electrophhc aromabc subsfimbon) Friedel-Crafts acylation, 498 Friedel-Crafts alkylation, 498,528 halogenation, 498,529 heat of combustion, 498 - 499 hydrogenation, 447

heat of, 498 -499 industrial source, 555 -556 isomer number, 494-497

and structure, 500 - 50 1 KeMB structure, 401 ,. 494-497 Kerner methqd of absolute orientation, 509 Ladenbun! vnsm formula, 5 15 mass spe&m of, 588 nitration, 497,521 -522,524-527 orbigs, 50 1 - 503,999 physlcal properbes, t553 "purple", 358 rate companson, 536 - 537

Benzenediazonium chloride 1

reactions, 497-498,529,530-531,560,575,689 vs. cyclohexene, t497

resonance, 500 - 50 1 stability and, 500 - 50 1

ring, 503,5 17,564 reactivity, 520

as source of aromatic compounds, 555 stability of, 497-499,500,503,507, 1002 structure, 400,494,500-504 sulfonation, 498, 527 thiouhene in, 106 1 vs. tbluene, 555

3enzenediazonium chloride, 849,867-868,874 3ensenediazonium fluoroborate, 868 3enzenediazonium ion, 880 1,4-Benzenedicarboxylic acid, see Terephthalic acid 3enzenesulfonamide, 860 3enzenesulfonadde, 848 3enzenesulfonic acid. 498.508.531.862

, S , ,

nitration, t520 3enzenesulfonyl chloride, 858

in Hins+rg lest, 876 3enzenomum ions, 526 3enzhydrol (diphenylmethanol) 704 3enzidme, t824 3enzil, 684,988 3enzilic acid, 684

rearrangement, 684 3enzoic acid, 508, 564,667, 713, t715,716, 739,

750.754.771 indushal source. 720 model of, 7 14 preparation, 482,562,563,578,720,761 reactions, t520, 725,726, 728,737, 739,748,

749,767,769,770 relative acidity, 73 1

3enzoic anhydride, 754

nitration, t520 3enzophenone, 660,967

preparation, 663 in Wittig reamon, 8 1 1

3enzouhenone oxime. 844 geometric isomers, 844 reactions, 1098

~Benzoquinone, 984 reactions, 983 -984

3enzotrichlonde hydrolysis, 720 physical constants, t169 preparation, 562,566

3enzotduoride, 546 ~Benzoylbenzoic acid, 765 ~Benzoylbenzoic acid, 695 3enzoyl chloride, 667,754, t755

preparation, 726,737 reactions, 663,761,762,858,899

3enzoylglycylalanine acid, 1222- 1223 V-BenzoylglyGne (hippuric acid), 880, 12 15 3enzoyl peroxide, 1084 l-Benzoylthiophene, 1063 3enzvl acetate. 768. t769

preparation, 726 . 3enzyl alcohol, 214, t216,552,576,768, 1097

esterificaaon, 726 infrared spectrum, 595 preparation, 222

3enzylamine physical constants, t824 ~re~aration. 833.835

3&$1 +on; 376. stab&@ of, 574-575

3enzyl chlonde, t169 preparation, 562,566 reactions, 222,557,574,722,829,830,833,847

Benzyl chlorocarbonate, 782, 121 5 acylation by, 1222 in peptide synthesis, 1222

Benzyl chloroformate, 782, 12 15, 1222 in mutide svnthesis. 1222- 1223 - -,--

~ e & i l Ganide (phenilacetoniae), 722,830 Benzyl&(n-butyl)armne, 847 Benzvldimethvlamine. 829 ~ e n z i l ethyl ether, 576 Benzyl free radical, see Benzyl radical Benzyl group, 552

spectroscopic analysis, t607 Benzylic hydrogen, 124,566 Benzylic substrates, nucleophilic substitution in,

575-576 . . . -

Benzyl iodide, t 169 Benzylmagnesium chloride, 691 Benzylmalonic acid, 12 13 Benzyl methyl ketone,

formation, 1042 nomenclature, 660

Benzyloxycarbonylglycine, 1223 Benzoxycarbonylglycylalanine, 1223 Benzyloxycarbonyl group, 1222 Benzyl phenyl ether, 909 Benzyl radical, 123

resonance s tabkt ion, 568-570 stability and ease of formation, 567

Benzyne (dehydrobenzene), 962,967 in nucleophilic aromatic substitution, 962-967 structure, 962

Bergmann, Max, 1222 Berson, Jerome, 1023, 1029 Beryllium, 1 1 - 13 Beryllium acetylacetonate, 38 Beryllium chloride, 1 1 Beta arrangement, 123 1 Betaines, 801,811-812, 1248 Bicyclic compounds, 449 cis-Bicyclo[6.2.0]deca-2,9-diene, I012 trans-Bicyclo[4.4.0]deca-2,4-diene, 1012 cis-Bicyclo[6.2.0]deca-2,4,6,9-tetraene, 1025 Bicyclo[2.2.1 heptane, 445 Bicyclo[4.l.O]heptane, 489 l, l'-BicyclohexenyI, 986 cis-Bicyclo[4.3.0]nona-2,4-diene, 1012 trans-Bicyclo[4.3.0]nona-2,4-diene, 1012 Bicyclo[2.2.2]oct-2-ene, 445 cis-Bicyclo[4.2.0]octa-7-ene, 1025 Bidentate, definition, 1042- 1043 Bijvoet, J.M., 140, 154, 155, 1164 Bilayers, 1130-1131 Bile acids, 1 135 Bimolecular displacement mechanism, 959 -96 1

(See also Nucleophilic aromatic substitution) Bimolecular elimination (E2 mechanism), 293 -

294 (See also Elimination reactions) Biochemical processes

biosynthesis of fats, 1 122 biosynthesis, of fatty acids, 1132- 1134 chvmotrvus~n acaon. 1236- 1240

hydroli&s, 1236- 1238 nucleoproteins and nucleic acids, 1241 vision, 285-287

Biochemistry, definition, 1 1 19 Bi+egra&ble detergents, 1 126- 1 127 Bio-inonose, 1 182 Biological oxi&tion and reduction, 1 103 Biomass, 2 Biomolecules, 69, 1 1 19 Biosvnthesis

offats, 1 122 I of fatty acids, 1 132 - 1 134 Biot, Jean-Baptiste, 130 Biphenyl, t553, 546,949 1,2-B/s(4phenylphosp$no)butane, 105 1 2,4-Bis(dIphenylphosphlno)pentane, 105 1 1,2-Bis(diphenylphosphino)propane, 105 1

2,2-Bis@-hydroxyphenyl)propane, 1099 Bisphenol A, 1099 Block copolymer, 1084 Boat conformation. 455 - 460 Boc-Glycine, 1224 ' Boiling point, 30 - 3 1

associated liquids, 30,2 17 - 2 18,89 1 chain branching and, 94 chain length and, 93 - 94 hy,&ogen-bonding

mtermolecular, 30,217-21 8,891 intramolecular, 89 1 - 892

ionic vs. non-ionic compounds, 30 molecular sham and. 94 molecular size and, 3 l, 93 polarity, 217, t2 17 '

Bombykol, 8 19 Bond angle, 13, 17 Bond dissociation energy, insidefiont cover, 9,2 1 -

'7'7 A 7 L&, -t I

comparison of cations, 197- 198,403 heterolytic, t22 homolytic, t2 1, 364

Bond energy, 2 1 - 22 Bond length, 10 Bond orb~tals, see Orbitals Bonds

bending, infrared absorption and, 590, 593-594 bent, 453 benzene, 500 breaking, 153, 160, 165 cleavage, 22 covalent, 4 -59- 1 1 dipole+lipole, 28-29, 259-260 double, see Carbon-carbon double bonds hvbrid. 395

, , ionic, 4 one-and-a-half, 395, 500, 733 orbitals, see Orbitals from overlap of orbitals, 9- 1 1 R, 274-275,426-427 polarity, 23 U, 274-275,426 single, see Carbon-carbon single bonds stretching, infrared absorption and, 593 - tri~le. 425 -427

~ o n d strength, see Bond dissociation energy 9-Borabicyclo[3.3. llnonane (9-BBN), 809, 8 18,

934-935 Borane, 348 Borane-tetrahydrofuran complex Borate esters, 386 Borazole, 503 Boric acid, 347 Borneol, 1 18 1 Boron, 13- 14,350 Boron trifluoride, 13 - 15 Boron trifluoride etherate, 1063 Bosnich, Brice, 105 1 Boyd, T.A., 1 19 Breslow, Ronald, 507 Bridged cation, 1036 Bridged intermediate, 1036 Bromination

of alkanes, 104- 118 of alkenes, 339 - 342 of alkylbenzenes, 566-568 of methane, 44-4576 stereochemistry, 1032- 1035 (See also Halogenation)

Bromine, 370, t588 addhon to 2-butene, 371 -372,

Bromine water, 1 150 pBromoacetanilide

preparation, 947 reactions, 848, 859

Bromoacetone preparation, 802,804 react~ons, 933

Bromoalkanes, 104 3-Bromo-4-aminotoluene, 86 1 m-Bromoaniline

physical constants, t824 preparation, 830 reactions, 872

eBromoaniline, t824 pBromoaniline, t824,848 pBromoanilinium chloride, 859 Bromoanisoles, 965 pBromobenzaldehyde, 662 m-Bromobenzamide, 830 Bromobenzene, 498,508,552,584,943,@45,951

nitration, t520 m-Bromobenzenediazonium chloride, 872 pBromobenzenesulfony1 group, 272 m-Bromobenzoic acld, t7 15 o-Bromobenzoic acid. t7 15. 72 1 pBromobenzoic acid; t715; 716 o-Bromobenzovl chloride. 769 m-~romobenzil alcohol, 552 l-Bromobutane, see n-Butyl bromide 2-Bromobutane, see sec-Butyl bromide 3-Bromo-2-butanol, 386, 1032- 1034, 1038 3-Bromo-l-butene, 417,423 l-Bromo-2-butene, 417,423 pBromo-sec-butylbenzene, 72 1 PBromobutyric acid, 975 m-Bromochlorobenzene, 524,969 l-Bromo-3-chlorocyclobutane, 645 2-Bromo- l-chloroethane, 34 1 Bromochloromethane, 133, 14 1 l-Bromo-2chloro-2-methylpropane, 124 3-Bromo-5-chloronitrobenzene, 509 l-Bromo-2-chloropropane, 124 l-Bromo- l-chloropropene, 28 1 2-Bromo- lchloropropene, 28 1 Bro~~cyclohexane (cyclohexyl bromide), t169,

a53 NMR and conformational analysis of, 628,644

2-Bromocyclohexanone, 800 l-Bromocyclohexene, 492 3-Bromocyclohexene, 323,391,414 2-Bromo-2-cyclohexenol, 10 12 2-Bromocyclohexyl brosylate, 1041 Bromocyclopentane, 448 l-Bromo-1,24chloroethene, 28 1 3-Bromo-2,24methylbutane, 246 4-Bromo-2,44methylhexane, 168 trans- l-Bromo- 1,2&phenylethene, 385 l-Bromo-1,2-diphenylpropane, 377- 379 Bromoethane, see Ethyl bromide 2-Bromoethanol (ethylene bromohydrin), 341,

'342.482 -, -- 2-~romoeth~lnitrate, 341 o-Bromofluorobenzene, 967 Bromoform, 45, t169 a-Bromoglutaric acid, 742 Bromohydrins, 342 D-(-)-3-Bromo-2-hydroxypropanoic acid, 1 163 pBromoiodoknzene, 509 2-Bromo-l-iodoethane, 34 1 a-Bromoisovaleric acid, 727 Bromomesitylene, 724 3-Bromo-4-methoxybiphenyl, 949 l-Bromo-3-methylbutane, 693 2-Bromo-2-methylpropane, see tea-Butyl bromide m-Bromonitrobenzene, 872 Bromonitrobenzenes, 524 Bromonium ions, 340.374-375376, 1033- 1034

1-Bromo-Zoctene, 392 3-Bromo-l-octene, 392 2-Bromopentane, 3 10 3-Bromopentane, 3 10 2-Bromo~entanedioic acid. 742 m-~romophenol, t890 '

preparation, 872 o-Bromophenol, t890,900,906

p-Bromophenol tert-Butyl bromide

7-Bromophenol, 509, t890 preparation, 901,906

I-Bromo-l-phenylethane (a-phenylethyl bromide), t169, 857

preparation, 170,550,566 !-Bromo-l-phenylethane, 566 X-@-Bromopheny1)ethyl alcohol, 967 hBromopheny1 ptoluenesulfonate, 900 -Bromopropane, see n-Propyl bromide !-Bromopropane, see Isopropyl bromide !-Bromopropanoic acid, 7 13 -Bromo-2-propanol, 2 15 -Bromo-l-propene, 429 !-Bromopropene, NMR signals, 602 - 603,6 17 I-Bromopropene, see Ally1 bromide K-Bromopropionic acid, 7 13

preparation, 833 reactions, 12 13

-Bromopropyne, t 169 -Bromopyridine, 1070 -Bromopyridine, 1068 -Bromopyridine, 1073 -Bromopyridine N-oxide, 1073 1-Bromosuccinimide (NBS), 323,390,392 r-Bromotoluene, 664,845 synthes~s, 872

-Bromotoluene, 72 1, t945 synthesis, 867, 871

-Bromotoluene. 662, t945 synthesis, 87 1 ' .

lromotrichloromethane, 322,583 -Bromo- l, l, l-trichloronane, 322

Irosyl group, 234 ,rown,H.C., 117, 161-162,347,349,389,933 -)-Brucine. 160 'S; 234 ' uckminsterfullerene, 3, 5 12 structure of. 512-513

uckyball, 5 12 unnett, Joseph, 299,855-857,944,948,960,970 ,2-Butadiene, 4 10, ,3-Butadiene, 397, 399, 406, 410, 412, 414,419,

983 1005 - - - > - - - - ~~polymerization of, 1095 cyclization, 1009 cycloaddition, 983, 1014- 1015 Diels-Alder reaction, 982-983, 1014- 1015 electronic configuration, 997 - 998 electrophilic addition, 4 15,4 17 -4 19 heat of hydrogenation, t4 10,4 1 1 molecul~ orbitals, 997 - 999 polymenzahon, 419, 108 1 preparation, 4 14 stabilization, 410-41 1 (See also Dienes)

utanal, see n-Butyraldehyde utane gauche interactions, 85 - 86,462,467 1,3-diaxial interactions, 467

.Butane, t84, t93 chlorination, 109, 152 conformations, 85-86,455,463 halogenation, 109 isobutane, 84 physical constants, t84 preparation, 98,431,447 thio~hene from. 106 1

addition of hydrogen halides, 329 dipole moment, 284 hydrogenation, 277

heat of, t326,326 ozonolvs~s. 323

ieadvity, 338, 348 2-Butene, 268-272,277-278, t277,279,

t285, 311,314,375, 384,386,883 adhtion of hydrogen hahdes, 329 cyclopropane from, 476 geometric isomerism, 278 -280 hydrogenation, 277 ~re~aration. 288 ~ea&vity, 338-

cis- and trans-2-Butenes, 277-280, 284-285, 372, ?RA

adztion of bromine, stereochemistry, 368-372 addition of carbenes, stereochemistry, 476478 addition of methylene, stereochemistry, 475 CMR spectra, 637-638 diol formation, stereochemistry, 372 dipole moments, 284 heats of hydrogenation, 326

stability and, 326 hydroxylation, stereochemistry, 372 physical properties, t277,284-285, t285

Butenedioic acid, 384, 1046 cis-Butenedioic acid (maleic acid), 973 trans-Butenedioic acld (fumaric acld), 973 cis-Butenedioic anhydride, 973 2-Butenolc acid, 7 16 2-Buten-l-01,423 3-Buten-2-01,283,423 tert-Butoxycarbonylglycine, 1224 tert-Butoxycarbonyl group, 1223 Butter, t112 1 Butvar, 1093 n-Butvl acetate. t769

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, 1 164 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

tert-Bbtyl acetate, 778 n-Butylacetylene (l-hexyne), 429, t429, 635 -636 n-Butyl alcohol, 38, t216, t217,218,229,238,

t272, 307, 314,660, 691, 883 dehydrauon, 239,288,311 industrial preparation, 808 - 809 oxidation. 662

677,348, 1051 sec-Butyl alcohol, t216,235,765,774,787,883

dehydration, 288,3 1 1 infrared spectrum, 595 optical activity, 159,246 preparation, 243,689

tert-Butyl alcohol, 124, 188, 215, t216,224, 225, 229,310,313,584,724,778

dehydration, 3 1 1 Friedel-Crafts allcylation with, 559 hydrogen halides reaction, 224 preparation, 33 1-332

n-Butylamine, 212, t824, 836, 883 sec-Butylamme, t824 tert-Butylamine, 822, t824 nButylbenzene, 653, 825

i@ared spectrum, 59 1 oxldahon, 562 preparation, 559,672

sec-Butylbenzene, t553,559 tert-Butylbenzene, t553, 559-560 sec-Butvl benzoate. 787

. , , , , , , 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, 1 134

n-Butyl chloride, t169,883 from n-butane. 104. 109 dehydrohalogenation, 288 Friedel-Crafts alkylation with, 559

sec-Butyl chloride, t169,385,883 from n-butane, 104, 109,15 1 - 152 dehydrohalogenation, 288 enantiomers of, 132, 135, 140, 142, 152 lithiumdialkylcopper from, 102 stereochemistry, 153, 157- 158

tea-Butyl chloride, 103, 1 16, 124, t169,229,3 10 dehydrohalogenation, 3 10 Fnedel-Crafts alkylahon with, 901 from isobutane, 104, 108 lithiumdialkylcop r from, 99 preparation, 224, $6 trimethylacetic acid from, 723 - 724

tert-Butylcyclohexane, 463 4-tert-Butylcyclohexene, 49 1 4-tert-Butylcyclohexyl ethyl ether, 491 cis-4-tea-Butylcyclohexyl tosylate, 49 1 trans-4-tert-Butylcyclohexyl tosylate, 49 1 sec-Butyldimethylamine, 822 n-Butyldimethylcarbinol(2-methyl-2-hexanol),

687,688,690 Butylenes, 277-278

physical properties, t277 structure, 277-282 (See also Butene; Isobutylene)

n-Butylethylamine, 836, 837 (R)-sec-Butyl ethyl ether, 246 tert-Butyl ethyl ether, 241,309 n-Butyleth lmethylamine, 837 tea-Butyl koride, NMR spectrum, 192,645 tert-Butvl free radical. see tert-Butvl radical Butyl &ups, 89 '

sec-Butyl hydrogen phthalate, 765 tert-Butyl hydrogen sulfate, 33 1 tert-Butyl hydroperoxide, 1055 tert-Butyl hypochlorite, 124,393 n-Butyl i h d e , t169 sec-Butyl iodide, t169,328 tert-Butyl iodide, t169,328 n-Butyl isopropyl ketone (2-methyl-3-heptanone),

664. n-Butylhthium, 932, 1085 n-Butylmagnesium bromide, 687,688,690 sec-Butylmagnesium bromide, 98,687 sec-Butylmethylamine, 836 n-Butyl methyl ether, 212 sec-Butyl methyl ether, 243 tert-Butyl methyl ether, 237,241 tert-Butyl methyl ketone (3,3-dimethyl-2-butan-

one), 705,800,935 ptert-Butylphenol, 90 1 tert-Butyl peroxide, 124,584, 1055 sec-Butyl phenyl ketone, 805 (+)-sec-Butyl phenyl ketone, 803 tert-Butyl radical, 1 16, 1 17,402 Butyl rubber, 1085, 1096 sec-Butyl tosylate, 235 m-(n-Buty1)to uene, 667 pmButylto!uene, NMR spectrum, 609 1Butyne (ethylacetylene), 428, t429

preparahon, 438,440 2-Butyne (dimethylacetylene), 428, t429,43 1 1,4-Butynediol, 1062 l-Butyn- l-yllithium, 438 n-Butyraldehyde, t217, t272,659,660, t661, 734

Cadaverine, 844 M e i c acid, 9 15 Cahn-Ingold-Prelog sequence, 140 - 144,28 1,12 12 Cahn, R.S:, 134,. 140 Calcite. Nicol Dnsm. 128 calcium acetaie, 7 17 Calcium aldonate, 1 154 Calcium carbide, 38,438 Calcium carbonate, 396,734 Calcium cyanamide, 782 Camphoronic acid, 941 Cannizzaro reaction, 674,683-684, 806

crossed, 674 Capric acid, 7 14, t7 15 Caproaldehyde, t66 1 Caproamide, 830 Caproic acid, 714, ~715, 745,901 Caprolactam, .l098 Ca~rovl chlonde. 663 capryiic acid, 7 1'4, t7 15 Carbamates (urethanes), 780-781, 782, 1223 . . Carbamic add, 78 1 ' -

Carbamide (urea), 779 -783 Carbanionoid compounds, 100, 102,775,811 -

812.967 carbzdns; 100,797-820,856,923-940

from acetoacetic ester, 8 14- 8 15,927 - 930 addition to aldehydes and ketones, 800-801,

805-807,809-811,816 in aldol condensaQons, 800- 80 1,805 - 807,

809-810 basicity, relative, 1071 - 1072 charge accommodation, 798,8 13 in Claisen condensation, 802,8 13 - 8 16 from cyanoacetic ester, 980-981 definition, 297 . in dehydrohalogenation, 298 in halogenation of ketones, 803 from malonic ester, 924-927,980-981 in Michael reaction, 979-982 in nucleophilic acyl substitution, 802 in nucleophilic addition, 976-978 in nucleophilic aliphatic substitution, 102.

927-933 in nucleophilic aromatic substitution, 955

962-963, 1070- 1071 sbitals, 438, 1072 in organoborane synthesis, 933-935 in Perkin condensation, 8 1 1 from pyridine, 1069- 107 1 reactions, summary, 800 - 802 resonance, 797 -798 shape, 827 in Wittig reaction, 8 1 1 - 8 12 from ylides, 811-812 (See also individual carbanions)

Carbazole, 1057 Carbenes, 473-478

addition of substituted, 476 -478 Carbenium ions, 19 1 Carbenoid compounds, 477 -478 2-Carbethoxycyclopentanone, 8 15 Carbitol, 484 - - Carbocations, 175, 188- 191,304,347,354,373,

682, 1033, 1037, 1040

Carbohydrates

in acetal formation, 68 1 in addition to a,P-unsaturated carbonyl com-

pounds, 975 -976 from alcohols and allcenes, 559 in ablation of alkenes, 345 from alkyl halides, 558 - 559 definition, l9 1 from dehydration of alcohols, 3 12 delocalization, 415 -417 ease of formation, 201 -203,335-338 electronic effect in, 193,202 in electrophilic addition, 332-338 in electrophilic aromatic substitution, 526-527,

528,529,531 -544 encumbered, 270 formation, 335 intermediacy of, 205 loss of proton from, 3 14 from naphthalene, 545 -546 nucleophilically solvated, 269, 270 from pyridine, 1069 rate of elimination from, 3 18 rate of formation, 201,304,336,338,405,575 reactions, 208, 304, 344-345, 560 rearrangement of, 203-208,305-306 relative stabilities, 196- 198,402 resonance-stabilized, 975 - 976 in &l reactions, 188, 195- 196 in solvolysis, 268 stability, 198, 199, 304-305, 336,403,574-575 stabilization, 199,406-407 structure, 193 and transition state, 202 (See also individual cations) arbohydrates, 676, 1132, 1143- 1204 classification, 1 144 definition, 1 144 disaccharides, 1185 - 1192 esterification, 764 fermentation, 2 19 fuel from, 2 19 -22 1 methylation, 1 174- 1 176 monosaccharides, 1 143 - 1 184 nomenclature, 1144,1146- 1149, 1177- 1178 o v o n e formation, 1 151 - 1 152 ondahon, 1149- 1150 polysaccharides, 1 192- 120 1 (See also Aldohexoses; Aldoses; Monosaccha-

rides; etc.) arbon ~ - - -

Age of, 3 a-, 291,294,380, 1049 analysis for, 72 B-, 291,294, 379

electrophilic, sources of, 485 migration, 1022, 1035 nucleophilic, 936 tetrahedral. 126- 128. 131 G b o s d s ; 297,798 ' arbonate ion, 396 arbonahon of ~henols, 902 arbon-carbon bonds in benzene, 499 - 500 comparison of, 427 -428,499 - 500 formation, 439,923

'arbon-carbon double bonds, 283,288,399,578- G 7 0

an;& for, 324,340,358-359,360-362,637- 638

in ethylene, 273 -275 hindered rotation about, 275,278 infrared spectra, 592 -593 length, 276 protecting, 290 reactions, 3 17 - 365 as substituent, 387-388

:arbon-carbon slnde bonds -.

in ethane, 78-82-

Carboxyl group

free rotation about, 79- 82 infrared spectra, 592- 594 length, 276 in methylacetylene, 276 rotational banier, 82

Carbon-carbon triple bonds, 425-427 Carbon-chain lengthening

aldol condensahon, 805 - 8 10 ofaldoses. 1152-1154 of alkanes, 10 1 of alkynes, 429 -430,438-439 synthesis of amines, 83 1 of carboxylic acids, 870

Carbon-chmn shortening of aldoses, 1 154 degradation of alkenes, 358 - 360 Hofmann degradation, 836

Carbon dioxide. 1 19 Carbon dioxide'balance, 120,2 19 -221 Carbon-halogen bonds, 408,544,951 Carbonyhy@ogen bonds, 63 Carbomc aad, 780,78 1

functions! derivatives of, 779 - 783 Carbonium Ions, 19 1 (See also Carbocations) Carbon monoxide, 720 Carbon-oxygen double bond, 669 Carbon tetrabromide, 45, t169 Carbon tetrachloride, 32,44, t169

addition to alkenes. 355 carbon-1 3 nucie&magetic resonance (CMR)

~pectro~~opy, 629 -639 a-effect. 636-637 analysis

of alcohols, 639,640 of aldehydes and ketones, 639,701 of alkanes, 639 of alkenes, 639 of alkyl halides, 639,640 of alkynes, 639 of carboxylic acids, 639,747 of hydrocarbons, 639

