Beyer »Walter Handbook of Organic Chemistry

Prof. em. Dr Wolfgang Walter Institut für Organische Chemie, Universität Hamburg

Translated by Douglas Lloyd Department of Chemistry, University ofSt. Andrews

Prentice Hall London New York Toronto Sydney Tokyo Singapore Madrid Mexico City Munich

V

Author's Foreword xv Translator's Foreword xvii

1 General

1.1

1.2 1.2.1 1.2.2 1.2.3

1.2.4 1.2.5 1.2.6 1.2.7 1.2.8 1.2.9 1.2.10 1.2.11

1.2.12 1.2.13

1.3

1.3.1 1.3.2 1.3.3 1.3.4 1.3.5 1.3.6

1.4

1.4.1 1.4.2 1.4.3

1.5

1.5.1

Introduction 1

Pure Substances 3 Recrystallisation 3 Distillation 4 Distillation and Sublimation in Low or High Vacuum 4 Zone Melting 5 Steam Distillation 5 Extraction 6 Adsorption Chromatography . . 6 Gel Chromatography 7 Partition Chromatography . . . . 7 Paper Chromatography 7 Thin-layer Chromatography (TLC) 8 Gas Chromatography (GC) . . . 9 Criteria for Purity of Substances 9

Qualitative Organic Elemental Analysis 10 Carbon 10 Hydrogen . 11 Nitrogen 11 Sulphur 11 Halogens 11 Other Elements 12

Quantitative Organic Elemental Analysis 12 Carbon, Hydrogen and Nitrogen 12 Sulphur 13 Halogens 13

The Determination of Chemical Formulae 13 Empirical Formulae 13

1.5.2 Determination of the Relative Molecular Mass and the Molec-ular Formula 14

1.5.3 Structural Formulae 16

1.6 The Nature of Chemical Bonding 17

1.6.1 Atomic Structure 17 1.6.2 Ionic Bonding 22 1.6.3 Covalent Bonding 22 1.6.4 C—H and C—C Bonding 23 1.6.5 Onium Complexes 25 1.6.6 Polar Covalent Bonds 26

1.7 Functional Groups. The Inductive Effect 28

1.8 Physical Methods in the Determination of Molecular Structure 29

1.8.1 Mass Spectrometry 30

1.8.2 IR spectroscopy 33 1.8.3 Electronic Spectra (UV and visi-

ble Spectra) 35 1.8.4 Photoelectron Spectroscopy (PE

Spectroscopy) 38 1.8.5 Nuclear Magnetic Resonance

Spectroscopy (NMR Spectro­scopy) 40

1.8.6 Electron Spin Resonance (ESR) 45 1