P-effect, 636.-637 chemcal sh&. 634-638.639 effect of methjl group, 637 effect of subsfituents, 636-637 y-effect, 636 -637 geometric isomerism, 637-638 hybridization of carbon, 634-636 off-resonance, 63 1 proton-coupled, 63 1 -633 proton-decoupled, 630 - 63 1 splitting of sipals, 630-633,640

Carbonyl chloride, see Phosgene Carbonyl compounds, 657

addihon to, 800 - 801,974 - 984 Diels-Alder reaction, 982 - 984 electrophilic addition, 974- 976, 978 - 979 interaction of functional groups, 974 Michael addition, 979 - 982 nucleophilic addition, 976-978 preparation, 973 proton chemical shift, t607 structure and properties, 971 -973 (See also Aldehydes; Keto acids; Ketones;

a , Unsaturated carbonyl compounds) Carbony6,up, 669

and acidty of a-hydrogens, 797-799 in aldehydes and ketones, 669-671 in aldol condensation, 807 bonding in, 756 in carboxylic acid derivatives, 755-759 in carboxylic acids, 728 geometry, 657-658,756

Carbowax, 1080 Carboxylate anion

basic~ty, 729 structure, 733-734

Carboxylate ions, structure of, 733-734 Carboxyl group, 713,725,739

electron withdrawal by, 728-729

1292 Carboxylic acid anhydrides Chao

Carboxylic acid anhydrides, see Acid anhydrides Carboxy$c acjd chlorides, see Acid chlorides Carboxyhc aads, 713-752,1125

acidity, 728-729,732-736 effect of substituents, 735 -736

acidity constants. 729.2735

a-amino, see Amino acids analysis, 744-747 aromatic

acidity, 736 nomenclature, 7 16 qreparation, 563,721 -722 nng substitution, 2520,728 sources, 7 19 - 720

biosynthesis, 1 132 - 1 134 conversion

into acid chlorides, 726 into amides, 727 into esters, see este@c+ion below into functional denvahves, 725-727 into salts, 7 19,725

effect of substituents, 735 - 736 estenficahon, 726,737-739 (See also Esters)

mechanism, 776-777 reactivity, 738

from fats, 7 19 functional derivatives, 725 - 727,744,753 -796

(See also individual families) analysis, 783-785 carbonyl group m, 756-759 compared with sulfonyl derivatives, 859 -860 hydrolysis, 761,764, 767-768, 771 nomenclature. 754 nucleophilic acyl substitution, 755 - 760 physical properties, 754-755, t755,2769 spectroscopic analysis, 784-785 structure, 753

halogenation, a , see Hell-Volhard-Zelinskv re- action

hy+ogen bonding in, 7 17 lolluabon, 729 keto, see Keto acids neutralization eqmvalent, 744 - 745 nomenclature. 7 14 - 7 17 odor, 717 '

physical properties, t715, 717 preparation, 360,720-723,811

acetoacetic ester synthesis, 939 carbonation of Grignard reagents, 72 1 - 722 via diazonium salts, 870 Grignard synthesis, 723 - 724 halofotm reaction, 676,698 hydrolysis of nitriles, 722, 724-725, 870 Kolbe reaction. 908 malonic ester synthesis, 924-927 organoborane synthesis, 933-935 via 2-oxazolines, 932 oxidation - .. .. -

of alcohols, 226,235 -237,72 1,722 of alkenes, 359- 360,699 of alkylbenzenes, 563 -564,72 1 of arena. 562.563.721 of methyl ketones, 6761677

periodic acid oxidation, 359 -360,699 Perkin condensation, 8 10 - 8 1 1

reactions, summary, 725 -728 reduction to alcohols, 727, 740 salts, 717,718-719,725

nomenclature, 7 17 physical properties, 7 18 - 7 19,744 - 745

solubility, t715,717-719 salts, 718-719

sources aliphatic, 7 19 aromatic, 720

spectroscopic analysis, t592, t607,745-747, t786

structure, 7 13 substitution, aa, 727

Hell-Volhard-Zelinsky reaction, 727,74 1 - 742

ring, 2520, 728 unsaturated

a,/?-unsaturated, 872, 972-973 electrophilic addition, 974 - 975 from fats, 719,1122-1123, 1125-1126 nucleophilic addition, 976-978 preparation, 973

(See also Dicarboxylic acids) Carboxylic acids, functional derivatives of, 753-

796 (See also Acjd aphydrides; Acid chlorides; Amides; Carbo~uc acld, fundonal derivatives of; Esters; Fats; Imides)

Carboxypeptic@se, 1220 Cardiac glycosides, 1 135 Carius method

analysis for halogen, 73 analysis for sulfur, 5 14

a-Carotene, 488 pcarotene, 286,488,599 y-Carotene, 488 &rvacrol, 9 16 3,8-Carvomenthenediol, 704 Carvomenthol, 705 Carvomenthone, 705 (+)-Carvotanacetone, 705 Castile soap, 1 124 Catalvsis

acid, 229-233 in 0x0 processes, 1052- 1053 phase-transfer, 264-266 by transition metal complex, 105 1 Ziegler-Natta, 1087- 1088

Catalytic cracking, 1 19, 120 Catalytic hydrogenation, 325 (See also Hydrogena-

ban) ~atal$:c'reforming, 96, 119, 555-556,720

of alicyclic hydrocarbons, 446 of alkanes. 120

Catechol, 889 Cationic polymerization, 1084- 1085 Cell membranes, 1 130- 1 13 1 (+)-Cellobiose, 1185, 1188- 1189 Cellobiose octaacetate, 1188 Cellobiuronic acid, 1203 Cellophane, 120 1 Cellulose, 220, 1 143 - 1 144, 1 192

molecular weights, 1200 properties, 1200 reactions, 1200 - 120 1 structure, 1200

Cellulose acetate, 120 1 Cellulose ethers, 1201 Cellulose nitrate, 120 1 Cellulose trinitrate, 120 1 Cellulose xanthate, 1201 Cerebrosides, 1 137 CFCs 69,71, 119 chair;-initiating steps, 70, 7 1, 1081 Chain-propagating steps, 70,71, 108 1 Chain-reaction polymerization, 1078, 1087 - 1089

coordination polymerization, 1087- 1089 copolymerization, 1083 - 1084 free-radical vinyl polymerization, 1080- 1083 ionic polymerization, 1084- 1086 (See also Free-radical polymerization)

Chain reahons chlorination of methane, 48-49 combustion of alkanes, 1 18 formation of ozone shield, 70- 7 1 halogenation of alkanes, 104- 106 photolysis of CFCs, 7 1

Chain-terminating steps, 7 1, 108 1, 1086 Chain transfer, 1082 Chair conformation, 455-460,463,467 Chalcone, 872 Chao, T.H., 161 - 162

Chavibetol Cinnamaldehyde

Zhavibetol, 9 18 Zhelation, 891, 1043 3hemical bonds, see Bonds 2he4cal pgeogenetics, 1227 -hemcal s m . 604-608. t607 Shichibabin reaction, l070 Zhirality, 133-136, 140-141, 151-153

bond breaking and, 153 - 154, 160 - 162 chiral centers, 135- 136, 148

generahon of, 151 - 153, 1050 generation of second, 156 - 158

1,2-dimethylcyclohexanes, 468-469 optical activity and, 139, 154- 155

reagents, chiral and achiral, 138 reactions of chiral molecules, 153 - 162

Zhiraphos, 105 1 Zhlorination. 43 -44

of alkanes,' 104 - 1 18 of alkylbenzenes, 565 - 568 aromatic, 529 mechanism of, 46 - 48 of methane, 43 -44,48 -49,76 and stereochemistry, 160- 162 (See also Halogenahon)

Zhlorine, 364 abundance of, 37C1, t588 36Cl as tracer, 1 18

Clhloroacetic acid, 750,829 preparation, 727 reactions, 743,902 relahve ac~hty, 736

Clhloroacetone, 364 z-Chloroacrylonitrile, 990 ,hloroalkanes (alkyl chlorides), 104, 124 Fhloroallybenzene, 967 ,hloroanilines, t824 Clhloroanisoles, 1204 z-Chlorobenzaldehyde, 674 ,hlorobenzene, 508, t945,968

nitration. t520 prepadon, 498 reactions. 542-544,827,894,953,970 resonan&, 950

W-Chlorobenzenediazonium hydrogen sulfate, 898 7-Chlorobenzenesulfonic acid, 509 W-Chlorobenzoate ion, 674 W-Chlorobenzoic acid, t7 15, t854 ~Chlorobenzoic acid, t715,745,749,750,943,970 ~Chlorobenzo~c ac~d, t7 15,750 W-Chlorobenzyl alcohol, 674 ~ndo-2-Chloro-exo-2-bromobicyclo[3. l .O]hexane,

In17 -~hiGbutane, see n-Butyl chloride :-Chlorobutane, see sec-Butyl chloride

;khl&ro-2-butene, tl69 I-Chloro-2-butyl free radical, 159 :hlorobutyricc acid, 736 :hlorocarbomc acid, 78 1 :hlorocyclopropane, 444,448

- 7 -

Aloroethane. see ~ t h v l chloride -~hloroethane, 92, tf69 I-Chloroethanol (ethylene chlorohydrin), 214,223,

1054 Chloroethene, 329 (l-Chloroethyl)benzene, see a-Phenylethyl chloride Chlorofluorocarbons, 43, 1 19

and ozone shield, 69 - 7 1 Chloroform, 44, 124, t169,583,902,908

addition to alkenes, 355 test for akylbenzenes, 580

l-Chloro-2-halopropane, 23 1 4-Chloro-2-hexene. 4 15

2-Chloro-3-hexene, 41 5 Chlorohydrins, 342,384

~hloroiodomethanesuifonic acid: 142 enantiomers, 132,134

Chloromethane, see Methyl chloride l-Chloro-2-methylaziridine, 827 l-Chloro-2-methylbutane

chirality, 154, i56 photochemical halogenation of S-(+)-isomer, 16 1

2-Chloro-2-methylbutine. see tert-Pentyl chloride y-Chloro-a-methylbutyric acid, 716 2-Chloro-l-methylcyclohexane, 445 3-Chloro-2-methylpentane, 142, 168 l-Chloro-2-methylpropane, see Isobutyl chloride 2-Chloro-2-methylpropane, see tert-Butyl chlonde 3-Chloro-2-methyl-l-prouene, 364 Chloromycetin, i37,863- m-Chloronitrobenzene, 509,943, t945,957-958

preparation, 947 o-Chloronitrobenzene, t945,954, pChloronitrobenzene, t945,953, 2-Chloro-4-njtrophenol, 509 4-Chloro-2-n~trotoluene. 523 . - - ~

4-~hloro-3-nitrotoluene; 523 Chloronium ions. 376 2-~hloronorbornene, 473 l-Chloropentane, 636 - 637 2-Chloropentane, 246 3-Chloropentane, 246 m-Chlorophenol, 898, t890 o-Chlorophenol, 889, t890 pchlorophenol, t890 3-(pChloropheny1)butanoic acid, 7 16 l-Chloro-l-phenylethane, see a-Phenylethyl chlo-

ride 2-Chloro-l-phenylethane, seePPhenylethy1 chlo-

ride fi(pChloropheny1)ethyI alcohol, 967 Chlorophyfl, 220, 1007, 1059, 1122 Chloroprene, 420 l-Chloropropane, see n-Propyl chloride 2-Chloropropane, see Isopropyl chloride l-Chloro-2-propanol (propylene chlorohydrin),

231,320,487 preparation, 342

l-Chloropropene, 442 3-Chloro-l-~ro~ene. see Allvl chloride .

h-~hlordvrdpionic acid, 750

pchloroityrene, 578 a-Chlorotoluene, see Benzyl chloride m-Chlorotoluene, 584, t945

nitration, 524 o-Chlorotoluene. 584. t945.947

preparation, 565,867 . ~Chlorotoluene, 523, 584, t945

preparation, 565 Chlorot@uoromethane, 69,76 Cholecalcfierol, 1030 Cholestane-3/3,6adol, 1 140 - 1 14 1 3-Cholestanone, 1 140 2-Cholestene, 1 141 Cholesterol. 421. 1134- 1137. 1140- 1141 Choline, 882, l130 Choline phosphoglyceride, 1 130 Chromatography, 1217 Chro+c anhydride, test for alcohols, 244,362 Chromum(VI), 236 Chymotrypsin

action, 1236- 1240 m-stmcture. 1234. 1236- 1237 -- ---- - ~ - - ~ > -

~hymotrypsino~en,' 122 1, 1237 (+)-Cinchonine, 160 Cinnamaldehvde. 677.872.973

synthesis, 80 l

1294 Cinnamic acid Crystallinity

Cinnamic acid (3-phenylpropenoic acid), 8 1 1,8 17, t972.977

cinnamyl alcohol, see 3-Phenyl-2-propen-1-01 cis and trans isomers, see Geometric isomerism Cit*, 705,9 15 Citnc aad, 1 114, 1139 Citronellol, 412 Claisen condensation, 772,802,8 1 1,8 13 - 8 16

crossed, 8 16 Cleavage

acid-catalyzed, 482,483 -484,910 by acids, 242 -243 of alkenes, 358-360 base-catalvzed. 483. 485 ofbonds, 22 ' '

of epoxldes, 482,483-484 of esters, 775, 777 of ethers, 242 -243 of ketones, 676 ozonolysis, 358- 360 by periodic acid, 699 by permanganate, 359 -360 Sw2.485-487

chik spectroscopy, 629 -639 Coal, 1,94,555

as source of aromatic compounds, 555 Coal gas, 555 Coal tar, 555

as s o k of carboxylic acids, 720 Cocaine, 159, 1073 Coconut oil, t 1 12 1 Cod liver oil, t 1 12 1 Codons, 1247 Coenzyme A, 882, 1128, 1132 Coenzvmes. 1229 coke, 355 ' Collagen, 1225, 1234 Collision energy, 57 - 58 Collision frequency, 55-58, 108 Collisions, 5 1 Combustion of hydrocarbons, 42-43,72,1 l

119 ~ombustion train, 73 Concentration, and reaction rates, 177 - 178 Concerted reactions, 1004, 1005 - 1024 Condensation polymerization, 356, 1079 Conessine. 1 140 configuration

absolute, 155, 183, 1165, 1166- 1168 of aldoses, 1160- 1162 of amino acids, 12 12 of carbohydrates, 1155- 1167, 1173- cis and trans, 279 D and L, 1162-1164, 1166 definition. 140 Eand Z, 281-282 of (+)-glucose, 1 155 - 1 160 inversion of, 182, 183, 367 and optical rotation, 141 R andS, 140-141, 1108, 1163 relative, 155 retention of, 840 sequence rules for, 140- 143, 148 x-ray analysis, 140

Configurational isomers, definition, 150 Conformation

anti, 85, 472 boat, 455 -460 chair, 458,463,467 definition, 79 eclipsed, 79 envelope, 490 gauche, 85 half-chair, 458 NMR and, 644, 1 184 skew, 79 stability, factors affecting, 454-455 staggered, 79 twist-boat, 455 -460

Conformational analysis, 79-82,85 - 86, 1 149-150

aldoses, 1178-1180 amylose, 1 194- 1 196 angle strain, 454 anomeric effect, 1 180 butanes, 85-86 cyclobutane, 459 cyclohexane, 455 -463

derivatives, 466 -47 1 1,3-diaxial interaction, 46 1 1,2-dimethylcyclohexanes, 466 - 470 dipole-dipole interachon, 454 E2 elimination, 472-473 ethane, 82 factors in, 454-455 D-(+)-glucose, 1 1 78 - 1 1 80 methycyclohexane, 462-463 NMR and, 644, 1 184 proteins, 1229 pyranoses, 1 178 - 1 180 torsional strain, 82. van der Wads swan, 86

Conformational isomers, definition of, 149 Conformers, 149- 150 Coniferyl alcohol, 9 19 Conjugated double bonds, 977-978

in al@nylbenzenes, 578 ultraviolet absorphon band shift, 599 in a,p-unsaturated carbonyl compounds,

Conjugated proteins, 1228 - 1229 Conjugation, 387-424,576-578 Conjugative effect, 406 Conrotatory motion, 1007- 1009 Converters, 1 19 Coordination polymerization, 1087 - 1089 Coordination sphere, 1043 Cope reaction, 8 1 1,927 Cope rearrangement, 10 19 Copolymerization, 1083 - 1084 Copolymers, 1083 Copper chromite, 780 Corey, Robert B., 1230 Corey-House synthesis, 101 - 102 Corn oil, t1121 a-Corticotropin, 12 17 Cortisone, 984, 1 135, 1 136 Colynebacterium diphtherium, 1 138 Corynomycolenic acid, 1 138 Cottonseed oil, t112 1 Coulson, C.A., 6,453 . Coumarane, 9 16 Counter-ion, 257 Coupling, of diazonium salts, 866,878 Coupling constants, 6 14 Covalent bonds, see Bonds C&phthienoic acid, 1 138 Craclun~. 96. 120- 121

- infrared spectrum, 9 13 m-Cresyl acetate, 901 Cresols, industrial source, 555 -556 Crick, F.H.C., 1242- 1246 Crossed aldol condensation. 809 - 8 10 Cross formulas, 1 148 Cross-links, in rubber, 420 Crotonaldehyde, see 2-butenal trans-Crotonic acid, 75 1, t972,975,978 Crotonyl-S-ACP, 1 134 Crotyl alcohol, t216 Crotyl chloride, t 169 Crotyl iodide, t169 Crown ethers, 272,478-481,916 Crystallini

degree o r 1094 of polymers, 1088, 1093 - 1094

stal structure f macromolecules, 1093- 1094 nd melting points, 27 nd physical properties, 945

.

umahnone, 916 nene (isopropyl+nzene), t553,559,894, 895 nene hvdro~eroxlde, 894.895 :arranpkmeit, 895 -897 '

nulated double bonds, 410 xic bromide, 935 tius rearrangement, 839 rnarn.de, 781,783,784 mnic acid, 78 1 mnides, see Nitriles noa acetic ester, see Ethyl cyanoacetate yocompou.nds, see Nitriles .yam- 1,3-d1phenyl- l-propanone, 976 inohvdrins. 678-679.1146 ?rm&on, 673 .yano-7-trifluoromethylnorcaradiene, 10 12 :yano-7-trifluoromethyltropylidene, 1012 :lic aliphatic compounds, 443-492 .nalysis, 487-488 .ngle strain, 450-454 5aeyer strain theory, 450-454 :onformational analysis, 455-463,466-471 :ycload&fion, 473-476, 1013-1018 lefinition. 1057 lehydrogenation, 446 ,3-dimal interaction, 46 1-463 :lectrocyclic reactions, 1005 - 101 3 ieats of combustion, 450-453, t451 ndustrial source, 446 -447 nethylene ad&bon, 473 - 478 iomenclature, 443 -446 ~hysical properties, t444 )reparation, 447 -448

cycloaddition, 473-476, 1013- 1018 methylene addIbon, 473 -478 ring closure, 447-448,452, 1005- 1013

.eactions, 448 ;449

.elative stabhbes, 450-453,458-459,466- 467

ing closure, 447-448,452, 1005- 1013 ing opning, 449 ;mall nng, 449 -450 ;tereoisomerism, 463 -47 1 See also Cycloalkanes; Cycloalkenes) $c anhydrides, 765 chc bromo~num ions, 374- 376 clic compounds, see Arenes, Aromatic com-

~ounds, Cyclic aliphatic compounds, Hetero- cyclic compounds

clic esters (lactones), 770 ~ l i c ethers, 478 (See also Crown ethers; Epoxides) rclic halonium ions, 340,376,487,952 ~ l i c mercurinium ions, 347,487 clization. 447. 556 (See also Cycloaddition reac-

tions; ~1ectroc~clic reactionsj cloaddition reactions, 473 -476 [2 + 21, 1014 [4 + 21,983 definibon, 448 Diels-Alder reaction, 982 - 984 and orbital symmetry, 10 13 - 10 18 rcloalkanes, 94,443-445, t444 (See also Cyclic

aliphatic compounds) rclobutane, 444, t444,45 1 conformations, 459 reactions, 449 -450 3-Cyclobutanedicarboxylic acid, 464 rclobutenes, electrocyclic reamons, 1005- 1024 rclodecane, 460 puckered ring, 452 5-Cyclodecanedione, 492 zns,cis,cis-Cyclodeca-1,3,5-triene, 10 12 Cyclodextrin, 1 199, 1200, 1204

~pentadienyl free radical

Cyclodextrins, 1198- 1200, 1204 uses, 1199, 1200

Cycloheptane, t444 1,3,5-Cycloheptatriene, 1076 Cycloheptatrienyl anion, 505 Cycloheptatrienyl cation (tropylium ion)

electronic configuration, 505,1000,1002 molecular orbitals, 1002 n electrons, 505, 1000

Cycloheptatrienyl radical, 505 Cyclohexadiene, 499 1,3-Cyclohexadiene, 400 - 40 1,414,444, t44

1005 reactions, 983

1,4-Cyclohexadiene, t444 Cyclohexane, t444,445,446,461

aqalysis, 487 m a l bonds, 460-463 bond dssociabon energy, 503 configuration, 456 conformational analvsis. 455 -463. . . derivatives

conformational analysis, 466 -47 stereoisomerism, 463 -473

equatorial bonds, 460-463 heat of combusbon, 45 1 industrial source, 446 NMR spectrum, 628-629 puckered ring, 452 shape, 456

Cyclohexanecarboxylic acid, 7 13,7 14, t7 15 1,2-Cyclohexaned$arboxylic acid, 764 1,2-CyclohexanedIol, 445,470 1,2-Cyclohexanediol decetafe, 1039 trans- 1,2-Cyclohexane&ol &acetate, 1040 Cyclohexanol, 2 14, t2 16

industrial source, 446 - 447 NMR spectrum, 624 reactions, 835

Cyclohexanone, 98 1 preparation, 835 reactions, 680,800,801,937

Cyclohexatriene, 497,499 Cyclohexene, 323,391,400-401, t444,448,

A99 pr&&ation, 835

Cyclohexene oxide, 1054 3-Cyclohexenol, 445 Cyclohexylamine, t824

preparation, 835 Cyclohexyl bromide (bromocyclohexane), t169,

628.644.835 ~~c lohexy l biosylate, substituted, 1041 Cyclohexyl chloride, t169

hydrolysis and neighboring group effects, 1038 Cyclohexyl tosylate, 1040 cis,cis-Cyclonona- l ,3-diene, 1027 cis,cis,cis-Cyclonona- 1,3,5-triene, 10 12 cis,cis,trans-Cyclonona- 1,3,5-triene, 101 2 Cyclooctadecanonaene, 1000 cis,cis-Cycloocta- l ,3-diene, 1025 cis,trans-Cycloocta-1,3-d+ne, 1025 1,5-Cyclooctadiene, reactions, 934 Cyclooctane, t444 1,3,5,7-Cyclooctatetraene, 516 Cyclooctatetraenyl dianion, 1000 1,3,5-Cyclooetriene, 1024 Cyclopentadene, 505,1028 1,3-Cyclopentadiene, t444, 445,982 Cyclopentadienyl anion

electronic configuration, 505 - 506, 507, 1000 - inn?

molec;1'& orbitals, 1001 - 1002 Cyclopen@dienyl cation

electroluc configurabon, 505, 1002 molecular orbitals, 100 1 - 1002

Cyclopentadlenyl free radical electronic configuration, 505,1001 - 1002 molecular orbitals, 100 1

1296 Cyclopentane Diastereomers

Cyclopentane, t444, 445,448,45 1 conformational analysis, 459 preparation, 672 stereoisomerism, 464 -466

Cyclopentanecarboxylic acid, 927 cis-1,2-Cyclopentanedicarboxylic acid, 764 1,3-Cyclopentanedicarboxylic acid, 464 1,2-Cyclopentanediol, 704

chirality, 465 -466 cis and trans isomers, 2 17,464-466

Cyclopentanol, t2 16,445 preparation, 672,677

Cyclopentanone, 672,763 formation, 763 reactions, 672,677

Cyclopentene, t444 reactions, 482,935

Cyclopentene- l-carboxaldehyde, 9 17 Cyclopentene oxide, 482 B-Cyclopentyl-9-BBN, 935 Cyclopentenyl cation, 101 1 Cyclopropane, 444, t444, 448,45 1

preparation, 447 reactions, 449-450

Cyclopropanecarboxylic acid, 927 Cyclopropenones, 1003 Cyclopropenyl anion, 1002, 1003 Cyclopropenyl cation, 1000, 1002, 1003, 101 1 Cyclopropenyl free radical, 1002, 1003 Cyclopropyl cauon, 10 1 1 2-Cyclopropyl-2-propanol, 646 2-Cyclopropyl- l, l , l-trideuterio-2-propanol 646 Cycloreversions, 10 17 m-, o- and pCymene, 1200 pCymene, t553 (-)-Cysteine, t1206 Cysteinylglycine, 1220 (-)-Cystine, t1206 Cytochrome c, 1248 Cytosine, 1243

in nucleic acids, 1241 - 1243, 1245,1246- 1247

D D, prefix, 1162-1164, 1166-1167 d, prefix, 1 163 Dacron, 744, 1090, 1094 "Dansyl" method, 1220 Deactivating groups, 520,522,538-539 Decalin (decahydronaphthalene), 489 c i s - W n , 644-645 n-Decane, i93 cis,cis,cis,cis,trans-Deca-1,3,5,7,9-pen, 1025 Decarbonylation, 106 1 Decarboxylation

of aromaucacids, 729 of keto aclds and malonic acids, 930 - 93 1

2,4,Q~eeatetraene, 101 1 l-Decene, t285 n-Decyl alcohol, t216 l-Decyne, t429 5-Decyne, t429 Degenerate pairs, 1001 Degradation, 12 1

determination of structure by, 358-360 Hofmann, see Hofmann degradation by oxidation, 359-360 by ozonolysis, 358- 360 Ruff, 1 154.

Dehalogenauon, of vicinal dihalides, 288,289 Dehydrafion, 3 12- 3 13

of alcohols, 288,289,306,310-315 mechanism, 3 12 order of reactivity, 3 1 1

of aldol products, 807 - 808 Dehydrobenzene, see Benzyne 7-Dehvdrocholesterol. 1030

Dehydrogenation of alicyclic hydrocarbons, 446 industrial, 555-556,576-577

Dehydrogenahon enzymes, 1228 Dehydrohalogenation

of allcyl dihalides, 429 -430 of alkyl halides, 174,288,290-293 E2,293-294,302 kinetics of, 293 order of reactnity in, 302 orientation of, 30 1 - 302,306 use in synthesis, 973 of vicina! dihalides, 429-430

Delocalizatmn energy, 398 (See also Resonance energy)

Delocahzation of electrons, 200, 398, 401 -402, 413,501 -502,568

Demercuration, 346-347 Denaturant, 22 1 Denaturation

of nucleic acids, 1226 of proteins, 1226

Denatured alcohol, 221 (See also Ethanol; Ethyl ' alcohol)

D,L-Dendroketose, l l83 Deoxyribonucleic acid, see DNA ~-2-Deoxyrib0~, 1241 Derivative, definition, 12 1 Desulfonation, 529- 530 Detergents, 1126- 1127

biodegradable, 1 126 - 1 127 manufacture of, 1089 non-ionic, 1 126 solubility and cleansing power, 253

m-Deuterioaniline, 839 m-Deuteriobenzamide, 839 o-Deuteriobromobenzene, 964 a-Deuterioethylbenzene, 132, 135 a-Deuterioethyl bromide, 142 o-Deuteriofluorobenzene, 964 3-Deuterioindene, 102 1 Deuterium

isotope effects, 295-297, 532-535,964,969, r nwa

label& ;or NMR spectra. 623 -625 - . separation, 1 17 tracer studies, 117,298, 364, 380, 807, 839,

1056, 1103- 1106, 11 13, 11 14 Deuterium exchange, 297-298,807,969 Deuterium oxide, 1 17,334 Deuteron. 298 "Dewar" benzene structure, 495,497, 1029 Dewar, Jarnes, 497 Dewar, M.J.S., 414, 952 Dextrans, 1 198 Dextrorotatory, definition, 129 Dextrose, 1 19 1 DHP (dihydropyran), 788 Diacetannde, 860 Diacylglycerol phosphate, 1 128 - 1 13 1 Dialkylacetoacetic esters, 927 - 929 Di3lkylmalonic esters, 925 Diallyl ether, t238 Diamides, 1092 1,4-Diaminobutane (putrescine), 844,986 Diaminobenzenes, 5 14,5 16 Diaminobenzoic acids, 5 16 1,4-Diaminobutane, 987 1,6-Diaminohexane, 830, 880 2,4-Diaminophenol (amidol), 9 15 Diamond, 3

structure, 446,5 12 Diarylmethanols, 704 Diastase, 1 185 Diastereomers, 125, 133, 144- 146, 159, 381

comparison of properties, 145 - 146 definition, l45 formation, by generation of second chiral Enter,

156-158

Diastereoselectivity Dienes

geometric isomers as, 279, 281 m resolution, 158 - 160 (See also Anomers; Epimers)

Diastereoselectivity, 383, 1046- 1049 Diastereospe&%city, 38 1, 1046 - 1049 Diastereotopic faces, 1 10 1 - 1 1 15 Diastereotopic ligands, 1 10 1 - 1 1 15 Diastereotopic protons, 603 1,3-Diaxial interactions, 461 -463,468 Diazo coupling, 519,878 Diazocyclopentadiene-2carboxylic acid, sodium

salt, 990 Xazomethane, 474,475 xazonium fluoroborates, 869 3azonium hexafluoro~hos~hates. 869 - - , Xazonium salts

coupling, 866,868,873-875,878 preparation, 864,866 reactions, 866 replacement of nitrogen, 866 - 868

by -CN, 866-867,870 by halides, 866-867,869-870 by hydrogen, 867-868,871 bv --OH. 867 -868.870

synbeses using, 87 1 1873 libenzalacetone, 872, 986 Xbenzyl ketone, 988 )iborane, 222,32 1,347 - 348 ,5-Dibromo4aminotoluene, 86 1 ,2-Dibromobenzene, 496,500 ,3-Dibromobenzene, 496,500 ,CDibromobenzene, 496,500 I-Dibromobenzene, 508,845,970 -Dibromobenzene, 508, 845 -Dibromobenzene, 508, 845,970 ,6-Dibromobenzenediazonium chloride, 969 ,3-Dibromobutane, 368-372, 1032- 1033 dehalogenation, 289 stereochemistry of formation

from 2-butenes, 368 - 372 from 3-bromo-2-butanols, 1032- 1034

zeso-2,3-Dibromobutane, 371, 373, 375,386 E-2,3-Dibromobutane, 371, 1034 ?,S)-2,3-Dibromobutane, 373 ,4-Dibromo-2-butene, 414 4-Dibromo-l-butene, 4 14 !3,3a-Dibromocholestane, 1 141 2-Dibromocyclohexane, 448 2-Dibromocyclopentane, 464 2-Dibromo-1,2diphenylethane, 385 l-Dibromoethane, t169 NMR spectrum, 610,612,615 2-Dibromoethane, t169 cis and tram isomers, 280 2-Dibromoethene, 280,34 1 6-Dibromo-2,4-hexadiene, 424 6-Dibromo- 1,3-hexadiene, 424 5-Dibromohexanes, 1028 ~,6~bromo-3j3-hydroxycholestane, 1 141 ibromomethane, t 169 6-Dibromo-2-methylphenol, 906 2-Dibromo-2-methylpropane, 340 NMR spectrum, 6 17 S-Dibromo-4-nitroaniline, 873 6-Dibromo-4-nitrobenzenWnium hydrogen

sulfate, 873 7-Dibromonorcarane, 174 S-Dibromo-l-pentene, 414 2-Dibromo- l -phenylethane, 6 19 2-Dibromopropane, 3 19,339,429 5-Dibromopyridine, 1068 -n-butylamine, 847, 859 N-Di-n-butylbenzenesulfonamide, 859 -tea-butyl carbonate, 1223, 1224 3-Di-tert-butylcyclohexane, 490 -n-butyl ether, t238,239 5-Dicarbonyl compounds, 820 carboxylic acids, 742-744,763 acidity, 744

physical constants, t742 preparation, 743

Dichloroacetic acid, 750 preparation, 727,741

2,4-Dichloroaniline, 868 m-Dichlorobenzene, 868, 845,946 o-Dchlorobenzene, 845,946 pDichlorobenzene, 845,946 2,6-Dichlorobenzoic acid, 745 1,2-Dichlorobutane, chirality, 153 1,4-Dichlorobutane, 830 2,3-Dichlorobutane, 146- 147, 156- 158,384 meso-2,3-Dichlorobutane, 157, 1107 Dichlorocarbene, 477,908 -909 l, l-Dichlorocyclopropanes, 938 2,2'-Dichlorodiethyl sulfide, 1037 1,2-Dichloro- l, l dduoroethane, NMR spectrum,

617 DicGi;odifluoromethane, 69 1,3-Dichloro-2,3dimethylbutane, 435 2,3-Dichloro-2,3dimethylbutane, 435 3,3-Dichloro-2,24imethylbutane, 435 3,3-Dichloro-1,2-dimethylcyclopropane, 476 trans-2,5-Dichloro- l ,Moxane, 1 184 1,2-Dichloroethane, t169,617, 833 l, l -Dichloroethene, 1094 1,2-Dichloroethene, 285

geometric isomerism, 280 Di(2chloroethyl) ether, 9 16 a,cu1-Dichloroglutaric acid, 742 Dichloromethane (methylene chloride), 43,44,

t169,258,442 1,2-Dichloro-2-methylbutane, 16 1 1,2-Dichloro-3-methylbutane, 142 2,3-Dichloro-3-methylpentane, 92 endo-cis-2,3-Dichloronorbomane, 473 trans-2,3-Dichloronorbomane, 473 2,3-Dichloropentane, 144- 145, 148 2,4-Dicbloropentaned1oic ac~d, 739 1,2-Dichloropropane, 389

conformations, 627 - 628 %R signals, 602

1,3-D~chloropropane, 447,449 3,4-Dichloro-1,2,3,4-tetramethylcyclobutene, 1003 Di(pcyanoethyl)amine, 978 Dicyclohexylcarbodiimide (DCC), 1224 Nfl-Dicyclohexylurea, 1224 Dicyclopentadiene, 10 18 Dicyclopentadienyliron (ferrocene), 505, 506,

1042,1044 Dieckm~n condensation, 8 1 1,8 15 Dielectric constant, 32 Diels-Alder reaction, 1028

orbital symmetry, 10 13 - 1018 retro, 1028 stereochemistry, 10 13 - 10 14

Dienes, 409 -4 12 denes, f411

stabhtv. 4 1 1

analysis, 4 12 - 422 conjugated, 409-4!0,411-422

1,2- vs. 1,4-addifion, 41 5 -419 bonds in, 41 1-412 cycloaddition, 982, 10 13 Diels-Alder reaction. 10 1 3 - 10 1 8 ease of formation, 4 f4 electrocyclic reactions, 1005 - 1013 electronic configuration, 996- 1000 electrophihc addition, 4 14-4 19

orientation, 4 15 -4 19 rate vs. equilibrium, 4 16 - 4 19

molecular orbitals, 996- 1000 polymerizauon, 420 resonance, 411-412 sigmatropic reactions, 10 19 - 1024 stability, 410-41 1

heats of hydrogenation, t411 nomenclature, 409 -41 0

1298 Dienophile 2,4-Dinitrochlorobenzene

Dienes, (cont.) stability, 410-41 1 structuk, 409-410

Dienophile, 982, 1013 l Diethylamine, 49 1, t82~

5,5-Bethylbarb~turic ac Diethylene glycol, 484 Diethvlenetriamine. 1099 Diethi1 ether, 34, 38, t217,237, t238,258, t272,

442.660 absolute ether, 240 hazards, 240 industrial source, 238 -240 preparation, 240' solubility, 218,238

3,3-Diethyl-5-isopropyl-4-methyloctane, 9 1 o-, m-, and pDifluorobenzene, t945 1,2-Difluorotetrachloroethane, NMR spectrum, 629 3,3-Difluoro-2,2,3-tnbromopropanenitrile, NMR

spectrum, 629 Diglyme, 348 Dihalocarbenes, 477 Dihydromyrcene, 424 cis-9,lO-Dhydronaphthalene, 1026 trans-9,lO-Dihydronaphthalene, 1025 Dihydrophellandric acid, 9 17 Dihydropyran (DHP), 788 2,3-Dihydro-4H-pyran (DHP), 696 Dihydroxyacetone, 1183 Dihydroxybenzenes, 889 (See also Hydroquinone;

Resorcinol) 3,4-Dihydroxybenzoic acid, 918 2,4-Dihydroxyphenyl n-pentyl ketone, 901 erythro-2,3-Dihydroxy-3-phenylpropanoic acid,

818 o-, m-; and pDiiodobenzene, t945 l , l-Diiodoethane, t 169 1,2-Diiodoethane, t169 Diiodomethane, t169 Diisocyanates, 1092 Diisopropyl ether, 233,237, t238,242 &Diketones. 939 'blcetopipekine, 1248 Dilactones, 789 Dimerization, of alkenes, 320,343 - 344 Dimers, 343 3,4-Dimethoxybenzaldehyde, 674 3,4-Dimethoxybenzyl alcohol, 674 N,N-Dimethylacetamide, 789 Dimethylacetoacetic acid, decarboxylation, 93 1 Dimethylacetylene (2-butyne), 428, t429, 431 Dimethylallyl pyrophosphate, 1137 Diplethylamine, 821, t824, 826, 846

industrial prepara~on, 828 reactions, 830,846 synthesis, 954,

3&Dimethylaminoconanin-6-one, 1 140 '3&Dimethylaminocon-5-enine, 1 140 5-Dimethylaminonaphthalenesulfonyl chloride,

1220 Dimeth~lammonium nitrate, 846 2,4-Dimethylaniline, t824 N,N-Dimethylaniline, 821,829,836

reactions, 846, 849, 865 N,N-Dimethylanilimum acetate, 846

2;2-Dimethilbutane, 8 3 p ' 2,3-Dimethylbutane, 83, 364 2,3-Dimethyl-2,3-butanediol (pinacol), 705 2,2-Dimethylbutanoic acid, 720,722 2,3-Dimethyl-2-butanol, 772 3,3-Dimethyl-l-butanol, 322

preparation, 349 3,3-Dimethyl-2-butanol, 230, 306

dehydration, 3 14 preparation, 32 1,346

3,3-Dimethyl-2-butanone (tert-butyl methyl ke- tone), 705,800,935

2,3-Dimethyl-l-butene, 305,306, 314 heat of hydrogenation, t326

2,3-Dimethyl-2-butene, t285, 305, 306,314 heat of hydrogenation, t326

3,3-Dimethyl-l-butene, 208,282,316, 321, 322, 335,347,349,442

he* of hydrogenation,.t326 3,3-Dimethyl-2-butyl cahon, rearrangement, 206 3,3-Dimethyl-l-butyne, t429,435 3,4-Dimethylcyclobutene, 1005, 1008 5,6-Dimethyl-1,3-cyclohexadiene, 1006, 101 1 1,2-Dimethylcyclohexane

C M @ , 468-469 conformational analysis, 467-469 stability of isomers, 467 - 468

1,3-Dimethylcyclohexane, 444, 445,468 1,4-Dimethylcyclohexane, 468 Dimethylcyclooctatriene, 101 1 l , l-Dimethylcyclopentane, 444 1,2-Dimethylcyclopentane, t444

industrial source, 446 3,5-Dimethylcyclopentane, 449 2,5-Dimethylcyclopentanecarboxylic acid, 489 2,s-Dimethyl- l, l-cyclopentanedicarboxylic acid,

489 cis- 1,2-Dimethylcyclopentanol, 490 1,2-Dimethylcyclopentene, 490 1,2-Dimethylcyclopropane

cis and trans isomers. 465.644 , ,

preparation, 475 Dimethyl ether, 36, t238 Dimethylethylamine, 830 Dimethylformam.de (DMF), 185,255,263

as solvent, 926 N,N-Dimethylformamide, NMR spectrum, 12 16 2,5-Dimethyfiran, 1062 2,3-Di-0-methyl-L-galactose, 1203 2,3-Di-0-methyl-D-galacturonic acid, 1203 2,3-Di-0-methyl-D-glucose, 1 198 2,4-Di-0-methyl-D-glucuronic acid, 1203 p,p-Dimethylglutaric acid, 742 2,2-Dimethylheptane, 99 l , l-Dimethyl-2-isopropenylcyclopentane, 423 3,4-Di-0-methyl-D-mannose, 1203 2,3-Di-0-methyl-D-mannuronic acid, 1203 2,7-Dimethyl-2,6-octadiene, 423 3,7-Dimethyl-3-octanol, 778 Dimethylolurea, 1092 2,2-Dimethyl-3-oxobutand, 937 3,3-Dimethylpentanedioic acid, 742 4,4-Dimethyl-l-pentene, 1326 Dimethyl-tert-pentylsulfonium ethoxide, 857 Dimethyl-tert-pentylsulfonium iodide, 857 2,2-Dimethyl-l-propanol, 215,727,772 Dimethyl-n-propylamine, 847 2,5-Dimethylpyrrole, 1062 6,9-Dimethylspiro[4.4]nona-l,3diene, 1024, 1028 Dimethyl sulfide, 264 Dimethyl sulfoxide (DMSO), as solvent, 255,263,

724,926 2,5-Dlmethylthiophene, I062 a$-Dimethylvalenc sad, 7 16 2,3-Di-0-methyl-D-xylose, 1 198 2,4-Dinitroaniline, t824

preparation, 949,954 2,4-Dinitroanisole, 954 Dinitrobenzenes, 954 2,4-Dinitrobenzenediazonium chloride, 874 3,5-Dinitrobenzoates, see specijic alcohol, deriva-

tivor

2,4-l%&obenzoic acid, 7 16 3,5-Dinitrobenzoic acid, 737, 762 3,5-Dinitrobenzoyl chloride, t755

preparation, 737 reactions, 762

2,6-Dinitro-4-tert-butyl-3-methylanisole, 9 15 2,4-Dinitrochlorobenzene, t945

reactions, 829, 898,949,953,954,968

line Electrophilic addition l

4,4'-Dinitrdphenylamine, 823 2,4-Dinitrofluorobenzene (DNFB)

reactions, 970, 1249, 1250 in terminal residue analysis, 12 18 - 12 19

1,5-Dinitronaphthalene, 5 10,547 1,8-Dinitronaphthalene, 547 2,4-Dinitronaphthol, 547 2,4-Dinitro- l-naphthylamine, 5 10 2,4-Dinitrophenol, t890,905,954

preparation, 898,949,953 N-Dinitrophenyl (DNP), .l2 18, .l249 N-(2,4-Dmtropheny1)amno acld (DNP-AA), 12 19 2,4-Dinitrophenyl ethyl ether, 949 2,4-Dinitrophenyl phenyl ether, 970 2,4-Dinitrophenyl phosphate, 1 137 2,6-Dinitrotoluene, 509 1.2-Diols (dvwls). 357-358 ' analysiS;-699 '. preparation, 322,357-358,578

l ,a-Dioxane, i238 industrial preparation, 478

Dipeptides, 12 15 (See also Peptides) Diphenylacetylene, t553 Diphenylamine, 330, 823, t824 1 -4-Di~henvl- 1 -3-butadiene. 8 12. 10 17

' preparatibn, 558 ' '

1,l-Diphenylethene, t553, 812 trans-1,2-Dphenylethene, 386 1,2-Diphenylethenes, 583 Diphenyl ether, t238 Diphenyl ketone, see Benzophenone Diphenylmethane, 546,551,1553,558,575 Di~henvlmethanol. 12 16. 552 %5hen$lmethyl biomide, t169 Diphenylmethyl chloride, t169 1.2-D~phenyl~rownes, 377 - 380,399

1,3-Diphenylpropenone, 8 10 1,3-Diphenyl-2-propen-l-one, 80 1 Diphosphopyridinenucleotide, see NAD Dipolar ions, 862-863

amino aclds as. 1208 - 12 1 1 phospholipids &, 1 130

Dipole-dipole bonds, 259 -260 Dipoledipole interactions, 28,454, 1 180

in macromolecules, 1093 - 1095 Dipole moments, t24,24-26,295 1 Dipoles, 23 Di-n-propylamine, t824 Di-n-propyl ether, t238

infrared spectrum, 596 Diradicals, 394,475 Disacchyides, 1 185- 1 192

defimbon, 1 144 (See also (+)-Maltose; Sucrose; (+)-Sucrose)

Disparlure, 105 5 D i s p e d of charge, 406,73 1 Disrotatory motion, 1007 - 10 1 l. Dissociation energy, see Bond mssociation energy

and insidefront cover pDivinylbenzene, 584 Divinyl ether, t238 DMF, 185,255,263,926 DMSO, 255,263,724,926 DNA (deoxyribonucleic acid), 69, 1250

structure, 124 1 - 1246 and genetics, 1246 - 1247

DNFB, see 2,4-Dinitrofluorobenzene DNP (N-dinitrophenyl), 12 18, 1249 DNP-AA (N-(2,4-dimtrophenyl)arn1no acid), 12 19 n-Dodecane, t93 Dodecanoic acid, 7 13,740 l-Dodecanol, 780 (E)-8-Dodecan-l-yl acetate, 382 (Z)-8-Dodecen-l-yl acetate, 382

(E)-9-Dodecen- l -yl acetate, 382 (2)-9-Dodecen-l-yl acetate, 382 n-Dodecyl alcohol, t2 16 6-Dodecyne, 430 Doebner reaction, 8 1 1 L-Do~a. 105 1 ~ou6le'bonds, see Carbon-carbon double bonds,

Carbonyl oup Double helix, &r DNA, 1244 Double irradiabon in NMR spectroscopy, 624-625 Double resonance in NMR spectroscopy, 624-625 Dow process, 894,948 Dry Ice, 723 Drying oils, 1127- 1128 Duck. D.. 474

gene, i553 Dyes, azo, 875 Dypnone, 872

E El mechanism, see Elimination reactions E2 mechanism, see Elimination reactions Eclipsed conformation, 79

in E2 elimination, 473 Edman, Pehr, 1219- 1220 Egg albumin, 1234 Elastic fibers, 1097 Elastomers, 1077, 1094 Electrocyclic reactions, 1005 - 10 13 Electromagnetic radiation

absorption, 590 -620 related to frequency, 589-590 wavelengths in, 589- 590

Electromagnetic spectrum, 69,589 - 590 Electron density, 6 Electronegative elements, 4 Electronegati@ty, 23,850 Electronegab~ty senes, 23,436 Electrogc configuration, 8, t8,996- 1000 Electromc effects

accommodation of charge, 199 and acidity, 735-736 In mines, 852-853 in aromatic substitution, 536- 544 and basicity, 850-852 in carbocations, 196 -203 in carboxylic acids, 728-729 effect of substituent groups, 852-853 in electrophilic addition, 336-339,978-979 of functional groups, 974 in Hofmann degradation, 841 -843 infrared absorption shift, 590 in nucleophilic addition, 670-671,978 in nucleophilic aromatic substitution, 952-956 in %l reactions, 200-203,961 in h 2 reactions, 185- 188,961 (See also Inductwe effects; Resonance effect)

Electronic structure, 5,37 Electronic transibons, 597 Electron-pair acceptor and donor, 34 Electron paramagnetic resonance, see Electron

spin resonance spectroscopy Electron release, 199,540- 542 Electrons

odd. 47.64 paired, 8

Electron sharing. 4 (See also Bonds) Electron spin, c 5 7 3 Electron spin resonance (ESR) suectra, 393,586, Electron @in resonance (ESR) ipectroscopy

of free radicals, 573 m reaction studes, 352

Electron transfer, 4 Electrophilic addition, 3 18,332- 333,353,974

976.978 to alkenes, 332-345

1300 Electrophilic aromatic substitution Esters

Electrophilic addition, (cont.) to akenylbenzenes, 579- 580 to alkynes, 430-433,434-435 to a$-unsaturated carbonyl compounds, 974-

976 to c&;gated dienes, 414-419 definition, 3 l8 effect of substituent groups, 338,974-975 hydroboration, 349 orientation. 337

and readvity, 335-338 oxymercuration, 346 - 347 reaction mechanism, 332 - 334 rearrangements, 334-335 (See also.Addition. reactions)

Electrophihc aromahc subshtution, 5 17 - 548 alkylbenzenes, 562,564 amines and amides, 848,852-853 couplin of diazonium salts, 873-875 effect ofhalogen, 944,948 effect of subfituent groups, 5 19 - 520 Friedel-Crafts acylation, 666, 901 furan, pyrrole, and thiophene, 1062- 1064 mechanism, 530-535 naphthalene, 545 -546 nitrosation of amines, 865 orientation, 5 19- 52 1, 522-525 phenols, 906 - 907 pyridine, 1068 - 1069 reaction mechanisms, 525 - 530 relative reactivity, 52 1 - 522

Electrophilic reagents, 31 8,333 Electrophoresis, 1227 Electropositive elements, 4 Element effect, 298 - 300,960 Elimination-addition mechanism, 944,962-967 Elimination reactions, 174,288 -3 15,334

by acetylides, 439 from alicyclic compounds, 47 1 -473 of alkyl halides, 242 of alkyl sulfonates, 234 in a-halogenated acids, 741 -742 anti-, 378- 380 j3- and a-, 477 dehydration of alcohols, 3 10- 3 15 1,l-, 477 1,2-, 246, 290-293, 308, 477 ElcB, 298 E l mechanism, 303 - 307

evidence for, 304-307 orientation, 306- 308 reactivity m, 304 vs. E2, 308

E2 mechanism, 293-294,855 absence of hydrogen exchange, 297-298 absence of rearrangement, 294-295 element effect, 298 - 300 evidence for, 294-306 isotope effects, 295-297 kinetics, 294-295 orientation and reactivity, 300 - 303 stereochemistry, 377 - 380,471 -473 vs. El, 308 VS. $42,308-310

Hofmann, 854-855 orientation of, 4 14 preparation of alkynes, 429 - 430 stereochemistry, 377 - 380 syn-, 378-380 vs. substitution, 175, 308-310, 833

Empirical formula, determination, 74 Emulsin, 1 188 Enarmnes, 935-937 Enantiomerism, prediction of, 133 - 134 Enantiomers, 125, 127, 133, 136- 139, 144,381

and enantiomerism, 130- 134 configurational, 139 conf&mational, 139

Enantioselective synthesis, 367 - 386 Enantioselectivity, 383, 1049- 105 1

Enantiospecificity, 38 1,111 2 - 1 1 1 3 Enantiotopic faces, 1050, 1101 - 11 15 Enantiotopic ligands, 1 10 1 - 1 1 15 Enantiotopic protons, 603 End group analysis, 1194- 1195 Endothermic reactions, 54 Enediol, 1 150 Energy of activation, see Activation energy Energy changes, 52-55 Energy content, 66 Energy factors, 59

in reaction rates, 56 Enolate anion, 798 Enolic proton chemical shift, t607 Enolization, 804-805 Enol-keto equilibrium, 435-436,976,977, 1149-

~ r m llJV

Enthalpy, 50 Enthalpy change, 730

in macromolecules, 1093 - 1096 Entropy change, 730

in macromolecules, 1093 - 1096 Entropy of activation, 67 (See also Activation en-

ergy) "Envelope" conformation, 490 Enzymeaction, 1112-1113, 1114, 1236-1240 Enzymes, 137, 1054, 1248

solubility and shape, 253-254 (+)-Ephedrine, 137 Epichlorohydnn, 1099 Epimers, 1 152,1153

interconversion of, 1 154 - 1 155 Epoxidation, 322,484 Epoxide ring, 48 1 Epoxides, 376,384,478

cleavage, 482 - 487 acid-catalyzed, 482,483 -484,9 10 base-catalyzed, 483,485 orientation, 485 -487

in formation of 1,2-diols, 482,483-484 in pinacol rearrangement, 704 preparation of, 48 1 protonated, 483,485 reactions, 482-483

with Grignard reagents, 483,485 in Williamson synthes~s, 9 10 - 9 1 1

Equatorial and m a l conformations, energy differ- ence, 463

Equatorial bonds in cyclohexane, 460-463 Equilibrium, 730-732

in estedcation, 737 . Equilibrium constant, 730 Ergocalciferol, 1030 Ergosterol, 1030, 1 136 L-Erythritol, 1 1 15 L-Erythntol-l-phosphate, 1 1 15 Erythro &astereomers, 377, 380 Erythrose, 380 (--)-Erythrose, 789, 1 16 1 ESR, see Electron spin resonance spectroscopy Essential oils, phenols from, 894 Estedcation

of alcohols, 226,726 by acid @oxides, 726,76 1 -762,769-770 by anhydrides, 764-765,769 bv carboxvlic acids. 726.737-739.768-770 bG esters. 771. 7771778' rilative reacti*, 738,769

of carboxvlic acids, 726,737- 739,768-770 bond cieavage, 739 . relative reactivity, 738

of dicarboxylic acids, 743 - 744 of glucose, l l45 intramolecular, 770 (See also Esters; Transesterification)

Esters, 753,755 alkylation of, 93 1 -932 carboxylic acid, 753,768-783

ammonolys~s of, 771, 778 analysis of, 783-785

Estrogen Ethylcyclopentane 1301

Claisen condensation, 772,802,s 13-8 16 cleavage of, 77 1 -774 conversion, into acids and acid derivatives,

771 -777 ,,. S , -

cyclic (lactones), 770, 989 hydrogenolysis, 77 1, 780 hydrolysis, 771

acid, 775- 777 alkaline, 772-775

hydroxy, 832 keto, see&Keto esters malonic, 924-927 nomenclature, 754 nucleophilic substitution, 755 -760 phenolic, 738, 762, 899, 905 physical properties, 754-755, t755, t769 preparation, 174,226,233,726,737-739,

768-770 reactions, 770 773

wth carbanions, 77 1 with Grignard reagents, 772,779

reduction, 772,779 saponilicafion equvgent, 784 spectroscopic analysis, 692, t607,784-782 structure, 753 transesterification. 771.777 -778 , , (See alsp Fa?)

phosphonc acld, 1128- 1130 hydrolysis, 1129

sulfonic acid, 1038 - 1039 preparabon, 233

Zstrogen, 1 136 Zstrone, 1 136 Zthanal, see Acetaldehyde Zthanamide, see Acetamide Zthane, 110,438

andiron formulas of, 80 conformational analysis, 79 - conformafions. 79 - 82 empirical fom'ula, 75 physical properties, 754-755, t755, t769 rotational b d e r in, 82 structure, 78 - 79,2i6

Zthanedioic acid (oxalic acid), 705, t742 L ,2-Ethanediol (ethylene glycol), t2 16, 1079

1090 polymer with terephthalic acid, 739, -.. - preparation, 223,358,482

Zthanenitrile (acetoniqe), 258,725 Zthanoic acid. see Acebc ac~d Zthanoic anhydride, see Acetic anhydride 3han01, 35, 210,258, 298

biological oxidation of, 1101 - 1106,1114 deuterated, 1 103 sources, 2 19,22 1 - 222 substituted, 247 uses, 220,22 1 - 222 (See also Ethyl alcohol)

Ztha?~ia,mine (2-aminoethanol), 483, 5 14, 822, 113u

Zthanolamine phosphoglyceride, 1130 Zthanoyl chloride, see Acetyl chloride Zthene, see Ethylene Zther, see Diethyl ether Zthers, 214,237-247

absolute, 240 analysis of, 244-245 w l , 909-912 of carbohydrates, 1175 - 1176, 1201 of cellulose, l201 cleavage by acids, 242 - 243

as nucleo~hilic reaction, 242-243 crown, 478148 1 cyclic, 478 (See also Epoxides) as Grignard solvent, 99,240,272,948 hydrogen bonding, 238 industrial source, 238 - 240 nomenclature, 237 peroxides in, 240 physical properties, 238, t238 preparation, 240-242

alkoxymercuration-demercuation, 24 1 dehydration of alcohols, 239 from phenols, 240,902 Williamson synthesis, 240,241 -242,902,910

protonated, 242 -243 reactions, 242-243,704 as solvents, 99, 478 sources, industrial, 238 - 240 spectroscopic analysis, t592,596-597, t607, t786 structure, 237

Ethide ion, basicity, 438 Ethoxyacetic acid, 745 3-Ethoxy-l-butene, 406 l-Ethoxy-2-butene, 405 2-Ethoxyethanol, 237,482,483 Ethoxylates, 1126 2-Ethoxyoctane, 242 Ethyl acetamidomalonate, 988 Ethyl acetate, 226,754, t769,802, 81 1,816

arnmonolysis, 771, 778 Claisen condensation, 802,s 13 - 8 15,s 16

Ethyl acetoacetate, 929,98 1 preparafion, 802,814 reactions, 929,981,988 relative acidity, 8 14 - 8 1 5 (See also Acetoacetic ester synthesis)

Ethylacetylene, 428 Ethyl awlate, 789, 978 EfPyl a,dipate

in D~eckmann condensation. 8 15 preparation, 738

Ethyl alcohol, 34,36,215, t21 771 778 774 . . - , . - , . . .

dehydration, 288 iodoform test, 244 preparation, 33 1,347 (See also Ethanol)

Ethyl alkylmalonate, 924 Ethylamine, t824, 829 Ethyl paminobenzoate, 828 Ethylammonium sulfate, 823 l-Eihylaziridine, 827 . Ethylbenzene, 550-55 I, t553

CMR, chemical shift, 634-635 reactions, 561,562-563,564,566,567,576,578

Ethyl benzoate, 546, 754, t769, 816 in Claisen condensation. 802 hvdrolvsis. 771. 775 pieparkion, 761 substituted. 776 tracer studes, 775

Ethyl benzoylacetate, 802, 816 Ethyl benzylmalonate, 12 13 Ethyl bromide, t169, 187, 188, 197,240,610, 836,

t95 1 m s p e c t n u n , 612,615

Ethyl bromoacetate, 933 Ethyl o-bromobenzoate, 769 Ethyl bromomalonate, 1214 Ethyl a-bromopropionate, 927 Ethyl bromosuccinate, 1072 Ethyl n-butylamine, 836 Ethyl n-butyrate, t769 Ethyl carbamate, 78 1 Ethyl carbonate, 780, 8 16 Ethyl cation, 191, 197

mass-to-charge ratio, 586 Ethyl chloriqe, 98, 104, 110,t169,447,829

confomahons, 627 NMR signals, 602-603,626-627

Ethyl chloroacetate, 12 13 Ethyl chlorocarbonate, 78 1 Ethyl cplorohydrin, 482 Ethyl cmnamate, 81 1,872,980 Ethyl crotonate, 976,980,987 Ethyl cyanoacetate, 980,981

reaaons, 927 Ethyl &c anobutyrate, 976 ~thylcycLhexane, 463,561,578 Ethylcyclopentane, 445

3-Ethylcyclopentene, 444 Ethyl cyclopentylacetate, 935 Ethyldimethylacetic acid, 722 Ethyl 2,2dimethylpropanoate, 772 Ethyl 2,4dimethyl-3-pyrrolecarboxylate, 1063 Ethyl 2,340~0-1,4-cyclopentanedicarboxylate, 8 16 Ethyl 1,3dioxo-2-indanecarboxylate, 8 16 Ethylene (ethene), 223,282, t285,338,342,358,

363,364,833,944 adhaon reamons, 328,33 1,337-339,341-342 cycloaddition reactions, 1014 - 101 6 electronic configuration, 997 heat of hydrogenation, t326 molecular orbitals, 997 polymerization, 1078, 1096 preparation, 288,3 1 1 structure, 273 -275 from thermal cracking 120

Ethylene bromide, 363 Ethylene bromohydrin, see 2-Bromoethanol Ethylene chloride, see 1,2-Dichloroethane Ethylene chlorohydnn, 214,223, 1054 Ethylenediamine, 82 1,833 Ethylene glycol, see 1,2-Ethanediol Ethylene oxide

detergents from, 1126 polymerization, 1086 preparation, 482, 1054 reactions, 482-483,687-688,910-911

Ethyl ethanoate, see Ethyl acetate Ethyl formate, t769, 816 Ethyl formylacetate, 8 16 Ethyl free radical, 1 12 Ethyl fumarate, 1072 Ethylhexadecanoate, 780 2-Ethyl-l-hexanol, 808 Ethyl hydrogen sulfate, 331 Ethyl iodide, t169, 902

preparation, 170,225,328 Ethyl a-isobutylacetoacetate, 928 Ethyl isobutylmalonate, 925 Ethyl isobutyrate, 772 5-Ethyl-5-isopentylbarbituric acid, 938 m-Ethylisopropylbenzene, 55 1 Ethyl fiketobutyrate, 8 14 Ethyllithium, 98,692 Ethylmagnesium bromide, 99,433 Ethyl malonate (malonic ester), 980, 981,986

preparation, 743 reactions, 720,783,925-926,979-98 1

Ethyl a-methylacrylate, 980 Ethylmethylamine, 822,829,848 Ethyl methyl ketone (butanone), 659, t661,679,836 Ethyl a-methyl-fiketovalerate, 8 15 Ethyl methylmalonate, 980, 990 (R)-2-Ethyl-3-methyl-l-pentene, 164 Ethyl a-methyl*-n-propylacetoacetate, 929 Ethyl methyl-n-propylmalonate, 926 Ethyl pnitrobenzoate, 828 2-Ethyloctanoic acid, 720 Ethyl oxalate, 816, 987 Ethyl oxaloacetate, 8 16 Ethyl oxamate, 88 1 Ethyl 3-oxobutanoate, 8 14 Ethyl 3-0x0-2-methylpentanoate, 815 Ethyl palmitate, 780 Ethyl tert-pentyl ether, 204 Ethyl phenylacetate, t769, 816 Ethyl a-phenylbenzoylacetate, 8 16 Ethyl y-phenylbutyrate, 738 Ethyl phenyl ether (phenetole), t238, 546

infrared spectrum, 596 preparaaon, 240,902

Ethyl phenylmalonate, 8 16 Ethyl l-phenyl-2-propyl ether, 183 Ethyl propionate, t769, 774-775, 1054

in Claisen condensation. 8 16 Ethyl n-propyl-n-butyl-n-hkxylmethane, 139 Ethyl radical, 1 12 Ethyl stearate, t769

ene Free radicals

m-Ethyltoluene, 584 o-Ethyltoluene, 584 pEthyltoluene, 551, 584 Ethyl ptoluenesulfonate (ethyl tosylate), 226,234 Ethyl tosylate (ethyl ptoluenesulfonate), 234,226 Ethyl trimethylacetate, 772

preparaaon, 726 Ethyl n-valerate, t769 Ethynyllithium, 438 Eugenol, 582,894,919 Excited state, of molecules, 997 Exothermic reaction, 50, 53 -54 Extinction coefficients, 597

Farnesyl pyrophosphate, 1137 Fats, 1119-1142

biosynthesis of, 932, 1 122 carboxylic acid source, 7 19 detergents from, 1 126 - 1 127 hydrolysis of, 1124- 1125 industrial uses, 740 occurrence and composition, 1 120 - 1 124 phospholipids, 1 128, 1 129 - 1 13 1 soan from. 1124- 1125 so& of bure acidsand alcohols, 1125- 1126 unsaturated, 1 127

Fatty acids, 1 120, 1 134 biosynthesis of, 1 132 - 1 134 in fats and oils, t1121 unsaturated, 1 122

Fehling's reagent, 1 144, 1 149 Ferguson, Lloyd, 443 Fermentation, carbohydrates, 2 19 Ferr.-ne, 505,506, 1042, 1044 Ferther. 784 Fibers (shthetic). 1077- 1078

propkities, 1094 Fibrin, 1226 Fibrinogen, 1226 Fibroin, 1225. Fibrous protems, 1225 Fischer, Emil, 1112, 1151,1155, 1169,!22 Fischer proof, of (+)-glucose configuraaon,

1160 Flagpole hydrogens, 457 Flash distillation, 38 Flavylium chloride, 1075' Fluorine, bond formation, 1 1

19F nucleus and NMR spectra, 6 17 Fluorobenzene, t520,867,1945,949 o-Fluorobenzophenone, 758 Fluoroborate ion, 37 Fluoromethane, 38 2-Fluoro-2-methylpropane, 92 m-, o-, pFluoropheno1, t890 m-, o-, pFluorotoluene, 1945 Formaldehyde, 364, 658, 659, 660, t661, 670, 674,

675,683,686,694, 1092 polymerization, 1090- 1092, 1097

Formalin, 660 Formamide, 258, t755 Formate ion, 674 Formic acid, 261, 397,405, 713,714, t715, t735

bond lengths, 734 Fossil fuels, 1, 94, 120, 220 Free energy change, 730 - 73 1 Free-radical addition, 3 18, 35 1 -356

to alkenes, 322,351 -356 to alkenylbenzenes, 579-580 orientation of, 352-355 peroxide-initiated, 35 1 - 352 (See also Addition reactions)

Free-radical halogenation, 562,565-568 Free-radical polymerization

of alkenes, 356-357 of dienes, 4 19 - 42 1

Free-radical substitution 1 D-Glucosazone

Free radicals alkyl, 47-49, 106- 109

relative stabilities, 1 1 1 - 112,390- resonance s tabht ion, 40 1 -402

allyl, 123,389-392 electroluc configuration, 999 molecular orbitals, 998 -999 relative stabhty, 567 resonance stabdizafion, 395 - 399

ben~yl, 123,567:568. resonance s t abhbon , 568 - 570

chain reaction, 70,7 1 combination of, 108 1 definition, 47 delocalization of odd electron, 395 - detection

by ESR, 573 triarylmethyl, 580

diradicals, 394, 1014 disproportionation of, 108 1 electron spin resonance (ESR) spectrum, 573,642 formation

by abstraction, 47-48 by addition. 35 1 -356 fiom alkanes, 47 -49 from alkenes, 351 -356,389-392 from alkylbenzenes, 567 in allylic substitution, 389- 392

by N-bromosucci+mide, 390 from tert-butyl peroxide, 124 ease of, 1 13, 39 1,567

stabilitv and. 113.353 in haloggnation, 47-49, 106- 109,389-392 from peroxides, 124,351 -356,357 from tetraethyllead, 76 from tetramethyllead, 76 from toluene, 567

hyperconjugation in, 40 1 -402 inhibitors, 49 -50 methyl, see Methyl radical Paneth mirror technique, 76 paramagnetism, 573 racemization and, 16 1 - 162,826 rearrangement, lack of, 1 16 resonance s tabht ion. 387 - 399.402 "scavenger" of, 60 stability, 111-112,391,567

ease of formation and, 1 13,353 hyperconjugation and, 401 -402 relative, ! 11 - 112,390-392

stereochemistry, 16 1 - 162 structure. 64 - 65 triarylmethyl, 580 triphenylmethyl, 570- 574 vinyl, 123, 357 (See also individua!free radicals)

Free-radlcal sub*tubon, 46-63,65 392,448-449

in alkenes, allylic rearrangement, Friedel, Charles, 557 Friedel-Crafts acylation

of benzene, 498,s 19 of heterocvclic comvounds. 1063 of phenol;, 90 1 - in preparation of ketones, 663-664,666

761,765 Friedel-Crafts alkylation, 556- 56 1,577

of benzene, 498,s 18 limitations of, 56 1 of phenols, 901,907 reaction mechanism. 528.558-560 test for aromatic compou'nds, 580

Fries rearrangement, 901,905 5-D-Fructofuranosyl a-D-glucopyranoside,

r ~ n ? l l7L

:-)-Fructose, structure determination, 1 146, 1 152, 1155

>~rUctOse, 1 183,1191 =uchsin-aldehyde reagent, 697 =uels, 94-96,218

from carbohydrates, 2 19 - 22 1 fossil, 1,94, 120,220 svnthetic. 120

~ u h i , K., 1004 Fullerenes, 3,5 12 - 5 13 Fumaric acid. t742.764. t972.973.977. 1046-

1048,1i15 . . ' ' . Fumaryl chloride, 987 Functional derivatives of carboxylic acids, 753 -

796 (See also Acid chlorides; Acid anhydrides; Amides; Carbonic acid, functional derivatives of; Esters; Fats; Imides)

Functions! groups, 167,3 17 electro~uc effects, 974

Furan. 478.990. 1057. t1058. 1065. 1074

reactions,-l062 - 1063 source, 1060- 1062 structure, 1059- 106 1

2-Furanwboxaldehyde, see Furfural Furanose, 1 178 Furanosides, 1 1 78 2-Furansulfonic acid, 1064 Furfural, t1058, 1062, 1203

reactions, 1062 source, 1062

Furfury1 alcohol, t1058 Furnace oil, 96 Furoic acid, t1058, 1063 2-Furoic acid, 1063 Furylacrylic acid, 1074 Fused-ring aromatic compounds, 5 10 - 5 1 3 Fuse1 03,2 18 cis-Fusion, 1 1 35 trans-Fusion, 1 135

Gabriel synthesis, 844, 1214 Galactaric acid, 1 16 1 a-~-Galact~pyran~se, 1 179 ~ - O - @ - D - ~ ~ ~ O ~ ~ ~ ~ ~ O S ~ ~ ) - D - ~ U W P ~ O ~ , 1 190 (+)-Galactose, 1 147, 1 16 1 D-(+)-Galactose, 1 189 - 1 190 D-Galacturonic acid, 1 18 1 Gas oil, 96, t96 Gasoline, 96, 119, 120

ethyl (or leaded), 1 19 natural, t96

Gasoline engine, 1 18 Gattermann reaction, 879 Gauche conformation, 85 -86 Gelatin, 1234 Genetic code, 1246- 1247 (+)-Gentiobiose, l202 Geometric isomerism, 275,279-282

prefixes, 283 Geranial, 705 Geraniol, 647,655 Geranyl pyrophosphate, 1 137 Globin, 1228 Global warming, 120 Globular proteins, 1225

structure, 1235 y-Globulin, 1221, 1234 Globuhns, 1226 Glucaric acid, 1145, 1 149, 1 159 (+)-Glucaric acid, 1 167 Glucitol, 1 145, 1 149 Gluconic acid, 1 145, 1 149 D-(-)-Gluconic acid, 1 189 - 1 190 a-D-Glucopyranose, 1 179 PD-Glucopyranose, 1 178 &D-(+)-Glucopyranose, 1 179 a-D-Glucopyranosyl p-D-hctofuranoside, 1 192 ~ - O - ( ~ - D - G ~ U C O ~ ~ O S ~ ~ ) - P . ~ U W ~ ~ ~ ~ ~ O ~ ,

1186-1188 4-O-(P~-Glucopyranosyl)-~-~u~0pyranose, 1 189 -

1191

1304 Glucose Halides

Glucose, 220, t1149 D-Glucose, 1 172

a - a n d s , 1172 (+)-Glucose, 146, 1 155, 1 171 D-(+)-Glucose

acetylation, 1 145 as aldohexose, 1144- 1146 a- and forms, 1 168, 1 174, 1 176 inamyopectinstructure, B 1195-1198 in amylose structure, 1193 - 1196 anomers, 1 170

configuration, 1 170 conformations, 1 169,1178 - 1 180 s@c rotahons, 1 168

biological importance, 1 143 - 1 144 in cellobiose structure, 1 188 - 1 189 in cellulose structure, 1 143, 1200 configuration, 1 159, 1 166

Fischer proof, 1 155 - 1 160 conformation, 1 178 - 1 180 cyclic structure, 1168- 1172

configuration, 1 169 conformahon, 1 178 - 1 180 methylation, 1169, 1174- 1176 ring size, 1176-1178

in dextrans, 1 198 enantiomeric forms, 1 166 epimers, 1 152 formation

from arabinose, 1 157 in photosynthesis, 1 143

y-glucoside of, 1 178 glucoside formation, 1 168 - 1 170 (See also Glu-

cosides) as hemiacetal, 1 1 68 - 1 1 70 inlactose structure, 1189-1191 in maltose structure, 1 185 - 1 188 methylation, 1 169,1174- 1 176 molecular models, 1 148 mutarotation, 1 1 68 - 1 1 70 nomenclature, of derivatives, tl149 openchain structure, in mutarotation, 1 170 osazone, see Glucosazone oxidation, 1145,1158, 1167

in body, 1 143 reactions, 1 145 reduction, 1 145 ring size determination, 1 176- 1 178 in starch structure, 1 143, 1 193 stereoisomers, 1 146- 1 149 structure, 1 145 - 1 146 in sucrose structure, 1191 - 1192

~-(+)-Glucose, 1 166 L-(-)-Glucose, 1 166 Glucose phenylhydrazone, 1145 D-Glucose-l-phosphate, 1 183 Glucosides, 1 17 1 as acetals, 1 169, 1 170, 1 175 configuration, 1 17 1 conformation, 1 17 1 formation, 1 168 - 1 170 hydrplysis, 1175

acld. 1 169 base: stability toward, 1 170 enzvmabc. 1 173

meth 1, see ethyl a-D-glucoside, Methyl jD-@ucoside

methylabon, 1 174- 1 176 oxidation by periodic acid, 1 173 - 1 174

Glucosone, 1 15 1 Glucuronic acid, t1149 DGlucuronic acid, 1 18 1, 1203 Glutamic acid, 137,930,1220 (+)-Glu-c aad, t1206 I+Kilutamne. t1206

Glutamyl~steiny&lycine, 12 17, 1220 Glutaric aad, t742 Glutathione, 12 17, 1220

Glyceraldehyde, 683 configuration, 143, 1162- 1163 relationship to glucose, 1 166 - 1 167 relationship to tartaric acid, 1 164- 1 165

(+)-Glyceraldehyde, 1163 D-Glyceraldehyde, 1 162, 1 183 ~Glyceraldehyde, 1162, 1212 R-Glyceraldehyde, 789 R-(+)-Glyceraldehyde, 679,703, 1153 D-(-)-Glyceric acid, 1 163 Glycerides, 1120, 1125

hydrolysis, 1124 G1 cerol, 214, t216,272, 1 1 15

gom glycerides, 772 polymers from, 1090

Glycerol-l-phosphate, 1 1 15 Glycine, 863, t1206,1209, 1220

isoelectric point, 12 1 1 preparation, 829 reactions, 1223, 1224

Glycine hydrochloride, 1213 Glycogen, 1132, 1143, 1198 Glycols, see 1,2-Diols Glycosides, 1 170 Glycylalanine, synthesis, 1221 - 1222, 1224 Glycylalanylphenylalanine, 12 15 Glycylglycine, 1215 Glyptal, 1090 Gomber& Moses, 570 Gossyplure, 706 Graduate student, naive, 704, 8 19,989 Graft copolymer, 1084 Grain alcohol, see Ethanol, Ethyl alcohol Grains, as alcohol source, 2 18 Gramicidin S, 48 1, 1250 Graphite, structure, 5 12 Greenhouse effect, 3,119 - 120 Greenhouse gases, 43,2 19 Griess, Peter, 5 16, 1 15 1 Grignard reagent, 99- 101,240,483,668,870

in alcohol synthesis, 222,223,675,685-692 choice of, 272,690,695-696 decomposition, 695 preparation, 99- 100, 124, 174,685,688-692,

948 reactions

with acids, 100- 101, 228 with aldehydes and ketones, 124,675,685-

692,692-693 with esters, 771,778 with water, 100- 101 '

vs. organocopper compounds, 668 Grignard synthesis, 722

of alcohols, 222,223,675,685-692 of alkanes. 100 - 10 1 of carboxjhic acids, 72 1 - 724 limitations, 695 -698 products of, 686 -688

Grignard, Victor, 99 Ground state, of molecules, 997 Guaiacol, 9 13 Guanidine, 783,784 Guanine, in nucleic acids, 1241 - 1245 Guanine-cytosine,-hydrogen bonding in, 1245 Gulose, 1 147 (+)-Gulose, 1159, 1167 (-)-Gulose, 1 159- 1 160, 1 162, 1 167 Guncotton, 1201 Gutta percha, 1095 Guvacine, 1076

H Halfchair conformation, 458 Halidejon, 176

relahve reamvity, 27 1,272 solvation, 257,263

Halides, see Alkyl halides, Aryl halides

a-Halo acids H o h a n n 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 Haloethane, t169

1076 five-membered rings, 1059- 1066

Halofonn reaction, 671,676,757,819 reactions, 1059- 1060, 1062 - 1064 a-Halogenated carboxylic acids, 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, 1 11 1 of benzene, 498,529 Heterotopic ligane, 1 1 10 of ketones, 800,802-804 Hexa-0-acetylgluatol, 1 145 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~aon state for, 1 13 - 1 14 Hexadecanoic acid, 1 123

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, 1 127 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 1 1,499 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, 1 169 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, 1 122 Hindered rotation, 275,278 [eptaldehyde, 1661,835 Hine, Jack, 909 [eptanal, 835 Hinsberg test, 876 -Heptane, f93, 1 18,238 Hippuric acid (N-benzoylglycine), 880, 1215 [eptanedioic acid, 1075 Histamine, 1076 [eptanoic acid, 1 145 Histidine, 1209, 1238, 1240 -Heptene, t285, t326 (-)-Histidine, t 1206 -Heptyl alcohol, t216 HMFT (hexamethylphosphorotriamide), 255,263 -Heptylamine, 835 H o h a n n , 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 4-1

Hofmann rearrangement, 838 - 843 stereochemistry at mi timing of steps, 840 - Gting 840

HOMO (Gghest occupied molecular orbital), 1007 Homocychc compounds, 443 -478, 1057 (See also

Cyclic aliphatic compounds, Cycloalkanes) Homologous senes, 86 - 87 Homologs, 87 Homolysis, 22,47, 165,427 Homopolymers, 1083 Homotopic faces, 1 1 1 1 Homotopic ligands, 1 1 10 Hordmene. 9 18 Hormone!

juvenile Hbst-gues House, Ht Hiickel, E Hiickel4n Hudson, C Hughes, E

1034

:rbert, l01 - ' rich, 504, 1001 + 2 rule, 504-507,1000- 1004 :.S., 1173 .D., 179, 183,293,294,303,

Hyalophora cecropia, 1 139 Hybrid bonds, see Bonds Hybridization of atomic orbitals

sp, 12,426,427 (See also Orbitals)

Hydration of alkenes, 320,332 of alkynes, 4!2,435-436

Hydratropic aad, 750 Hydrazine, 673 Hydrazones, 673 Hvdride ion. 345 ~ i + d e shift, 206 Hydndotetracarbonylwbalt, 1052 Hydriodic acid, 9 1 1

used for identification, 245 HydroboraQon

mechanism of, 349 - 350 orientation of, 348 - 349

Hydroboration-oxidation, 222,321,347-348,898 Hydrocarbons, 39

acidity, 107 1 aromatic, 287 combustion, 42-43, 1 18 homolytic bond dissociation energies, 2 1 NMR and CMR spectra of, 639 unsaturated, 273 (See also.Allc?nes;pllcenes; Alkynes; Arenes;

Cychc ahphaQc compounds) Hydrocracking, 120 Hydrodealkylation, industrial, 556 Hydrogen

abundance, t588 allylic, 124, 390 CU, 235,683,814-815, 1102

ionization of, 797 p, 29 1,300,303 benzylic, 124,566 bond formation, 10 classification, 92 diastereotopic, 1 109 different kinds of, 393 enantiotopic, 1107- 1109 equivalent, 393 flagpole, 457 hydride character, 35 1 isotope effects, 295-297,532-535,964,969,

l099 migration, 206, 1020- 1024 relative reactivity, 103, 1 10 vinylic 124,390. (See aho Deuterium; Protons; Tritium)

Hydrogenation of alkenes, 319,323-327 of alkynes, 430-431,433 of alkylbenzenes, 56 1 of aromatic hydrocarbons, 447

Hydroxy- 1,3-benzenedisulfonic acid

of esters, 77 1 heat of, see Heat of hydrogenation heterogeneous, 324 homogeneous, 324, 1042 - 1046

stereochemistry, 384, 1046 - 105 1 of &o compounds, 828 of oils, 1 127 quantitative, 42 1

Hydrogen atoms, 1 10 ease of abstraction, 110- 11 1,391

Hydrogen bonds, 32,217-218,255,454,640, 1235 in alcohols, 2 17 - 2 18 in armdes, 755 in amines, 823 boilingpoint and, 217-218,891 m carboxyhc aads, 7 17 in ethers, 238 formation, 10 and infrared absorption shift, 592 in macromolecules, 1093 - 1096 and molecular shape, 29 in nitrophenols, 89 1 - 892 in phenols, 890 and physical properties, 890 - 89 1

Hydrogen bromide, 327 addition to alkenes, 330,35 1 - 352

Hydrogen chloride, 31,38,43,76,327 addition to alkenes, 333,335

Hydrogen-chlorine bond, 63 Hydrogen exchange, 297-298,807,969 Hydrogen fluoride, 24,30,38

dipole moment, t24 molecular orbitals, 994

Hydrogen hahdes addition to alkenes, 3 19,327 - 329 addition to alkynes, 432 heterolytic bond dissociation energies, t22 homolytic bond dissociation energies, t2 1 reactivity, 224,242 reaction with alcohols, 229 - 233

Hydrogen iodide, 76,327,544 addition to alkenes, 334-335

Hydrogen isotope effects, 295-297,532-535,964, 969. 1099 - - . > - - - -

Hydrogen migration, 206, 1020- 1024 Hydrogenolysis, of esters, 77 1,780 Hydrogen sulfide, 3 1 Hydrolysis

alkahne, relative rates, 776 of alkyl hydrogen sulfates, 33 1 - 332 of amides, 767 in biochemical processes, 1236- 1238 of carboxamides vs. sulfonamides, 864 of carboxylates, 729 of carboxylic acid derivatives, 759,764,772 of esters, 77 1 of fats, 1124- 1125 of glycerides, 1 124 of (+)-maltose, 1 187 of methyl glucosides, 1174- 1176 and neighboring group effects, 1038 of nitriles, 724 paaial, 1217- 1221 of phosphates, 1 129 - 1 130 of substituted amides, 859 of urea, 783

Hydronium ion, 176 Hydroperoxides, 894

aliphatic, 898 rearrangement of, 895

3-Hydroperoxycyclohexene, 844,9 17 Hydrophiliq, definition, 253, 1 124 Hydrophobic, defimhon, 253,1124 Hydroquinone,.330,889,984,985 Hydroxamic acid, 842,844 Hydroxide ion, 176 o-Hydroxybenzaldehyde, see Salicylaldehyde p-Hydroxybenzaldehyde, t66 1 4-Hydroxy- 1,3-benzenedisulfonic acid, 547

o-Hydroxybenzoic acid (salicylic acid) Ionization

Hydroxybenzoic acid (salicylic acid), t715,748, ona

~ i g x ~ b e n z o i c acid, 889,t7 15 Hvdroxvbutanal. vrevaration. 800.806 Hjldroxjrbutyralddhyde, preparation, 806 .P-Hydr~xybut~l-S-ACP, 1 133 Hydroxy-2'-chlorodiethyl sulfide, 1037 Hydroxy-2,2dimethylpropanoic acid, 987 Hydroxyesters, 932 ydroxylamine, 673,679,705,977 ydroxylamine hydrochloride, 679 (N-Hydroxy1amino)-3-phenylpropanoic acid, 977 ydroxylation of alkenes. 223.322.357 anti, 483-484 ' '

formation of 1,2-diols, 357 - 358 with permanganate, 358,372,384 with peroxy acids, 357,372 with peroxyformic acid, 358,384 - X . - . .- - 'ydroxyl group, 725 proton chemical shift, t607 -)-Hydroxylysine, t 1207 .Hydroxy-2-methylpentanal, 806 .Hydroxy-4-methyl-2-pentanone, 800,806,807 .Hydroxymethylphenol, 109 1 .Hydroxy-a-methylvaleraldehyde, 806 .Hydroxynaphthalene, 547 .Hydroxyphenyl ethyl ketone, 905 .Hydroxyphenyl ethyl ketone, 905 -)-Hydroxyproline, t1207, 1234 -Hydroxypropionic acid, see Lactic acid .Hydroxypropionic aad, 975 .Hydroxypropjophenone, 905 .Hydroxypropiophenone, 905 IY*~, 1% [ygnmc aad, 1066 lyperconjugation, 200,401 -402,413 in alkenes, 4 13

Iypnotic, 221 [ypochlorous acid, 529 Iypohalites, 237,676, 698, 783 [ypohalous acid, 342 [ypophosphorous acid, 87 1

-Icosane, t93 I-D-Idopyranose, 1 180 -)+dose, 1 162 &on test, 745 midazole, 1057, 1238 ring, 1238

mides, 767 - 768 mine-enamine tautomerism, 935 mines, 834-835,935 mimum ions, 937 ndanone. 8 18 ndigo, 76 ndole, t1058, 1064 nduced dipoles, 29 nductive effects, 200,406, 670 in aromatic substitution, 537 definition, 200 of halogens, 542,944 of substitutent groups on acids, 735-736 (See also Electronic effects; Resonance effect)

nfrar=+bsorption bands, for organic groups, 590, LJ7L

nfrared absorption shift, 590, 592 nfrared radiation, 1 19 . nfrared spectra, 585,590-592,592-594

analysis, 121, 122,590-592 ofalcohols, 217,594,912-913 of aldehydes and ketone, 70q- 70 1 of amines and subshtuted amdes, 877 - of carboxylic acids, 745 -746 of carboxylic acid derivatives, 784-785

of ethers, 596- 597 of hydrocarbons, 592 - 594 of phenols, 912-913

Ingold, Sir Christopher, 134, 140, 179, 183, 191, 199,293,294,303, 1034

Inhibitors, 49- 50,7 1,330 in chlonnation of methane, 49 definition, 49, 1082; 1083

Imtiators, for polymembon, 357, 1085 Inorganic compounds, 1 Insecticide, 5 16 Insertion reactions

of alkenes, 1045 of methylene, 476

Insulin, 76, 1220, 1226, 1234 structure of, 1249 - l250

Interionic forces, 1235 of liquids, 3 1 of solids. 27 and solubility, 3 1

Intermolecular forces, 28 -33 in liauids. 30

in solids, 28 and solubility, 250-258

Intermolecular reacC1ons. and intramolecular reac- tions, 296

Intramolecular fonres, 20-2 1 Intramolecular nucleophilic substitution, 841,

1035 (See also Rearrangement) Intramolecular reactions. 448

competition with int&no~cular reactions, 296 Inversion

of ammonia, 19 of configuration, 182- 185,375,826,1023 of radicals, 65 of sucrose, 1 19 1

Inversional isomers of sucrose, 1 19 1 (See also Stereoisomerism)

Invertase, 1 19 1 Invert sugar, 1 19 1 Iodine, 59

as tracer, 1 18 Iodine azide, 384,487 0-Iodoaniline, 509 Iodobenzene, 508, t520,867, r945 2-Iodobutane, 329 l-Iodo-2-butene, t169 2-Iodocyclohexyl brosylate, 1041 2-Iodo-2,3dimethylbutane, 208,335 3-Iodo-2,2dimethylbutane, 208 Iodoethane, t169 Iodoform, 671,800

boiling point, t171 Iodoform test, 698 2-Iodohexane, 1 145 2-Iodo-2-methylbutane, 168,329 1 -1odo-l -methylcyclopentane, 448 l-Iodo-2-methylpropane, 92 2-Iodooctane, 1 83 2-Iodopentane, 329 3-Iodopentane, 329 m-Iodophenol, t890 o-Iodophenol, t890 pIodopheno1, t890 2-Iodopropane, 3 19 3-Iodopropene, t169 3-Iodopropyne, t 169 m-IodotoIuene, t945 0-Iodotoluene, t945 pIodotoluene, 943,845,970 Ion-dipole bonds, 25 1,258 - 26 1 Ionic bonds, see Bonds Ionic character, 400,967 Ionic polymerization, 1084- 1086 Ionic solutes, 3 1,254-258 Ionization, see Acidity, Acidity constants, Basicity,

Basicity constants

1308 Ionizing power Kekult structures

Ionizing power, 260 Ion pair, 30, 196,254-258,265,270

loose, 257-258,270 tight, 257,270

Ions, solvated, 249,255 Isoalkane, 90 Isobutane, t84,91, t93, 103, 116,345,364 Isobutyl alcohol, 215, t216, 349,694,721,769 Isobutvlamune. t824

i n f d spekum, 878 N-Isobutylaniline, 830 B-Isobutyl-BBN, 934 Isobutylbenzene, 55 1, t553 Jsobutjll benzoate, 769 Isobutyl bromide, 124, t169, 190, 330, 925,928 Isobutyl chloride (l-chloro-2-methylpropane), 10

104, 108, 168, t169, 560 Isobutylene, 277, t277, 282, t285, 31 1, 321, 323,

364.559.724. 1099

heat of hyclrdgenation, t326 NMR signals, 602, 6 17 reactio~q.336, 338, 340,343, 345,

Isobutyl idde,!l69 Isobutylmagnesium bromide, 687,69 Isobutylmalonic ester, 926 Isobutyl methyl ketone, t661 Isobutyl radical, 1 16, 1 17 Isobutpldehyde, 830 Isobutync aad, 247, 72 1 Isobutyryl chloride, 664 Ismproaldehyde, 659 Isocaproic acid, 925 Isocrotonic acid, 872 Isocyanates, 839

reactions, 839,844, 1092 Isodurene, t553 Isoelectric point

in amino acids, 121-1 - 1212 in ~roteins. 1226 - 1228

Isoeugenol, 582,894 Isohexane (3-methylpentane), 90, 9 1, t93 Isohexyl chlonde, 90 Isolability, 149,28 1 Isolated double bonds, 410 Isoleucine, 219, 927, 1238 (+)-Iso!eucine, t 1207 Isomensm, 36- 37

alicyclic compounds, 463 -467 alkanes, 88 alkenes. 277-280 alkyl groups, 89 -90 alkynes, 427 butanes, 83 - 85, t82 butylenes, t277,277-2?8,280 cis-trans, see Geometric isomerism concept of, 36 hexanes, 87 o~tical. 133 sibstitu!ed benzenes, 495 -497

IsomenzaQon catalytic, 96 industrial, 555-556

Isomer number, 84,126- 128 benzene and, 495 tetrahedral carbon and, 126- 128

Isomers cis and trans, 463-467,470 configuratioral, definition, 149, 28 1 conformational, 149 - 150,28 1 definition, 36 mirror-image, see Enantiomers stereo-, see Stereoisomers torsional, 28 1

Isoniadd, 1068 Isoecoti+c a4d, see 4-Wdinecarboxylic acid IsomcoQmc aad hydrazlde, 1068 "Isooctane", see 2,2,4-Trimethylpentane

Isopentane, 87,90, t93,95 Isopentenyl pyrophosphate, 1 128, 1 136, 1 137, 1 140 Isopentyl acetate, t769 Isopentyl alcohol, see 3-Methyl-l-butanol Isopentyl chloride, 90 Isophthalic acid, 564, t715, t742 Isoprene, t4 1 1,420-42 1

polymerization, 420,420- 42 1, 1088 Isoprene rule, 4 12 Isopropyl alcohol (2-propanol), 21

225,233,316,320,331,691 Isopropylamine, t824, 830 Isopropylbenzene (cumene), t553, Isopropyl bromide, 124, t169, 187

242,308,310,319,330,353 dehvdrohalo~enahon. 290 -29 1 infiked s p e h m . 591 NMR spectrum, 6 18

Isopropyl cation, 19 1 ionization pqtential from bromide, 197

Isopropyl chlonde, 89, 104,134,168, t169,335,388 NMR signals, 602

Isopropylcyclohexane, 463 Isopropyl ether, see Diisopropyl ether Isopropyl fluoride, 645 ~Isopropylglutaric acid, 705 Isopropyl hydrogen sulfate, 320, 331 Isopropyl iodide, t169,3 19, 328 Isopropylmagnesium chloride, 100 4-Isopropyl- l -methylcyclohexane, 940 Isopropyl methyl ketone, 660 Isopropyl n-propyl ether, 240 Isopropyl radical, hyperconjugation, 402 Isopropylsuccinic acid, 705 Isopropyltoluenes (cymenes), t553, 1200 Isopropyltrimethylammonium ion, 316 Isoquinoline, 1057, t1058 Isotactic polypropylene, 1089 Isotope effects, 295 -297

in electrophilic substitution, 532 - 535 in elimination reactions, 297 in free-radical chlorination, 295 in nucleophilic aromatic substitution, 964,969 in polymerization, 1099 primary, 295

Isotopes, heavy, abundance of, t588 Isotopic exchange, 183,297-298, 313,774,777,

807,969 Isotopic peaks, in mass spectra, 588, t589 Isotopic tracers, 1 18

in addition, 364 in aldol condensation, 807 in biological oxidation-reduction, 1103- 1106,

1113, 1114 in elimination, 298, 313, 380 in halogenation of alkanes, 1 16 - 1 18 in hydrolysis of esters, 774,775,777,778 in nucleophilic substitution, 183,963 in rearrangements, 839,896, 1056

(-)-Isotrehalose, 1202 Isovalent hyperconjugation, 413 Isovaleric acid, 727 IUPAC system of nomenclature, 90-92, 168, 215,

282,428,659,716,754 (See also individual farnilzes)

J Johnson, W.S., 623 Juvenile hormones, 1 139

Kekulk, August, 2,494 benzene structure, 401,494-497,500,503

68, 574,903,950,

Kelvin, Lord Light

Kelvin, Lord, 134 Kendrew, J.C., 1235 a-Keratin, 1225

proposed helm structure, 1233 - 1234 Kerosine, 96, t96, 124 Ketals, 681 Ketene. 474. 763 -- Keto a&ds, from tetra-O-methyl-D-glucose, 1 177 a-Keto acids, preparation, 930 PKeto acids, decarboxylation, 930-931 8-Keto esters, formation of, 8 13 - 8 15 a-Ketobutyric acid, preparation, 930 Keto-enol tautomerism, 435-436,804-805,977

acjd and base catalysis, 820 and-catalyzed aldol condensation, 8 18 bromination, 804-805 in carbohy.drate% 1 149 - 1 150 electropluhc conjugate adduon, 976 nucleo hi!.ic conjugate addition, 977 (See a l o Imine-enamlne tautomerism)

FKeto esters, 802,8 13 ; 8 16 (See also.Acetoacetic ester synthesis; Clsusen wndensauon; Ethyl acetoacetate)

a-Ketoglutaric acid, 1 1 15 2-Ketohexose, (-)-fructose as, 1 146 2-Ketohexoside, 1 178 Ketones, 359,440,657-712,692,797-814, 1103

addition of alcohols, 674,680-683 of ammonia derivatives, 673,679-680 of carbeons, 675 of cyamde, 673,678-679 of Grignard reagents, 685-688

aldol condensation. 805 - 809 aliphatic, 665 . alkylation, 93 1 -932 analysis, 697-698 aromatic, 665 Clemmensen reduction, 667,672,677 crossed Claisen condensation, 8 16 enamine formation. 935-937 ~p~ ---p- ~ - .

enolization, 804 - 805 in Grignard synthesis, 685 - 692 halogenation, 675,800

aad-catalyzed, 804- 805 base-promoted, 802-804

industrial source, 661 nomenclature, 658 - 660 nucleophilic addition, 669-675, 800-801 oxidahon. 67 1.675 -677

A acetoacetic ester synthesis, 664,927-930 from acid chlorides. 664.665.668.762 . , , via enamines, 935-.937 Friedel-Crafts acylation, 663-664,666-667,

765 ~ries'&man~ement, 901,905 organoborane synthesis, 933 -935 w n g organocopper compounds, 664,665,

668-669,762 oxidation of secondary alcohols, 226,236,

237,663,665 ozonolvsis. 358-360 pinacoi r e b g e m e n t , 705

reactions, 669-675 wrth Gngnard reagents, 685 - 692

reduction, 556-557 to alcohols, 672 to hydrocarbons, 672,677-678

reductwe amination, 672,834-835 spectroscopic analysis, 692, 700-701, t786 structure. 657-658 unsaturated, preparation, 973 Witti reaction, 801 81 1-812 ~o lkKishner reduction, 667,672,677 (See also a,&Unsaturated carbonyl compounds)

7-Ketonorbornene, 988 Ketopentoses, dehuon, 1 144

Ketoses definition, l l44 effect of alkali, 1 150 oxidation, 1 149

Kharasch, M.S., 102, 161,330, 351 Kiliani, Hemrich, 1 152 Kiliani-Fischer synthesis, 1152- 1153, 1162 Kimball, G.E., 374,.1034 Kinetic energy htnbuhon. 56 Kinetics --

definition, 177 - 178 of dehydrohalogenation, 293 in the E2 mechanism, 295 first-order, 178- 179, 188,293 second-order. 178 - 179. 182

- 2 - - - ~jeldahl methddj 513-5 14 Kloosterziel, H., 1024 Knocking, in gasoline engine, 1 18 Knoevenanel reaction. 927.8 10-81 1 Knoop, FGnz, 1 134 .

'

Kolbe reaction, 5 19,902,908 Komer, Wilhelm, 509 Korner method of absolute orientation, 509 Kossel, Walther, 4 Krebs, H.A., 1 1 14

~ , p r e h , 1162-1164, 1166 I, preh, 1 1 63 Labeling experiments, 1 17 - 1 18 (See also Isotope

effects; Isotopic tracers) (R)-Lactaldehyde, 1 1 15 Lactams, 840, 1248 Lactic acid, 135, 138,716,770

enantiomers, 132 (+)-Lactic acid, 159, 1163 D-(-)-Lactic acid, 1 163 L-(+)-Lactic acid, 1163, 1164 Lactide, 770 Lactobacillus bulgaricus, 1 189 Lactobionic acid, 1 189, 1 190 p-Lactoglobulin, 1248 Lactones, 770 FLactones, 989 Lactonic acid, 789 Lactosazone, 1 189- 1 190 (+)-Lactose, 1185, 1189-1191

properties, 1 189 source, 1 189 structure, 1 189

Ladenburg, Albert, 5 15 benzene structure, 5 15

Lanosterol, 1 136, 1 137 Lapworth, A., 803 Lard, t1121 Lauric acid, 7 13, t7 15,725,740 Lauryl alcohol, 780, 1 126 Lauryl hydrogen sulfate, 1 126 LCAO (linear combination of atomic orbitals)

method, 993-994 Lea:;! grryps, 172- 173, 175, 177,

synthesis, 12 14 (-)-Leucine, t 1207 Levorotatory, definition, 129 Levulinic acid. 705

Lewis, G:N., 4 acid and base definition, 34 - 36

Lewis acids, 528,557,559,561 Life, origin of, 4 1 Ligands, 1042 - 1045 Light, detection of, 285

1310 Ligroin (light naphtha) Methanethiol

Ligroin (light naphtha), 96, t96 Limonene, 492 Linalool, 647 Lindlar's catalyst, 433 Linear combination of atomic orbitals (LCAO),

993-994 Linear free energy relationships, 732 Linear polymers, 1088- 1089, 1096 Linoleic and, t7 1 5, 1 1 22 Linolemc aad, t7 15, 1 122 Linseed oc,. 1100, 1128

composltIon, t1121 Lipids, 1 120, 1 137, 1 138 (See also Fats; Steroids:

Terpenes) Lipophilic, definition, 253, 1 124 Lithium acetylacetonate, 38 Lithium acetylides, 429,437,438 Lithium aluminum hydride, 349,351,677

in reduction of acids, 728,740 Lithium apide, 437,1085 L~thium dpllcylcopper, 10 1 Lithium halkylcuprate, 668 Lithium diarylcuprate, 668 Lithium di-tert-butylcopper, 122 Lithium di-n-butylcuprate, 664 Lithium diethylcopper, 98 Lithium diisopentylcuprate, 669 Lithium dimethylcopper, 102 Lithium dimethylcuprate, 668 Lithium di(ppitrophenyl)cuprate, 669 Lithium hvdnde. 35 1 Lithium ishpropylacetylide, 433 Lithium methylacetylide, 433 Lithium n-pentylacetylide, 430 Longuet-Higgins, H.C., 1004 Lossen rearrangement, 844 Lowest unoccupied molecular orbital (LUMO),

1015-1016 . . . - . . . . Lowry-Bronsfed, acid and base definition, 33 Lubricat~ng ofi, t96 Lucas, Howard, J., 386, 1032, 1034 Lucas reagent, 244 Lucas test, 230,244 Lucite, 973, 1081, 1096 LUMO (lowest unoccupied molecular orbital),

1015-1016 Lycopene, 488 Lycra, 1097 (+)-Lysine, t1207 (-)-Lyxose, 1 16 1

Macromolecules, 1077- 1 100 definition, 1077 structure and properties, 1093 - 1096

"Magic" acid, 102 Magnesium-halogen bonds, 100 Magnesium perchlorate (Dehydrite), 73 Magnehc moments

in free radicals, 573 of nuclei, 600 - 60 1

Magnetogyric ratio, 600 Malaprade, L., 1 150 Malicacid, 144, 159, 160, 751, 1115 Maleic aphydride, t755, t972, 973, 983 Malic aad 144, 159, 160, 11 15,751 Malonic akd, 742, t742

decarboxylation, 930 - 93 1 Malonic ester, see Ethyl malonate Malonic ester synthesis, 924-927 Malonyl CoA, 1133 Malonyl-S-ACP, 1 133 Malonvlurea. 783 ~al task, 1 187 Maltobionic acid, 11 87 - 1 188 (+)-Malto~, 1185-1188, 1195

from amylose, 1 193 reactions, 1 186 - 1 188, 1204 structure, 1185-1188

Mandelic acid, 144,673,750, 751 Mandelomtnle, 673 ManganeHW), 236 Mannan, 1203 Mannaric acid, t1149 Mannitol, t1149 Mannonic acid, t1149 &D-Mannopyranose, 1 179 Mannose, 1149 (+&Mannose. 1 147.1 155

itructure &termihation, 1151 - 1152,1157-1 160 Mannuronic acid, t1149,1203 Markovnikov, Wadimir, 328 - 329 Markovnikov's rule, 329, 336-337, 342,346,349,

959 ~ar&&, 41 Mass spectra, 586- 589 Mass spectrometry, 122,586 Mass spectrometers, 586 Mass-tocharge ratio, 586,588 Maximum overlap, principle of, 10 Maximum rotation, 156 Mayo, Frank R., 330,35 1 Meerwein, Hans, 19 1,204,306 Melander,. W, 532 (+)-Melezitose, 1202 Melibiose, 1202 Mellitic acid, 745 Melting point, 27-28

and crystal structure, 27 -28 ionic vs. non-ionic compounds, 27 - 28 and molecular symmetry, 553-554

pMenthane, 492,492,940 2-Menthene. 473.491

Menthone, 940 (-)-Menhone, 663 Menthyl chloride, 473,49 1 Mercuric acetate, 222,321,346 Mercuric trifluoroacetate, 24 1 Mercurinium ions, 347 Memfield, R. Bruce, 1225 Mesitoic acid, 724, 738,739 Mesitylene, 535,546, t553, 584,724,765,

1174 &R spectrum, 606,608,643

Mesityl oxide, see 4-Methyl-3-penten-2-one Meso compounds, 147 Meso structures, 146 - 147 Mesotartaric acid, 750, 1 161, 1 165, 1 166 Messenger RNA, 1247 Mesyl group, 234 Metabolite antagonism, 864 Meta-directing groups, 520-525,954 (See also

Orientation) Metal acetylides, 430

reactions, 433,438-439 Metal hydride, 678 (Seealso individual compounds) Methacrylmde, 789 Methacrylic acid, 673,789, t972,973 Methallyl chloride, 364,645 Methanal, see Formaldehyde Methane, 39-76, 119

bond formation, 15 - 17 bromination, 44-45 1 18 chlorination, 43 -44,48 -49 heat of combustion, -42 phys* properties, 28, 31,32, reachons, 42 -49

halogenation, 42,44-46 oxidation, 42-43

source, 4 1 - 42 structure, 17,20,40, 126 - 128

Methanesulfonic acid, 234 Methanethiol, 35

Methanoic acid m Methyl cis-9-octadecenoate

dethanoic acid, 7 13 dethanol, 31, 32,43,88,215, t216,255,256,674,

683,726,739, 1125 and methyl bromide, 172, 178, 181

-)-Methionme, t1207 tethoxyacelic acid, 745 -Methoxy-4-acetoxyphenylalanine, 105 1 -Methoxy-4-allylphenol (eugenol), 582,894,919 Iethoxyaniline (anisidine), t824,965 -967 -Methoxybenzaldehyde (anisaldehyde), t66 1,683 eMethoxybenzoic acid, t7 15 -Methoxybenzo$ acid, t7 !5. -Methoxybenzo~c acld (amsic acid), t7 15,912,9 18 -Methoxvbenzvl alcohol, 683 -~ethoxjrhexabe, 237 dethoxymethyl chlonde, 407 -Methoxy-4-methyl-2-pentanone, 975 -(pMethoxyphenyl)propene, 583 (ethyl acetate, 757, t769 infrared spectrum, 786 preparation, 764

dethylacetylene, 276 dethyl acrylate, t972, 973 dethyl alcohol, see Methanol dethylamine, 821, t824,826, 828, 836, 846, 977 -(n-Methylammo)heptane, 822 -(n-Methy1amino)-4-methyl-2-pentanone, 977 dethylaniline, see m-, o-, and pToluidine tJ-Methylaniline, 546,821,836 infrared spectrum, 878 preparation, 859 -reaction with nitrous acid, 865

~Methylanisole, 724, 905, 912 dethyl a-L-arabinoside, 1 178 dethyl aryl ethers, 9 1 1 ~Methylbenzaldehyde, 898 tJ-Methvlbenzanilide, 859 dethyl&nzene, see Toluene dethyl benzoate, 726, 739 v-Methylbenzyl alcohol, 727 cMethylbenzy1 bromide, 576 cMethylbenzy1 hydroperoxide, 898 v-Methylbenzyl tosylate, 576 ~Methylbenzyl tosylate, 576 dethyl bromide, 45,88, 102, t169, 178, 187, 190,

243,262,837,926 and methanol, 172, 178, 181

:-Methyl-l-bromobutane, 225 :-Methyl-1,3-butadiene, see Isoprene !-Methylbutanoic acid (a-rnethylbutyric acid),

716,721 chirality, 155 preparation, 226

!-Methyl-l-butanol, 135, 136, 138, 215, 225,226, 313.560.721

enantiomek, 132 from fermentation, 159 from fuse1 oil, 129, 130, 156 ~re~arat ion of, 687 ieadons, 154 specific rotation, 130, 156

I-Methyl- l-butanol (isopentyl alcohol), t2 16, 560, 694

synthesis, 694 !-Methyl-2-butanol, see tea-Pentyl alcohol L-Methyl-2-butanol, 2 15,560

preparation, 349 L-Methyl-2-butanone, 660 L-Methyl-2-butenal, 8 19 !-Methyl-l-butene, 305,306, 313, 347

heat of hydrogenation, t326 preparation, 301,857

3-Methyl-l-butene, t285, 305, t326, 335 synthesis, 693-694

!-Methyl-2-butene, t285, 305,306, t326, 334, 336, 349,720

preparation, 300,313,693,857 !-Methyl-2-butenoic acid, 679, 987 I-Methyl-2-butenoic acid, 67 1

3-Methyl-2-buten-2-y1 group, 409 3-Methyl-2-buten-2-y1 triflate, 409 3-Methyl-2-buten-2-y1 trifluoroethyl ether, 409 3-Methyl-2-butyl tosylate, 305 Methyl n-butyl ketone, 688,690 3-Methyl-l-butyne, 1429 2-Methyl-3-butyn-2-01,692 a-Methylbutyric acid, see 2-Methylbutanoic acid a-Methylcaproic acid, 1 146 Methyl cation

ionization potential from bromide, 197 structure, 193

Methyl chloride (chloromethane), t24,43,46,74, 88, t169,283, 564

a-Methylcinnamic acid, 677 Methylcyclohexane, t444,446

conformation, 46 1 -463 1,3-diaxial interactions, 46 1,462 industrial source, 446

3-Methylcyclohexene, 49 1 Methylcyclopentane, 322, t444

industrial source, 446 1-Methylcyclopentanol, 346 2-Methylcyclopentanol, 490, 703 trans-2-Methyl-l-cyclopentanol, 322 l-Methylcyclopentene, 322, 347, 448, 490 3-Methylcyclopentene, 703 Methylcyclopropane, 602 5-Methyl- 1,3-dihydroxybenzene, 9 15 N-Methyl-2,4-dinitroaniline, 829 Methyl dodecanoate, 780 Methylene, 473-476,763 Methylene bromide, 45 Methylene chloride (dichloromethane), 43,44,

t169, 258,442 Methylenecyclohexane, 801 Methylene group, 43 Methylenetriphenylphosphorane, 801,812 N-Methyl-N-ethylaniline, 822 N-Methyl-N-ethylbenzamide, 848 Methylethyl-n-butylamine, 837 N-Methyl-N-ethylbutyramide, 858 N-Methyl-Nethyl-ptoluenesulfonamide, 848 Methyl fluoride, 38 N-Methylformamide, 258 Methyl free radical, 48, 64-65, 76, 112 Methyl p-D-fructofuranoside, 1 178 Methyl a-D-fructoside, 1178 Methyl /?-D-glucopyranoside, 1 17 1, 1 178 . Methyl a-D-glucos~de

formation, 1 169- 1 173 reactions, 1171, 1173 structure and properties, 1 169 - 1 173

Methyl &D-glucoside formation, 1 169 - 1 173 reactions, 1 174, 1 176 structure and properties, 1 169 - 1 173

Methyl group, 88 2-Methyl-3-heptanone, 664 2-Methyl-2-hexanol, 687,688,690 3-Methyl-2-hexanone, 929 5-Methyl-2-hexanone, synthesis, 928,934 2-Methyl-4-hydroxyacetophenone, 901 4-Methyl-2-hydroxyacetophenone, 901 Methyl iodide, 88, t169, 91 1 Methylisopropylacetylene, 428 Methylisourea, 784 Methyl ketones, 671,676 Methyl laurate, 780 Methylhthium, 102 Methylmagnes!um bro.mide, 688,690 Methylmagnes~um i e d e , 99,772 a-Methylm~dehc acld, 804 Methyl mesltyl ketone, 765 Methyl methacrylate, 872, 973

polymerization, 1081, 1083, 1085, 1096 4'-Methyl-3-nitrobenzophenone, 66 Methyl pnitrophenyl ketone, 668 Methyl cis-9-octadecenoate, 773, 1 137

3-Methyloctane, 102 Methyl oleate, 773, 1137 Methyl orange, 75,875 Methyl 4oxo-7-'pethy1octanoate, 669 y-Methylpamomc acid, 8 1 8 2-Methylpentanal, 659 3-Methylpentanal, 659 4Methylpentanal, 659 2-Methvl~entane. 91.638 3-~eth$fpentie'(isdhe&e), 90,9 1,193 2-Methylpentanoic acid (a-methylvaleric acid), 926 4-Methvloentanoic acid (isoca~roic acid). 925

2-Methyl-l-peniene, 307 2-Methyl-2-pentene, 307, 359 (&3-Methyl-2-pentene, 1055 4-Methyl-2-pentene, 282, 307 4-Methyl-3-penten-2-one (mesityl oxide), 67 1,800,

1972.973 reactions, 975,977,982

Methyl n-pentyl ether, 238 2-Methyl-3-pentyl tosylate, 307 4-Methyl-2-pentyne, 428 Methyl phenyl ether, see Anisole Methyl phenyl ketone, see Acetophenone 2-Methyl-3-phenylpentane, 55 1 2-Methyl-l-phenyl-2-propanol, 690 2-Methyl-3-phenylpropenoic acid, 676 Methylpropane, see Isobutane 2-Methyl-l-propanol, see Isobutyl alcohol 2-Methyl-2-propanol, see tert-Butyl alcohol 2-Methylpropene, see Isobutylene 2-Methylpropenoic acid, see Methacrylic acid Methyl-n-propylamine, 847 Methyl n-propyl ketone, 659 Methyl-n-propylmalonic ester, 926 N-Methylpyridinium iodide, 1072 Methyl rahcal, 48,64-65,76, 112 Methyl salicylate, 9 14

1 175,

Metd;lptolyl ether @methylanisole) 724,905,912 Methyltriphenylphosphonium bromide. 8 12 a-Methylvaleddehyde, 659 &Methylvaleraldehyde, 659 y-Methylvaleraldehyde, 659 a-Methylvaleric acid, 926 Methylvinylmethanol, t216 Methyl vinyl ketone, reactions, 981 Methyl &D-xyloside, 1 178 Mevalonic aad. 1139. 1140 Meyers, A.I., 932 '

MIBK (Isobutyl methyl ketone), t66 1 Micelles, 1 124 - 1 125 Michael addition, 979-982 Michael condensation, 927 Micrococcus ureae. 783 Microscopic revekibility Middey, T.C., Jr.. 119 Mi - t o b aptitude, 842, M E , Stapley, 42 "Mixed a c q , 525 Modena, G~orgo, 408 Moffitt. W.A.. 453

principle,

896-897

~olecular biology, 1235- 1236 Molecular forrpula, determination, 72,75 Molecular orbltals,.9,99! - 1030

bonding and anbbonhng orbitals, 994-996 LCAO method, 993-994 orbital symmetry and chemical reactions, 1004-

1024 theo&%9 1 -992 wave equations, 992-994

7

Neomenthyl chloride

Molecular weight of cellulose, 1200 end-group analysis, 1193- by mass spectrometry, 75, of pepudes, 12 1 8 of polysaccharides, 1 195

Molecule of the Year, 446 Molecules

flat, 15 linear, 13 polarity of, 23 -26

Molozonides, 359 Monomer, 356, 1078 Monosaccharides, 1 143 - 1 184

analvsis. 1 149 - 1 1 50, 1 152 +---, - - - - - - - classipcation, 1 144 defimtion, 1144 effect of alkali, 1149- 1150 reactions, 1149-1150, 1175 (See also Aldohexoses; Aldoses; ~-(+)-Glucose:

. . etc.) - - 7

Morphine, 159 Morpholine, 937 Ms. 234 MUCG acid, 1 16 1 Mulliken, R.S., 402 Muscalure, 442 Muscarine, 164 Musk (synthetic), 91 5 Mustard gas, 1037 Mutarotation

of ~-(f)-gl~cose, 1 170 of (S)-maltose, 1 187

Mutations, 1247 (-)-Mycarose, 1 184 Myoglobin, 1235 Myosin, 1225 Myrcene, 424 Myristic acid, t715

NAD (nicoti namide adenine dinucleotide) 114, 1229 3, 1105-1106 !- 1106 tinamide adenine dinucleotidr

Naphthalene? 510-513,s41, s electroph&c substituQon in, 34s - industrial source. 555 -556 nomenclature, 5 l0 structure, 511-512 test for, 580

Naphthalenesulfonic acids, 547 l-Naphthol, 547 2-Naphthol, 5 10,889 &Naphthol, 510, 876, 889 1,4NaphthoqUinone, 986 Natta, Giulio, 1087, 1089 Natural gas, 41,94 Natural rubber, 420-421,422, 1095 NBS (AJ-bromosuccinimide), 323,390, Neighboring group effects, 386,103 1 -

by acetoxy group, 1039- 1040 anchirnenc assistance, 1037 - 104 1 by bromine, 1032- 1035, 1037 bv carbon. 1037 in enzyme action, 1240 intramo~ecdar nucleo~hilic attack, 1035-1037 by nitrogen. 1037 - by oxygen, i037 reaction rate, 1037 - 1041 stereochemistry, 1032- 1035 by sulfur, 1037, 1038

Neohexane. 364

Neopentane W N-terminal residue

Neopentyl alcohol, 230,231,316,560,720,727 Neopentyl bromde, 188,305 Neopentyl cation

mass-tocharge ratio, 586 rearrangement, 204- 205

Neopentyl chloride, 1 10, 171 Neopentyl ethyl ether, 204 Neopentyl hahdes, 203 Neoprene, 420, 1080 (+)-Neotrehalose, 1202 N e d , 705 Nerol, 492,647 Nerolidol. 939 Ne~onic.acid, 1 137 Neutralization equivalent, 744 - 745 Newman, M.S., 8 1 Newman projections, 81,463 Niacin, see 3-Pyridinecarboxylic acid Nicol prisms, 128 Nicotinamde adenine dinucleotide, see NAD

reduced,.see NADH Nicotinarmde adenine dinucleotide phosphate,

NADP reduced, see NADPH

Nicotine, 1059, 1073 (-)-Nicotine, 1075 N~cotinic acid see 3-Pyridinecarboxylic acid Nitration

of benzene, 497,5 18 orientation of in substituted benzenes, t521 of phenols, 900,906 - 907 of pyridine, 1068 of pyrrole, furan and thiophene, 1064 reaction mecha&m, 525 - 527,532- 533

Nitriles hydrolysis, 678-679,722,724,870 infrared absorption frequencies, t592 nomenclature, 725 preparation, 678-679,723,724,870 reduction, 830,83 1

Nitnle synthesis of carboxylic acids, 722,723,724-725

o-Nitroacetanilide, 546,832 pNitroacetanilide, 546,86 1 pNitroacetophenone, 668 m-Nitroene, t824 o-N~t rodne , t824 p-Nitroaniline, t824, 828,873 - preparation, 861 o-Nitroanisole, 902 m-Nitrobenzaldehyde, 695,678 pNitrobenzaldehyde, 659,683

preparation, 662,663 Nitrobenzene, 508, t520,667,827,872,947

orientahon of electrophilic subst~tut~on, 539 - preparation, 497 rate comparison, 536- 537

pNitrobemenediazonium ion, 880 m-Nitrobenzoic acid, 509,667, t715,750

o-%L'obeGo$ acid, t7 15 0-Nitrobenzoic acid. 563.713, t715.721.750 . .

relative acidity, 73 l Nitrobemo~c aads, 524 - 525 m-Nitrobemophenone, 666 - 667

-m-Nitrobemoyl chloride, 667 pNitrobenzoy1 chloride, 663,668, t755 mNitrobenzv1 alcohol. 683 >NiGObenZyl benzoaie, 564 pNitrobenzy1 bromide, 552,902 pNjtrobenzy1 isophthalate, 564 pN~trobenzyl phthalate, 564 ~Nitrobenzyl terephthalate, 564 pNitrobenzyl ptolyl ether, 902 pNitrobiphenyl,547 o-Nitrocinnamic acid, 750 Nitro compounds

,772

see

.540

hydrogenation, 828 importance, 869,-870,878,946-947 mfrarg absorphon frequencies, t592 redudon, 828,830,832 removal of nitro group, 871

m-Nitrodiphenylmethane, 547 pNitrodiphenylmethane, 584 o-Nitroethylbenzene, 550 pNitroethylbemene, 550 Nitrogen -

armno, Van Slyke determination, 12 15 analysis, 513-514 electrondeficient, 838-839 electronic configuration, t8 lSN as tracer. 1 18

Nitrogen-hydrogen bond, 18 Nitrogen tntluoride, t24,25 Nitro group, 396 m-Nitromandelic acid, 678 Nitromethane, 384,396 l-Nitronaphthalene, 547 Nitro~llum Ion, 525-526 Nitronium salts, 526 m-Nitrophenol, t890

~ntermolecular h drogen bonding, S90,89 1 - 892 o-Nitrophenol, t89( 902

chelation, 89 1 preparation, 900,906 - 907

pNitrophenol, 769, t890 intermolecular hydrogen bonding, 890,89 1 - 892 preparation, 900

Nitrophenols idtared bands, t892 models of, 892

pNitropheny1 acetate, preparation, 769,900 o-Nitropheny! meeyl ether, 902 3-Nitrophthahc aad, 750 l-Nitropropane, 828 3-Nitropyridine, 1068 4-Nitropyridine n-oxide, 1073 Nitroquinolines, 1069 Nitrosation, 5 19,864

of phenols, 901,907 pNitroso-N,Ndmeth laniline, 822,954

preparation, 849,8d;. N-Nitroso-N-methylahe, 865 4-Nitroso-2-methylphenol, 90 1 Nitrosinium ion, 865 pNitrosophenol,907 PNitrostyrene, 986 o-Nitrotoluene, 509,871

preparation, 562 pNitrotoluene, 563,662,721, 832, 870, 871, 872

preparation, 562 pNitrotriphenylmethy1 hydroperoxide, 897 N~t roq aad

reaeons yith amines, 849,864-866 readon wth urea, 783

NMR, see Nuclear magnetic resonance spectroscopy Nodal plane, 992 Nodes, wave, 992 Nomenclature, see specific families Nonadn, 48 1 n-Nonadecane, t93 n-Nonane, t93,98,102 Non-bonding orbitals, 996 l-Nonene, 1285 Non-ionic solutes, 252-254 Non-stereoslective addition, 476 l-Nonyne, t429 Noradrenaline, 9 15 Norbornane, 445 Norbornene, 32 1 exo-Norbornene, 1023 exo-Norborneol, 32 1 Norcarane, 174,489 Nortricyclene, 445 Novocaine, 882 N-terminal residue, 12 19

1314 Nuclear magnetic resonanc X spectra n-Octyl bromide

Nuclear magnetic resonance spectra, com~licated, 623 -625

Nuclear magnetic resonance (NMR) 192,585,600-629

absor&onfrequency, 600 of alcohols, 640 of aldehydes, 70 1 of amides, 786,877 of amines, 877 carbon- 13 (CMR), 629 - 639 of carboxygc acid derivatives, 785 of carboxyhc aclds, 747 chemical shifts. 604-608. t607 6 scale, 605 ' of 1 ", 2", and 3" hydrogens, 604-607 reference mint, 605 7 scale, 605

conformational analysis and, 625 - 629 coupling constant, 6 14,620

conformations and, 620 decoupling spins in, 624 - 625 deuterium labeling, 625 double resonance method, 624-625 of esters. 786 field strength, 600 - 60 1 of fluorine, 617,629 of hydrocarbons, 623 -624,639 inversion of molecules and, 626 magnetic moment in, 600 molecular changes and, 625 -629 of monosaccharides, 1 184 peak area and proton counting in, 609 of 2,4-pentanedione, 820 of phenols, 9 13 of l -phenyl- 1,3-butanedione, 820 proton exchange, 626 protons in, 600

aromatic, 606, t607 chemical shifts, 604-608 counting of, and peak area, 609 deshielded, 604 &astereotop~c, 603 enantiotopic, 603 eqgvalent, 60 1 - 604,625 -629 nelghbonng, 6 16 non-eqmvalent, 605,6 16 shielded, 604 side-chain, 607 - 609

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 structural information from, 602-603 temperature effects, 629 theory, 600- 60 1

Nuclear spin, 600 Nucleic aci*, 1077, 1128, 1182, 1241- 1246

denaturaaon, 1226 genetic code, 1246 - 1247 heredity and, 1246 - 1247 primary structure, 1241 - 1242 secondary structure, 1242 - 1245

Nucleophiles, 172- 173, 175 - 178 ad&uon effect, 34 1 concentration of, 2 10 nature of, 2 10

Nucleophilic acyl substitution, 758 acid-catalyzed, 758 in acid chlorides, 76 1 -762 acylation of organocopper compounds, 668 - in carboxylic acid derivatives, 755 -760 in Claisen condensation. 802.8 13 - 8 15 , , in esters, 770- 771 in Friedel-Crafts acylation, 666 - 667 in hydrolysis of amides, 767, 859

vs. addition, 756 vs. allcyl substi!ution, 759-760

Nucleophilic ad&aon acid-catalyzed, 67 1 to aldehydes and ketones, 671 -684 in aldol condensation, 800 - 80 1,s 13 in Cannizzaro reaction, 683-684 to carbonyl compounds, 800 - 80 1 to a$-unsaturated carbonyl compounds, 974,

976-978 vs. acyl substitution, 756 in Wittig reactions, 8 1 1 - 8 12 (See also Addition reactions)

Nucleophilic aliphatic (alkyl) substitution, 166, 175-181

alcohols. 229.232.239 in alkylation of esters, 802,924-930 alkyl halides and organometallic cornpun&,

101 - 102,172- 175,802 +kyl sulfonates, 233-234 m ammonolys~s of halides, 832-834 in cleavage of ethers, 242 - 243 electronic effects, 961

alkyl halides and orga$omet&c co&pun&, 101 - 102,172- 175,802

+kyl sulfonates, 233-234 m ammonolys~s of halides, 832-834 in cleavage of ethers, 242 - 243 electronic effects, 961 energy c w e , 956 and epoxides, 485-487 a-halogenated acids, 741 -742 kinetics, 178 mechanisms, 179- 181,955-956 in Michael addition, 979-982 vs. acyl substitution, 759-760

Nucleophilic aromatic substitution, 944,952-967 bimolecul~ displacement, 952- 956

mechamsm, 955-956,959-961 orientation, 957-958 reactivity, 952-955,956-957

elimination-addition (benzyne), 949,962-967 energy curve, 956 in pyridine, l069 - 107 1

Nucleophilic assistance, to solvolysis, 269 -271 Nucleoph&c power, 176,257,269 Nucleophdx reagents, 172 Nucleophilic substitution

!n allylic substrates, 404-406,407 m benzyhc substrates, 575 -576 in vinylic substrates, 407 -409

Nucleophihc sulfonyl substituaon, 859 Nucleoprote~ns, 1241 - 1246 Nucleosides. 124 1

Oblivon, 8 18 Octa-o-acetylcellobiose, 1200 Octacarbonyldicobalt, 1052 9,12-Octadecadienoic acid, 1 100 n-Octadecane, t93 c@-9-Octadecenoic acid (Oleic acid), 7 13, t7 15,1122 cz3-9-Octadecen-1-01.773 n-Octadecyl alcohol,'t216 1,4,5,8,11,12,13,14-Wydro-9,lO-anthraquin-

one, 983 A'~9-Octalone, 98 1 Octa-o-methyl-D-maltobionic acid, 1 187 - 1 188 n-Octane, t93

mass spectrum, 587 Octane number, 118 2-Octanol, 242 (+)-2-Octanol, 182 (-)-2-Octanol, 182 2,4,6-Octatriene, 1006, 101 1 l-Octene, t285,322,355,392

CMR spectrum, 634-635 infrared spectrum, 59 1

n-Octyl alcohol, t2 16 n-Octyl bromide, t169

n-Octyl chloride m 1,3-Pentadiene

I-Octyl chloride, t169 z-Octyl iodide, 102, t169 .-Octyne, t429 l-Octyne, t429 Idor -

acid chlorides, 755 amines, 823 carboxylic aci+, 717 and configurabon, 137 esters, 755

Yi of wintemeen, 9 14 - 3ils

definition, l l20 drying,. l l27 hardemng of, 1 127 hydrogenation of, 1 127

31+, George, 192,347,376,526,535 31eic acld, 713, t715, 1122 3leomargarine, 1 127 31eyl alcohol, 773 3ligosaccharides, 1 198 Olive oil, t1121 Olivetol, 9 ! 5. Optical act~nty, 128 - 130

in armnes, 825 in amino acids, 1049 - 105 1 and ckahty, 1.39, 154- 155 and configurat~on, 140-141, 1173-1174 and enantiomerism, 133 in naturally occumng substances, 159

Optical families, 1162- 1164 Optical isomers, see Stereoisomerism Optical purity, 156,194 Orbitals. 6.992

atomic, 6-7 bond, 9,10 geometry of, 15,275 hybrid, 1 1 - 19,276 molecular, 9,99 1 - 1030 overlap of, 9 - 10 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 sp 11-13,426 S$, 13-15,67-69,274-275,502 S$, 15-19,453 (See also Molecular orbitals)

Orbital symmetry, 1004- 1024 Orcmol, 9 15 Organoborane compounds, 933-935 Organocopper compounds, 102

in preparation of ketones, 664,668-669 reactivity, 668

Organolithiumcompounds, 102,685,696,966-967 Organometallic compounds, 100,437,686

adhhon of carbenes, 477 -478 coupling with alkyl halides, 10 1 - 102 Gripard reagent, 99, 100 use in synthesis, 923

Organosodium compounds, 102 Orientation, 538 - 540.

of free-radd adhbon, 352-355 of halogenation, 107 - 109 in hydroboration, 348 - 349 reactivity and, 114- 115,300-303,307,335-

338,337,391,536-540,579 Saytzeff S rule, 3 14 in substitution, 520-521,522-524,545 -546 and synthesis, 524- 525

Orlon, see Polyacrylonitrile Ornithine, 1250 Ortho effect, 736, 853 Ortho,para-directing groups, 519-525, 542, 848,

860,900,905,948 (See also Orientation) Osazones, 1 15 1 - 1 152 Osmium tetroxide, 484 Osones, l l5 1

Oxalic acid (eeanedioic acid), 705, t742 Oxaloacehc acid, 1 1 14, 1 139 Oxazole, 1057 2-Oxazoline, 932, 1058 Oxidation

of alcohols, 226,235-237,662,663,665, of aldehydes and ketones, 675 - 677 of alkenes, 359-360 of alkvlbenzenes. 563-564 if amines, 823 ' biological, 1 103 - 1 106

of ethanol, 1 101 - 1 106 of carbohydrates, 1 149 - 1 150 in determination of structure, 699 of 1,2-diols, 699 of methane, 42-43 of methylbenzenes, 662,665

Onmes, 673,679,697 Oxirane ring, 48 1 Oxonium ions, 34,906 0x0 Drocess. 218. 1052- 1053 oxygen, 178 .

electron-deficient, 895 - 896 as tracer, 1 18 transuort of by hemoglobin, 1235

Oxygen exchange in hydrolysis of esten, 774-775,778 in rearrangement studies, 896

Oxygen-hydrogen bond, 20 0xym~;curation-demercuration, 222,32 1,

54 1 Oxytocin, 1216- 1217 Ozone. 70. 1 19.359 ozone'layer .

deplebon of, 3,69-71, 120 formation of, 70

Ozonides, 359 Ozonolysis

of alkenes, 358-360 of dienes, 422

Paints. 1 127 e g , 1100

Pal1111bc acld, t7 15 biosynthesis, 1 134

Palm kernel oil, t 1 12 1 Palm oil, t1121 Pamaquine, 1075 Pan, S.C., 1203 Paneth, Fritz, 76 (+)-Panose, 1203 Pantothenic acid, 882 Papaverine, 75 Paraffin-based petroleum, 96 ParafEns, see Alkanes Paraflin wax, 96 Paraformaldehyde, 660,661 Paraldehyde, 66 1 Paramagnetism, 573 Para red, 875 Pasteur, Lams, 130, 138, 1164 Pauli, Wolfgang, Jr., 8 Pauli exclusion principle, 8,398 Pauling, Linus, 10, 1230 Peanut oi, t1121, 1137 Pectic acid, 1203 Pectin, 1203 Pedersen, Charles J., 479,916-917 Pendant groups, 1080 Penicillin G, 863, 1059 Penicilliurn glaucum, 137 D-Penta-o-acetylglucopyranose, 1 184 Penta-o-acetylglucose, 1 145 D-Penta-o-acetylmannopyranose, 1 184 n-Pentadecane, 8 3 1,3-Pentadiene, t411,442, 1017

1316 14-Pentadiene Phenylacetyl chloride

1,4Pentadiene,.410, t411 Pentadienyl cabon, 101 1 Pentaeryhitol

physical constants, c216 synthesis, 8 18

Pentamethylbenzene, t553 Pentamethylsalicin, 1 182 n-Pentane, 87, t272,599

CMR, chemical shift, 636,637 nomenclature, 90 physical constants, t93, t217,442,660

2,4Pentanedione, 798 NMR spectrum, 820 preparation, 8 16

Pentanenitrile (valeronitrile), 212, 722, 724, 725

~ent&es, 90 - 92 isomers of, 87,95

Pentanoic acid (valeric acid), t7 15,7 16, 722, 750, 1175

reductive amination, 835 3-Pentanone, 226,659, t661 l-Pentene, t285, 306, t326, 360,599,855 2-Pentene, t285,306, ~326,326, 329,442,855

isomers of. t285. t326.327 Pentosan, l062 '

Pentose. 1062 n-pent$ acetate, t769 n-Pentyl alcohol, t2 16,224 tert-Pentyl alcohol (2-methyl-2-butanol), 2 15,t2 16,

314 7211 - - . , . - - n-Pentylamine, 830 tert-Pentylbenzene, 560 n-Pentyl bromide, 99,1169 tert-Pentyl bromide, 306,3 10 tert-Pentyl cation, 205 n-Pentyl chloride, 89, t169,430,224 tert-Pentyl chloride (2chloro-2-methylbutane), 722

preparation, 230,336 Pentylenes (amylenes), 282 n-Pentyl iodide, t 169 tert-Pentyl iodide, see 2-Iodo-2-methylbutane n-Pentyl phenyl ketone, 663,667 2-Pentyl tosylate, 306 2-Pentyltrimethylammonium ion, 855 2-Pentylurethane, 783 l-Pentyne, t429,442 2-Pentyne, ~429,438 3-Pentyn-2-01,692 4-Pentyn-1,2,3-triol, 1 18 1 Peptide chains, 1226, 1230 Peptides, 12 15; 1225, 1240

molecular weights, 12 18 peptide linkage, 12 15 - 1217

geometry of, 1 2 16 structure determination. 12 17 - 122 1 synthesis, 1221 - 1225

solid-phase, 1225 Periodic acid, 237,359- 360 A

analys~s of carbohydrates, 1150 analysis of 1,2-diols, 699

Per idc Table, inside back cover Perkin condensahon, 8 10-8 1 1,973 Permanganate test, 694 Peroxide effect. 330- 33 1

mechanism. '35 1 - 352 Peroxides, 330

analysis for, in ethers, 238. effect on orientation, 579- removal from ethers, 240

Peroxy acids, 357-358 Peroxybenzoic acid, 322,48 1 Peroxyformic acid, 358,484 Perutz, M.F., 1235 Petroleum, 1,2 19,220

constituents, 94, t96 source of alcohols, 218

source of aromatic compounds, 555 source of carboxvlic acids. 720 uses, 96

Petroleum coke, t96 Petroleum ether, 8 6 Petroleum jelly, 96 Phases -

of orbitals, 992-994 of waves, 992

Phase-transfer catalysis, 265 (+)-Phellandral, 9 17 (-)-Phellandral, 9 17 (-)-PheUandric acid, 9 17 Phenamn, 9 16 Phenanthrene. 5 10

test for, 580 Phenetole, see Ethyl phenyl ether Phenol, 889, t890

industrial source, 555-556,894 reactions, 240,447, t520,531, 540-541, 899-

902.905-911 , - - - - - - relative acidity, 899 , , use, 893 (See also Phenols)

2,4-Phenoldisulfonic acid, 907 Phenol-formaldehyde resins, 109 1 PhenoGc an&, 908 Phenohc esters, 738 Phenolic ethers

preparation, 902 spectroscopic analysis, 596, t607,

913 Phenolic ketones, 905,907 Phenols, 2 14,889-922

acidity, 843, 874-875, t890, 903- 1009 effect of substituents, 904

aldehydes from, 902,908-909 analysis, 843,912-913 carbonation, 902,908 coupling with diazonium salts, 868,873-875 electrophili~ substitution, 900 - 902,906 - 907 fiom essephal oils, 894 estenficahon, 738, 899,905 ether formation, 902 formation, during diyotization, 870 Friedel-Crafts acylahon, 90 1 Friedel-Crafts alkylation, 90 1 Fries rearrangement, 901,905 halogenation, 901,906 hydrogen bonding, 89 1 - 892 industrial source, 893 - 894 ionization, 843 Kolbe reaction, 902 nitrosation, 90 1 in polymerization, 1090- 1092 preparabon, 895 -899

from diazonium salts, 868, 870,898 reactions, 240,868

with d i~on ium ,salts, 873- 875 with femc chlonde, 9 12 with forpaldehyde, 1090- 1092

Reimer-Tiemann reaction, 902,908 ring substitution, 906-908 salts. 843 speckoscopic analysis, t592,t786, 9 sulfonation, 900 Williamson synthesis, 902, 910 (See also Hydroquinone)

o-Phenolsulfonjc acid, 900, 906 pPhenolsulfomc acid, 900, 906, 907 Phenoxyacehc and, 902 2-Phenoxvethanol. 9 10 ~henoxid; ion, 843; 903,904,910 Phenylacetaldehyde, 659, t661 Phenylacetamide, 727 N-Phenylacetamide, see Acetanilide Phenyl acetate, c769 Phenylacetic acid, 713, t715,722,727 Phenylacetomtrile, 830 Phenylacetyl chlonde, 727

Phenylacetylene Polyamides

Phenylacetylene, 55 1, t553 Phenylalanine, 1209 (-)-Phenylalanine, t 1207, 12 13 Phenylalkanes, 55 1 p(Phenylazo)phenol, 868 2-(Phenylazo)pyrrole, 1063 N-Phenylbenzenesulfonamide, 848 Phenyl benzoate, 547

preparation, 762,899 l-Phenyl-I,3-butadiene, 583, 801 l-Phenyl- 1,3-butanedione, 820 2-Phenyl-2-butene, 55 1 4-Phenyl-3-buten-2-one, 801,810,973 3-Phenyl-2-butyl tosylate, 1055 y-Phenylbutyic acid, 7 16,738 Phenyl carbitol, 484 l-Phenyl-l-chloroethane, 552,577 2-Phenyl-l-chloroethane, 552 l-Phenyl-2-chloropropane, 577 l-Phenylcyclopentene, 473 2-Phenylcyclopentyl tosylate, 473 l-Phenyl-3,4-dibromo-l-butene, 583 m-Phenylenediamine, t824 o-Phenylenediamine, t824 pphenylenediamine, 5 14, t824,828, 1099 Phenylethanal, 659 l-Phenylethanol, see a-Phenylethyl alcohol 2-Phenylethanol, see&Phenylethyl alcohol a-Phenylethyl alcohol (l-phenylethanol), 170, 194,

t216, 552, 557, 577 preparation, 672,689

/3-Phenylethyl alcohol, t2 16,552 preparation, 688

a-Phenvlethvlarmne, f824

. preparation, 830 a-Phenylethyl bromide (l-bromo-1-phenylethane),

t169. 857 p G ~ t i o n , 170,550,566

B-Phenylethyl bromide, t169,296-297,857 cu-Phenyle%yl chloride, 159, t169, 194,552,567

preparaaon, 563 /3-Phenylethyl chloride, t169,552,557,567

preparation, 563 Phenylethylene, see Styrene a-Phenylethyl hydroperoxide, 896 p-Phenylethyl iodide, t 169 Phenylglyoxal, 684 Phenyl group, 296 Phenylhydrazine, 673 -674,679,680

in carbohydrate studies, 1 15 1 Phenylhydrazine hydrochloride, 679 - 680 Phenylhydrazones, 673-674,679 Phenyl isothiocyanate, 12 19 Phenyllithium, 1070

reactions, 949,966 Phenylmagnesium bromide, 688,689,704 Phenvlmalonic ester. 748. 816 - 2 -p~ - -

l-~hen~l-3-meth~l-2-bu&l, 691 5-Phenyl-2,4-pentadienal, 8 10 3-Phenylpropanoic acid, 716 1-Phenyl-2-propanol, 183,577 l-Phenyl-2-propanone, 660 3-Phenylpropenal, 677 3-Phenyl-2-propenal, 801,8 10,973 l-Phenylpropene

cis and trans isomers, 583 preparation, 577

2-Phenvlurouene. 584

. . , . . . - , . , . propen-1-01 (cinnamyl alcohol), t216,

Phenyl n-propyl ketone, 672 2-Phenylpyxidne, 1070 Phenylthiohydantoins, 12 19 Phenyltrimethylammonium iodide, 829 Pheromones, 382,442,491,819, 1055 Phillips, Henry, 180 Phloroglucinol, 9 16 Phosgene (carbonyl chloride), 780,78 1-782,789,

1222 manufacture, 78 1 reactions, 782

Phosphate esters, 1 128 - 1 130 Phosphatidic acid, 1 128 Phosphatidyl choline, 1 130 Phosphatidyl ethanolamine, 1 130 Phosphoglycerides, 1 128 - 1 130 Phospholipids, 882, 1 128,1129 - 1 130

in cell membranes, 1 130 - 1 13 1 Phosphonium salts, 8 12 Phosphoric acid, 1128, .l 129 Phosphorus pentachlonde, 737 Phosphorus trichloride, 737 Phosphorus trihalides, 225,692 Phosphorus ylides, 8 12 Photolysis, 69 Photosynthesis, 220, 1 143, 1 182 Phthalamic, acid, 768 Phthalic acld, 564, t715, t742

lndustnal source, 720 Phthalic anhydride, t755

in polymerization, 1090,109 1 preparation, 763 reactions, 765,768

Phthalimde, t755,844 acidity constant, 768 preparation, 768

Phthalimidomalonic ester method, 1214 Phytol, 1 122 Picolines, t1058, 1067- 1068 Picolinic acid, t1058 x-complexes, 506 -507, 1045, 105 1 Picric acid{2,4,5-trinitrophenol), 547,

preparabon, 899,907,953 Picrvl chlonde. t945.953-954 Pimklic acid, h75 ' Pinacol(2,3-dimethyl-2,3-butanediol), 705 Pinacol rearrangement, 705 Piperic acid, 9 18 . Pipendine, 837,982,988,

in alkalojds, 1073 preparaaon, 9 18, 1073

Piperine, 9 18 Piperonal t66 1, 9 19 Piueronvlic acid. 9 18 &er, $.S.? 468 Plane-polarized light, 128 Plasticizers, 1 126 Plastics

industry, 420 preparabon, 1077 structure. 1096 uses, 1077 - 1078 (See also Polymers)

Plemglas, 973, 1081, 1096 PMR, 600,629 Polar effect, 185 - 186, 199 (See also Electronic ef-

fects) Polar factors

in free-radical addition, 354 in Hofmann orientabon, 855 - 857

Polarimeter. 128- 129 Polarity ,

of bonds, 23 ,

of molecules, 23 -26 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 copolymers, 1096

Polychloroprene, 420 Polycyclic compounds, 445 -446 Polyester resin, 1097 Polyesters, 1090 Polyethylene, preparation, 356, 1088 Polyhalomethanes, 7 1 cis-Polyisoprene, 420 -42 1, 1089, 1095 Polyme.rization, 356-357, 1077- 1100

addibon, 1079 of alkenes, 356-357,419 anionic, 1084- 1085 "back-biting", 1083 cationic, 1084- 1085 chain-reaction, 1078 condensation, 1079 definition, 356 of dienes, 4 19 -42 1 free-radical vinyl, 1080- 1083

of alkenes, 356-357 of dienes, 4 19 -42 1

stepreamon, 1078- 1079 stereochemical control, 1088 transfer constant. 1082 vinyl, 1080

Polymers, 356,419-421, 1077- 1100 branched, 1096 crystallinity, 1088- 1096 formation, 356,419-421 linear, 1096 living, 1084- 1086 surface-active, 1097

Poly(methy1 methacrylate), 973, 108 1, 1096, Polynuclear aromatic compounds, 5 10- 5 12 Polvnucleotide chains. 124 1 ~ol~(oxyprop~lene) glycols, 485 Polypeptides, 12 15 (See also Peptides) Polypropylene, 1088- 1089 Polysaccharides, 1077- 1078, 1 192- 1201

definition, 1 144 Polystyrene, 108 1, 1082

copolymers, 1083- 1084 properties, 1096

Polystyrene(co-methyl methacrylate), 1083 Polyurethane foam rubber, 485 Polyurethanes, 1092 Poly(viny1 acetate), 1093 Poly(vinyl chloride)

preparation, 356, 1080 properties, 1094, 1096

Poly(vinylidene chloride), 1094 Ponnamperuma, Cynl, 159 Porphin, 1228 Porphyrin system, 106 1 Potassium permanganate, 358 Potassium tert-butoxide, 476,703

preparation, 225 Potassium 2,3dibromopropanoate, 7 17 Potassium (~j3-dibromopropionate, 717 Potassium d-tert-butylphenoxlde, 934 Potassium isopropoxide, 227 Potassium phthalimide, 1213,1214 Potassium triphenylmethide, 970 Potential energy changes

in 1,2- vs. 1,4-addibon, 418 in chlorination of allcanes, 107 and conformation, 82,85,458 in halogenation of methane, 52,53,61,66, in hydrogenation of alkenes, 325 in simple dissociation, 55

Power sources, 2 Pre-cholecalciferol, 1030 5a-Pregnane-3a-ol-20-one, Prehnitene, t553 Prelog, V., 134, 140 Primeverose. 1202 Prismanes, 51 5 Probability, and orbitals, 6

Probability factor, 59 and reaction rates, 55 - 56

Prochiral center, 1 107, 1 1 1 1 Progesterone, 1141 - 1142 (-)-Proline, t 1207

synthesis, 1248 Proline residue, 1234 1,2-Propadiene, t4 1 1 Propanal, see Propionaldehyde Propane, 83-85, t93,319,397,449

rotational barrier in, 83 Propanedioic acid, see Malonic acid 1,2-Propanediol, t216, 322,485,491

preparation, 322,358, 11 15 (+)- 1,2-Propanediol, 1 163 1,3-Propapepiol, t2 16 Propanemtnle, 247 1,2,3-Propanetriol, see Glycerol 2-Propanol, see Isopropyl alcohol Propanone, see Acetone Propargyl chloride, t169 Propenal, see Acrolein Propene, see Propylene Propenenit.de, see Acrylonit.de Propenoic acid, see Acrylic acid 2-Propen-l-ol,2 14,283 Properties, and structure, 1 - 38 Prophos, 105 1 /l-Propiolactone, 1098 Propiolic acid, 988 Prppionaldehyde, 226,323,659, t661

in aldol condensahon, 806 Propionamide, t755 Propionic acid, 660, t715,717,750, 833, 973,

infrared spectrum, 745 - 746 Propionyl chloride, 2755 Propiophenone, t66 1 n-Propyl acetate, t769 n-Propyl alcohol, 170, t216,226,229,316,348 n-Propylamne. t824. 847

preparation, 828 '

n-Propylbenzene, 551, t553,559,584 NMR spectrum, 6 18

n-Propyl bromide, 124, t169, 170, 188,240,31 330,353,388,926

n-Propyl chloride, 89,104, t169, t217,229,t272, NMR sienals. 602

n-~ro~~ldi'heth~lamine, 847 n-Propy13,5dinitrobenzoate, 762 Propylene, 276,280,282,284, t285, 316, t326,

337-339,397 CMR and NMR analysis; 637-638 polymerization, 1088, 1097 preparation, 290-291 reactions, 319-320,322,323,335,338,342,

349,358,364,388 structure. 276

Propylene bromide (1,2dibromopropane), 3 19, 339.429

Pro~vlene chloride. 389 ProGlene chlorohydrin (l-chloro-2-propanol),

23 1,320,342,487 Propylene oxide, 485,491 Propyl groups, 90 n-Propyl iodide, t169 n-Propylmagnesium chloride, 100 n-Propylmalonic ester, 925 n-Propylmethylamine, 847 n-Propyl m-tolyl ketone, 664, 667 n-Propyltrimethylammonium iodide, 847 Pro~yne, t429.436.437

preparation; 429. Propyn-l-yllithium, 437 Propyn- l -ylmagnesium bromide, 437,692 Pro-R. 1 108

7 - - - - pro-~, 1 108 Prosthetic groups, 286, 1228- 1229 Protecting groups, 696,861, 1222, 1224 Proteins, 1 132, 1205 - 1206, 1225 - 1235

Protein sequenator Rearrangement

p-,' 1234 classification and function, 1225 - 1226 conformational analysis, 1229 conjugated, 1228 - 1229 denaturation, 1225 - 1226 DNA and synthesis, 69, 1246- 1247 fibrous, 1225 globular, 1225 - 1226, 1234 isoelectric point, 1226 peptide chains, 1226 side chains, 1226 structure, 1226

'rotein sequenator, 12 19 'rotic solvents, 254-258 'rotium, 1 17,969 'rotocatechuic acid, 9 18 htodesulfonation, 530 3otonated alcohol, 176 'rotonated epoxide, 9 10 - 9 1 1 %otonated ether, 242 -243 ?rotonation, of aromatic compounds, 5 19, 530 Proton counting, 609 Proton exchange, 640 Proton magnetic resonance (PMR), 600,629 Protonolvsis. 934 Protons ih nuclear magnetic resonance

alignment, 600-60 1 chemical shifts for, characteristic, t607 counting, 609 equivalence, 601 - 604,605 -606,625 - 629 and psitlon of W R signals, 604-608 shleldmg and desbeldmg, 604 spin-spin coupling, 6 10-620 vicinal. 620 vinylic; 620

Pseudocumene, t553 Pseudotropine, 1076 D-Psicose, 1 162 Puckered rings, 452 Purine, 837, 1057 Purity, of syntheac products, 871 Putremne. 844.986 .- . -

PVC, see P d ~ ~ ( ; i n ~ l chloride) Pyran, 1 177 Pyranose ring, 1 178 Pyranosides, 1 178 *ale, l057 Pyridine, 385,837, 1057, t1058, 1064, 1073

in alkaloids, 1073 as base, 762 basicity, 1071 - 1073. electrophibc aromahc substitution, 1068- 1069 nitration. 1068 nucleopf;ilic aromatic substitution, 1069- 1071,

I n77

reduction, 1073 source, 1067- 1068 structure, 502-503, 1066- 1067, 1073 sulfonation, 1068

Pyridineacetic acids, 1076 Pyridinecarboxylic acids, 1069, 1074 2-Pv~idinecarboxvlic acid, 1067 - 1068.1074. 1076 3-P$dinewboxj4ic acid.(niacin, nicotinic acid),

t1058, 1067- 1068, 1074 decarboxylation, 1076

4-Pyridinecarboxylic acid (isonicotinic acid), 1067- 1068. 1074 - - . - - - - 7 - - -

physical constants, t1058 preparation, 1068

Pyridine methiodide, 1072 Pyridine N-oxide., 10/2- 1073 3-Pvridinesulfomc a a d 1068 F'yridinium chlorochromate, 237,662 Pyrimidine, 837,1057 Pyrolysis, of alkanes, 120- 121

Pyrro!el 516, 548, 837, 880, 1057, t1058 b a ~ ~ a t y , 1060 - 1062, 1064 reactiops, 1062- 1063, 1064,1074 reactinty, 1064 Source, 1060- 1062 structure, 548, 1059-1061, 1065

2-Pyrrolecarboxaldehyde, 1064 Pyrro!kjine, 837,880, t1058

basicity, 1065

reactions, 937 structure, 1057, 1065, 1066 . '

h n h n e . 1074

Q Qualitative elemental analysis, 72 - 73 Quantitative elemental analysis, 5 13 - 5 14 Quantum mechanics, 4,5,991 Quat, 265 Quaternary ammonium hydroxide, 854 Quaternary ammonium salts, 258,265,834,849,

854-855, 1072 (-)-Quinine, 159, 160 Quinoline, 1057, t1058,1069 Quinones, 984-985

R, prefix, for configuration, 140- 141, 1 108, 1 163 R, symbol for alkyl group, 97 Racemic m d c a t i o n

definition, 138 formation, 15 1

Racemization, 368 through free-radical formation. 161 partid, 194 resolution, 138, 153, 158- 160 in,%l reactions, 194, 196

Ra&abon, biolo@cally harmful, 70 Radical-anion, 1085 - 1086 Radical character, 1 15 Radicals, see Free radicals Radioactive labeling, see Isotopic tracers (+)-Ra5nose, 1202 Rancidity, of fats, 1127 Rappaport, Zvi, 408 Rate constant, 178 Rate-determining step, 188,297 Rate equation, 57 Rates of reaction, 55-59, 166- 167, 177,

1041 and activation energy, 56 and molecular structure, 1 14 and probability factor, 55 -56 relative, 58-59 and temperature, 58

Rayon, 1201 Reactant state, 579 Reaction constant, 732 Reaction mechanisms, 45 Reaction progress, 52- 55 Reaction rate, see Rates of reaction Reactions

intermolecular. 448

andselectivity, 115-116 Rearrangement

of carbocations, 203 - 208 in dehydration of alcohols, 3 14 in electrophilic addition, 334-335

1320 Reducing sugars Skewphos

Rearrangement, (cont.) in Friedel-Crafts alkylation, 559 in Hofmann degradation, 838 - 843 of hydroperoxides, 895 - 898 Lossen, 844 in SN1 reactions, 204-208,405-406

Reducing sugars, 1 144 ondabon rate, 1 182

Reduction biologcal, 1 103 - 1 106 (See also Hydrogenaaon and specijic compouj

orfamily) Reductive amination, 831,834-835, 1214 Reeves, R.E., 1 179 Reface, 1111 Reformatsky reaction, 939 Reforming, see Catalyhc reforming Regioselective reactions, 327 - 329,346 Re~mer-Tiemann synthesis, 5 19,902,908 - 909 Relaave reactivity, 45 Replication, 1246 Repulsive forces, 20 Reserpine, 1059, 1073 Resins

structure, 1096 synthesis, 1090- 1092

Resolution, of racemic modification, 138, 153, 158-160 ..- -..

Resonance, 387-424 alkenes, 4 13 allyl radical, 395 - 399 aromatic amines, 85 1 aryl and vinyl halides, 950-952 benzyl cation, 574 b e q l radical, 568-570 carbanions with a-ionization, 798 carboxybc acids, 733 chloromtrobenzenes, 957- 959 conjugated dienes, 4 1 1 -4 12 definition, 394 electron withdrawal by, 958-959 hybrid, 394,526 phenols, 904 theory of, 394

use of, 399-401 Resonance effect, 200,406 Resonance energy

alkyl free radicals, 40 1 allyl radical, 397-399 benzene. 498 - 500 beGi&-c;?, 568 -570 conjugated denes, 41 1 definition. 394 pyrrole, &n, and thiophene, 1059- 1060 triphenylmethyl radical, 570-574

Resonance s tabht ion aromatic F n e s , 851 -852,860-861 b e w l rad~cal, 568-570 carboxylic acids, 733 phenols, 904 urea, 781-782

Resonance structure, 500 Resorcinol, 677,889,901 Respiration, 1 1 14 Retinal, 286-287 Retinol, 286 Reversible reactions, 730-732 Rhodopsin, 286 Ribitol, 1 160 Ribonucleic acids, see RNA (-)-Ribose, 1 160, 1 162 D-Ribose, 124 1 Ring closure, 452 (See also Cyclization) Ring-opening reactions, 449 RNA (ribonucleic acids), 1241 - 1243, 1250

and geneucs, 1246 - 1247 messenger, 1246 structure, 1241 - 1242, 1245 transport, 1247

Roberts, L, 374, 1034

Roberts, John D., 395,626,963 Rosanoff, M.A.? 1 166 Rotational barner

in carbon-carbon single bonds, 79 - 83 in ethane, 82 in Drouane. 83 ( ~ i e dso.&bon-carbon bonds)

Rotaaonal isomers, see Conformational isomers Rubber, 419 -421

preparation, 420 ~d structure, 420, 1095 - 1096

vulcanization, 420, 1096 (See also Natural rubber, cis-Polyisoprene)

Ruberythnc acid, 1202 Ruff degradation, 1 154 Russell. Glen. 1 17 "~uss&ndoll" molecule, 5 12

S S, prefm for configuration, 140- 141, 1 108, 1 163 Saccharic acid, see Glucaric acid Sacrificial hyperconjugation, 413 Safrole, 894, 919 Salicin, 1 182 Salicylaldehyde, 546,659, t661,1182

preparation, 902,908 Salicylic acid, t7 15,748

preparation, 908 Saligenin, 1 182 Salmine, 1 2 1 8 Sandmeyer reaction, 866,879 Sanger, Frederick, 12 18, 1220- 122 1, 1249 - 1250 Saponification, 1124- 1 125, 1 138 Saponification equivalent, 784 Saran, 357,1080, 1094 Sarett, Lewis, 984 Saytzeff, Alexander, 301 Saytzeff orientation, 301,306 - 307 Saytzeff's rule, 301,307,314 SBR (styrene-butadiene rubber), 1096 SchX test, 697 Schlesinger, H.L, 349 Schleyer, Paul, 202,270 Sch8niger oxidation, 72,211 Schotten-Baumann reaction, 762,770,858-859,

1072 Schr&linger, Envin, 5 Seagram, Joseph E., 1203 Second. 939 Secon& structure, of proteins, 1229 - Selectivity, 105

and reactivity, 1 15 - 1 16 Semicarbazjde, 673,679,680,705,990 Se*carbazide hydrochloride, 679 Semcarbazones, 673,679,697,990 Sequence rules, for configuration, 140- Serine, in chymotrypsin, 1237- 1238 (-)-Serine, t1207 Sex attractants, 382, 706, 1029 Sex hormones, 1 136 Sex pheromones, 442,819, 1055 Sheehan, John C., 1248 1,2-SW, 206-207,839, 895, 1041

stereochemisty, 840 S i c k l e 4 anemia 1227. 1247 S i f a ~ , l l l l ' '

a orbitals, see Orbitals, Molecular or1 Sigmatropic reamons, 10 19- 1024 Silk fibroin, proposed structure, 123 1 Silver ammonia ion, 676 Silver mirror test, 671, 676 Silver nitrate, 2 1 1 Simmons. H.E.. 477-478 ~immons'-smith reaction. 477-478 Singlet methylene, 474-476 Skell, P.S., 475 Skew conformations, 79 Skewphos, 105 1

Smalley, Richard E. Steric repulsion

Smalley, Richard E., 5 12 Smith, R.D., 477-478 &l reactions, 232,409

mechamsm and lanetics, 188 - 189 migration, 841, 1035 reactivity, 200-203,404-406 rearrangement, 204-208,405 -406 role of solvent, 258-26 1 stereochemistry, 194- 196,368 theory, 19 1 vs. &2 reactions, 180,208-210,576

&2 reactions, 232 cleavage of epoxides, 485-487 migrahon, 841, 1035 mechanism and kinetics, 181,955-956 phase-transfer catalysis, 264-266 reactivity, 185- 186,407 role of solvent, 26 1 - 264 stereochemistry, 182- 184,367 steric factors, 187 - 188 vs. &l reactions, 180,208-210,576

Soaps cleansing power and solubility, 1 124- 1 125 manufacture, 1 124 - 1 125 ,

Sodioacetoacefic ester, 8 14,927 Sodiomalonic ester. l2 13 Sodium, 229 Sodium acetate, 680,939 Sodium acetylide

formation, 436 reactions, 438

Sodium &oxides, 227,241 -242 Sodium amide, 1070 Sodium azide, 839 Sodium benzenesulfonate, 894, 1200 Sodium benzoate, 717,725,771,859 Sodium borohydride, 346,349,35 1 Sodium a-bromopropionate, 1034 Sodium tert-butoxide, 241 Sodium butyrate, 767 Sodium chloride, 27,30 Sodium chloroacetate, 743 Sodium cyanoacetate, 743 Sodium cyanohydridoborate, 834 Sodium 2,4-di111trophenoxide, 899 Sodium ethoxide, 225,227,309,483,814,815 Sodium formate, 683,749

bond lengths, 397,734 Sodium hslon, 72,211 Sodium hydroxide, 684 Sodium 0-hydroxybenzoate, 902 Sodium isopropoxide, 240 Sodium lactate, 1034 Sodium laurate, 725 Sodium lauryl sulfate, 1126 Sodium mandelate, 684 Sodium methoxide, 684 Sodium o-nitrobenzenesulfonate, 954 Sodium pnitrobenzoate, 683 Sodium periodate, 359-360 Sodium phenoxide

formation, 899 reactions, 894,902

Sodium ecylate, 902,908 Sodium tnchlorocetate, 938 Soft soap, l l24 Sofid-phase peptide synthesis, 1225 Solubility

and interionic forces, 3 1 and intermolecular forces, 250-258 and structure, 3 1 - 33

Solutes, see Ionic solutes, Non-ionic solutes Solvating power, 254 Solvation. 228 Solvents

alcohols as, 217,255,256-257 aprotic and protic, 26 1 -264 effect on rafe of reaction, 258-264 and reactinty, 175 role of, 210,249-272

Solvolysis, 268-271, 1039 nucleophilic ass~tance to, 269 - 27 1

Solvomercuration, 347 Sorbic acid, B72 Sorbitol (gucitol), 1 145, 1 149 D-Sorbose, 1 162, 1 183 Soybean oil, t 1 12 1 Space-network pol&ers, 1090, 109 1 structure, 1096 - .

Spandex, 1094, 1097 Specific rotation, 129 - 130 Spectra, analysis of, 642 S~ectrometers. 585 ~&ctroscopic methods, 585 - 586 Spectroscopy, and structure, 585 - 586 Suermaceti. 1 137 Skrmine, 986 Spin-spin coupling, in NMR, 610-620 Squalene, 1 136 - 1 137 Standing (stationary) waves, 992 Stang, Peter, 408 Stannic chloride, 35 Starch, 219,220, 1143- 1144, 1192-1193 Stark, Charles M., 265 Steam cracking, 120 - 12 1 Stearamide, l755762 Stearic acid, t715,726,762 Stearoyl chloride, 726, t755,762 Stepreaction polymerization, 357,1078- 1079,

1089- 1092 Stereochemical control, 234-235, 1088 Stereochemistry, 125- 164, 175,367-386, 1106

in addition of halogens, 368- 376 m U n e hydrolysis of esters, 772-775 and chlonnation. 160- 162.368 control of ~olymerization, 1088 definition,-125 in Diels-Alder reaction, 10 13 - 10 18 of electrocyclic reactions, 1005 - 10 13 of elimination reactions, 377-380,471- of epoxide cleavage, 483-484 of fatty acids, 1 122 of(+)-~~UCOS, 1146-1149,1155-1160 of Hofmann elimination. 855 of homogeneous hydrogenation

diastereoselectinty, 1046 - 1049 enantioselectivity, 1049- 1052

of hydroboration, 348-349 of neighboring group effects, 1032- 1035 of nitro en compounds, 825 - 827 optical families D and L, 1162-1 164 sequence rules, 14 1 - 144 of &l reactions, 194- 196,368 of &2 ieactions, 182 - 184,367 of stero~ds, 1134- 1136 of (+)-sucrose, 1 19 1 - 1 192

Stereoisomerism cyclic compounds, 464 -47 1 definition, 125,149- 150 diastereomers, 144- 146 enantiomers, 130 - 138 geometric (cis, trans) isomers, 279 mterconvertibility, 149 meso structures, 146 - 147 reactions, 150

Stereoselective reactions, 367-386,433-434 addition, 475 definition, 369 reduction of alkynes, 433 vs. stereospecific reactions, 382-383

Stereospecific reactions, 367- 386 definition, 370,38 1 vs. stereoselective reactions, 382 - 383

Steric factors. 354.454 in butane, 86 . in este&ication, 738 - 739 in Hofmann orientation, 857 in &2 reactions, 187 - 188

Steric hindrance, 185- 188,209,231,738 Steric repuls~on, 86

1322 Steric strain 1,3,5,5-Tetramethyl-l,3cyclohexadiene

Steric strain, 86,454 Steroids, 421,984, 1030,

1140, 1141- 1142 Sterols. 1 134 stigmkterol, 1 141 - 1 142 cis-Stilbene, t553, 583 trans-Stilbene, t553, 583 Stork, Gilbert, 936 Strecker synthesis, 12 14 Structural theory, 3 Structure, 1 - 38

atomic, 6 molecular, 6

Strychnine, 159, 1073 (-)-Strychnine, 160 Styrene (phenylethylene, vinylbenzene), 298, 551,

t553. 557.578 commercial'preparation, 577 polymerization, 108 1 - 1084, 1085 - 1086, 1096

Styrene-butadiene rubber (SBR), 1096 Suberic acid, 750 Substitution nucleophilic bimolecular reactions,

see &2 reactions Substitution nucleophilic unimolecular reactions.

see G 1 reactiois Substitution reactions, see Free-radical substitu-

tion, In$molecular nucleophilic substitution, &l reamons, &2 rea&ons

Substrate. 173 alcohols as. 177 nature of, 209 reactivity of, 179-181. 185. 188

Succinamk acid, 764 Succinic acid, l i 15,742, t742 Succinic anhydride, 1755,763,764 Succinimde, 390, t755 Succinoylsulfathiazole, 864 Sucrose. 218. 1144. 1 146

7 - - - inve&on of. l 19 1

(+)-sucrose, 1185; iiw-1192 Sugar cane, as alcohol source, 2 18 Sulfa drugs, 863-864 Sulfamerazine, 864 Sulfa@-imide, t824,.863 -864

anhbactenal a&vlty, 863 - 864 preparation, 863 N-substituted, 864

Sulfanilic aad, 547, t824 preparation, 862 properties, 862, 1210, 1212

Sulfhydryl group, 1132, 1227 Sulfolane, 258

sblvent, 258,1066 Sulfonamides, 857,863

hydrplysis? 859 relabve aadlty, 860

Sulfonation of aromatic amines, 862 - 863 ofbenzene, 498,518,527,534 of phenols, 900 of pyridine, 1068 of pyrrole, furan, and thiophene, 1062- 1063 reaction mechanism, 527,534-535

Sulfonic acids, 233,529,744 akyl esters of, 177,233-234

Sulfonium ions, 857, 1037 Sulfonyl chlorides, 857 Sulfw, analysis for, 5 14 Sulfur dioxide, 258 S M c acid, 770

reaction with alkenes, 320,33 1-332,333 Sulfur trioxide, 1063 Superacid, 192 Superconductors, 5 13 Superimposability, 127, 149 Suprafaci&reactions, 10 16 Surface-a&ve polymer, 1098 Symmetrical ethers, 237

Symmetry, orbital, 994 Symmetry-allowed reactions, 1004 Symphona, 175,383, 1031- 1056, 1088

definition, 1032 syn-addlbon, 368 -370, 1047- 1048 Syndiotactic polypropylene, 1088 - 1089 Synthesis

procedure, 247 working backwards, 690

Synthetic fkels, 120 Szwarc, Michael, 1086

D-Tagatose, 1 162 (+)-Talose, 1 16 1 Tamelen, E.E., van, 1030 Tanret, C., 1 169 Tarbell, D.S., 989 Tartaric acid, 154,9 18

configuration, 140, 1 164- 1 166 optical activity, 130, 154- 155

(+)-Tartaric aad, 1 164- 1 166 (-)-Tartaricacid, 1161,1167 w(-)-T*c acid, 1 1 65 L-l+bTartanc aad. 1 165 Tauiomerism '

enol-keto, 435 -436 imine-enarnine, 935

Tautomers, 436 . Teflon, 357 Terebic acid, 94 1 TerephthaIic acid (1,4-benzenedicarboxylic acid),

546, 563, 564, t715, t742, 1079, 1099 Terminal residue analysis, 12 18 - 122 1 Terpenes, 421,424,488,492,647,705,915,917,

919,.939:940,941, 1120, 1128 Temnyhc aad. 94 1

y-Te6inene; 42 1 a-Terpineol, 492,9 19,941 Terpin hydrate, 492 Terramycin, 863 Tervlene. l094 ,- - , - Testosterone, 1 136 D-Tetra-0-acetyIribopyranose, 1 184 D-Tetra-0-acetylxylopyranose, 1 184 1,2,4,5-Tetrabromopentane, 4 14 2,2,3,3-Tetrachlorobutane, 644 Tetrachloroethylene, t169,356 Tetrachloromethane, see Carbon tetrachloride Tetracosanoic acid, 1 137 Tetracyclone, 988,990 n-Tetradecane, t93 n-Tetradecyl alcohol, t2 16 Tetraethyllead, 76, 119 1,2,3,6-Tetrahydrobenzaldehyde, 983 A'-3,4-tram-Tetrahydrocannabinol, 9 15 Tetrahydrofuran. t238.258.478. t1058

is solvent, 346, 1066 5,8,9,10-Tetrahydro-1,4-naphthoquinone, 983 cis-1,2,3,6-Tetrahydrophthalic anhydride, 983 Tetrahydropyranyl esters, 788, 1058 Tetrahydropyranyl (THP) ethers, 696,704,

1058 Tetr;thy$othiophene

ondabon, 1066 preparation, 1065

Tetraiodoethylene, t169 Tetraiodomethane, t 169 B-Tetralone, 937 Tetramethylammonium chloride, 258 Tetramethylammonium hydroxide, t824 Tetramethylammonium ion, 264,827. 2,2,4,4-Tetramethyl-1,3-cyclobutan~one, 990 1,3,5,5-Tetramethyl- 1,3-cyclohexad~ene, 490

1,1,3,5-Tetramethylcyclohexane, 468 Tetramethylenediamne, t824 Tetramethylene sulfone, see Sulfolane Tetramethylethylene, 282, 990 1,3,4,6-Tetra-0-methyl-D-fructose, 1202 2,3,4,6-Tetra-0-methyl- galactose, 1202 2,3,5,6-Tetra-0-methyl-D-gluconic acid, 11 86,

1187-1188

oxidation of. i 177 reactions, 1 176- 1 177

a-2,3,4,6-Tetra-0-methyl-D-glucose, 1175 - 1178 /l-2,3,4,6-Tetra-O-methyl-~-glucose, 1 175, 1176 3 7 1 1,15-Tetramethylhexadecanoic acid, 1 122 cis-?(R), 1 1 (R)-3,7,11,15-Tetramethyl-2-hexadecen-

, - --- ~et-ethyllead, 76 2,3,4,6-Tetra-0-methyl-D-mannose, 1203 Tetramethylsilane, 605 Tetraphenylethylene, t553 4,5,6,7-Tetraphenylindene, 990 Tetraphenylmethane, 570 rf, 234 rhallium acetate, 529 rhermoplastic polymers, 1096 rhermosetting polymers, 1096 rhiamine, 1059 l'hiazole, 1057 rbiele, Johannes, 504 rhioglycolic acid, 355 rhiois, 1 132 rhionyl chloride, 726,737 rhiophene, 1057, t1058

reactions, 1062- 1064, 1074 source, 1060- 1062 structure, 1059- 1061

rhiourea, 784 THP ethers, 696,704, 1058 .-Threitol, 1 1 15 ,-Threitol- l-phosphate, 1 1 15 rhreo diastereomers, 377,380 keonine, 12 12 -)-Threonine. t1207 :hreose, 380 '

-)-Threose, 789, 1 16 1,1167 'hymine, 1243, 1245, 1246- 1247 'hymol, 894,9 16 'hyroglobulin, 1226 'ollens' reagent, 676,697,705, 1 144, 1 149 'ollens' test. 671. 676 2-~olualdeh~de,'t66 1 -Tolualdehyde, 1661 -Tolualdehyde, 659,1661 'oluene, 508, 551,1553, 562, 568-570,667, 720,

8'31 brimination, 1521 industrial source, 446,555-556 nitration, t520,t521 NMR spectrum, 606,608 orientation of electrophilic substitution, 538 -540 vrevaration. 557 ktd compdson, 536-537 reactions, 171,519,525,562,565-566,567,

690? 870,871 sulfonahon, t521 vs. benzene, 555

.Toluenediazonium bromide, 87 1 ,Toluenediazonium bromide, 87 1 ,Toluenediazonium chloride. 867.947 ~oluenediazonium chloride: 870' Toluenediazonium hydrogeh sulfate, 867 Toluenesulfonates, 234 Toluenesulfonic acid, 5 19,562 Toluenesulfonic acid; 234; 5 14,5 19,562 Toluenesulfonyl chloride (tosyl chloride), 226,

234,703,900

m-Toluic acid, 17 15, 716, 727 c-Toluic acid, t7 15

infrared spectrum, 746 preparation, 722

pToluic acid, 546, t7 15 preparation, 870

Toluic acids, 7 16 m-Toluidine, 1824 o-Toluidine, 750,1824

reactions, 859,867,868, 871 pToluidine, 822, t824,832

protection of amino group, 86 1 reactions, 870,871,872

c-Tolumtnle, 722, 867 pTolunitrile, 725, 870 2,4-Tolylene diisocyanate, !092 a-(p-~Tolyloxy)isobutyric acld, 9 19 Tors~onal energy, 82 Torsional strain, 79-83,454 Tosylates, 234 Tosyl chloride (ptoluenesulfonyl chloridt

234,703,900 Tosyl group, 234 Tracers, see Isotopic tracers Transcription 1246 ~ransesteri fidtion, 77 1,777-778 Transfer constant, 1082 Transition metal complexes, 1042 - 1046

catalysis by, 1031 - 1056 Transition state? 65-67,579

for halogenahon, 1 13 - 1 14 reactivity and development of, 67-69

Transport proteins, 1 13 1 Transport RNA, 1247 (+)-Trehalose, 1202 Triacylglycerols, 1 120, 1 134 Trialkylborane, 934, 898 Trialkylborane, 898, 934 2,4,6-Trikomoaniline, 509, 547, 822

preparahon, 848 3,4,5-Tribromoaniline, 873 1,2,3-Tnbromobenzene, 873 1.2.4-Tribromobenzene. 509

3,4,5-~ribrornobe&enediazonium chloride, 873 1,1,2-Tribromoethane, NMR spectrum, 6 10,6 12,

h15 ~ribi~moethylene, t169 Tribromomethane (bromoform), 45, t169 3.4.5-Tribromonitrobenzene. 873 - . - . . . -. -.

l; (3-~ribromononane, 355 ' - 2,4,6-Tribromoghenol, preparation, 900,906 Tricarballylic ac~d, 989 Trichloroacetic acid. oreoaration, 727,74 1

Trichloroethylene, t169 Trichloromethane, see Chloroform l, l, l-Trichloro-2-methyl-2-propanol, 909 l , l, l -Trichlorononane, 355 Tricyclo[2.2.1 .OZ6]heptane (nortricyclene), 445 Tricyclopropylmethanol, 646 n-Tridecane, t93 Tridentate, definition, 1042 - 1043 1,3,5-Triethoxybenzehe, 9 16 Triethylaluminum-titanium trichloride, 1087 Triethylamine, t824 Triethylboron, 347 Triethylene glycol, 484 Triflate. 246.408 -409 Trifluoroacetic acid, 26 1 2,2,2-Trifluoroethanol, 26 1 Trifluoromethanesulfonate. 246,408 Trifluoromethanesulfonic acid, 234 Trifluoromethanesulfonyl group, 408 Trifyl group, 234,408 - - - 1,3,5-Trihydroxybenzene (phloroglucinol), 916 l , l, l -Triiodo-3,3-dimethyl-2-butanone, 800 Triiodomethane, t169

1324 1,3,5-Tnmethoxybenzene 8 Vinyl chloride

1,3,5-Trimethoxybenzene, 9 16 Trimethoxyglutaric acid, 1 178 Trimethylacetate ion, 800 Trimethylacetic acid, 724, 726, 727,739 Trimethylamine, 264,316,821, t824,826,846,854

industrial preparation, 828 Trimethylammonium nitrate, 823 2,3,5-Tn-0-methyl-L-arabinose, 1203 1,3,5-Trimethylbenzene, see Mesitylene 2,4,6-Trimethylbenzoic acid (mesitoic acid), 724,

778 719 . U - , . U <

Trimethylethylene, 442 1 ,4,6-Tn-0-methyl-D-fructose, 1202 2,3,4-Tri-0-methyl-D-glucose, 1 198, 1202, 1203 2,3,6-Tn-0-methyl-D-glucose, 1 194, 1 196, 1 197,

1203 2,3,4-Tri-0-methyl-D-galactose, 1203 2,4,6-Tri-0-methyl-&galactose, 1203 Trimethylisopropylammonium ion, 3 16 2,4,6-Tn-0-methyl-D-mannose, 1203 3,4,6-Tri-0-methyl-D-mannose, 1203 2,2,4-Trimethylpentane, 9 1

manufacture, 344 - 345 mass spectrum, 587 octane number, 1 18 preparation, 321,343

2,2,4-Trimethyl-3-pentanol, 316 2,4,4-Trimethyl-l-pentene, preparation, 320,343 2,4,4-Trimethyl-2-pentene, preparation, 320, 343 Trimethyl-n-propylammonium hydroxide, 854 1,1,2-Tnmethylpyrrolidinium hydroxide, 855 1,1,3-Trimethylpyrro~lidinium hydroxide, 855 Trimethylsulfonium ion, 264 2,3,4-Tn-0-methyl-D-xylose, 1198, 1202 2,4,6-TrinitroaniJine, t824 2,4,6-Trinipoanisole, 960

DreDaraoon. 954 2,4,6-'Tri1+trok&enediazonium chloride, 874 2,4,6-Trirutrobenzo~c acid, 750

decarboxylation, 930 2,4,6-Trinitrochlorobenzene (picryl chloride), 845,

957-94A -U- * W .

Trinitrophenetole, 960 2,4,5-Trinitrophenol, see Picric acid 2,4,6-Trinitrophenol, t890,905,906,953

preparation, 898 Trioxane. 660 ~ripeptides, 12 15 (See also Peptides) Triphenylamine, t824 Triphenylmethanol, t216,575,583 Triphenylchloromethane, 558,570,572,575 Triphenylethylene, 2553 Triphenylmethane, 1553

preparation, 558 Triphenylmethyl bromjde, t169 Triphenylmethyl chlonde, t169 Triphenylmethyl dimer, 572 Triphenylmethyl free radical, 570-574 Triphenylmethyl peroxide, 57 1 Triphenylphosphme, 8 12, 1044 Triphenylphosphine oxide, 8 1 1 Triplet methylene, 474-476 Tri-n-propylamine, t933 -934 Triptycene, 1200 Tris(triphenylphosphine)chlororhodium(I), 1044 Tritium. 1 17. 295

isofob effects, 295 Tropic acid, 750 Tro~ilidene. 1076 Trobine, 1076 Tropinone, 1075 - 1076 Tropolone, 1025 Tropylium bromide, 505 - Tropylium ion, 505,507 (-)-Tryptophane, t1207 Ts erou~. 234 ~ubrck'bacillus, 1 138 Tuberculostearic acid, 1 138

~ < n ~ oil, 1100, 1128 composition, t112 1

Turanose, 1202 Twist-boat conformation, 455 -460,457,458 Tyramine, 9 15 (-)-Tyrosine, t1207

Ultraviolet absorption bands, 597 Ultraviolet light, 69, 70, 71 Ultraviolet .spectra, 586,597-598

in analysis of aldehydes and ketones, 701 Umnoluna. 439 n-UndeGe, 83. Unimolecular elunination (El mechanism), 303-

?(l4 Unsaturated acids, 676 a,FUnsaturated acids, 742 a$-Unsaturated carbonyl compounds, 97 1 - 990 Unsaturated fatty acids, 1 122 Unsaturated hydrocarbons, 29 1 (See also AUcenes;

Allcynes; Arenes) Unshared pairs, 17 -20,255 Unsymmetrical ethers, 237 Uracil, 1243 Urea, 780,789

manufacture, 782 reactions, 783 resonance stabilization, 78 1 - 782

Urea-formaldehyde plastics, 782, 1092 Urease, 783 Ureides. 783 ~rethanes (carbamates), 780- 78 1,782, 1223 Urey,.Harpld C., 42 Uroluc aclds, t1149

Vaccenic acid, 1 1 38 Valence electrons, 1006 Valence shells, 4, 5 n-Valeraldehyde, t661 n-Valeramide, t755 Valeric acid (pentanoic acid), t7 15, 7 16, 722, 750,

825 Valeronitrile (pentanenitrile), 212,722,724,725 n-Valeryl chloride, t755 . (+)-Vahe, t 1207 Valinomycin, 48 1 Vampire, lack of mirror image, 132 Van der Waals forces, 29,30,3 1,85 -86, 170,467,

1235, 1240 in butane, 85 in macromolecules, 1093 - 1096

Van der Waals radius, 29 Van der Waals strain, 454 Vanillin, t66 1, 894 Van Slyke, nitrogen determination, 12 15 Van't Hoe J.H:, 126, 131, 1155 Variable translbon state theory, 855-856 Vennesland, Birget, 1 104, 1 1 13 Veratraldehyde, 674 Veratrole, 9 13 Veronal, 938-939 Vicinal dihalides

dehalogenauon, 289 dehydrohalogenation, 429 -430 preparation, 339-340

du Vigneaud, Vincent, 1224 Vinegar, 719 Vinyl alcohol, 435 Vinyl alkyl ethers, 704 Vinylbenzene, see Styrene Vinyl bromide, 845,951 Vinyl chloride, 283,39 1, 845

Vinyl free radical Zwitterions )

NMR signals, 602 polymerization, 356,1080 reactions, 329,544,944 relative reactivity, 338, 949-950 resonance, 95 1

Vinyl free radical, 123 Vinyl group, 283 Vinyl halides, t169,408

reactivity, 949 - 950 vs. aryl halides, 944

Vinyl-halogen bond, 408 Vinylic cations, 408 Vinylic hydrogen, 124,390 Vinylic spectroscopic analysis, t607 Vinylic substrates, nucleophilic substitution in,

407-409 Vinylidene chloride, 1094 Vinyl monomer, 1080 Vinyl radical, 123 Viscose, 1201 Viscosity, of macromolecules, 1093 Vision, organic chemistry of, 285-287 Vitamin A, 286,488,599 Vitamin A,, 412 Vitamin B,, 1059 Vitamin D, precursor, 1 1 36 Vitamin D2, 1030 Vitamjn D,, 1030 Vitamns, 1229 Vulcanization, of rubber, 420, 1096 Vycra, 1094 Vycron, 1094

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

Watson, J.D., 1242 - 1246 Wave amplitude, 992 Wave equations, 5,992-994 Wave functions, 5, 992 Wave mechmcs, 6 Wavenumbers, 590

Westheimer, Frank H., 1104, 11 13 Wheland, G.W., 395 Whitmore, Frank, 192,206 WiUcinson, Sir Geofiey, 1044, 1053 Wilkinson's catalyst, 1044, 1053 Williamson, ILL., 623 Williamson synthesis, 241 -242,309,

stereochemistry of, 24 1 -242 Winstein, Saul, 270, 386, 468, 1032. Wittig, Geofg, 8 1 1 Wittigreackon, 801,811-813 Wobier, Friedrich, 3 WoH-Kishner reduction, 556,667,672,677 Woodward, R.B., 984, 1004, 1029 W~odward~HoBnann rules, t10 10, t 10 17 Wurtz rea&on, 102

Xanthates, 120 1 X-ray analysis

for configuration, 140 for proteln structure, 1229

Xylans, 1198, 1203 Xylaric acid, 1 16 1 m-Xylene, 551, t553,554,564, 570,583-584 o-Xylene, 551, t553, 554,562, 564, 570, 583-584,

720

NMR spectrum, 606,608 Xylenes, 551, 554,555 (+>Xylose, 1 161, 1 167

z Zerewitinoff active hydrogen determination, 124 Zervas, Leonidas, 1222 Ziegler, Karl, 1087 Ziegler-Natta polymerization, 1088- 1089, 1096 Z ~ n c acetate, 725 Zwitterions, 862 (See also Dipolar ions)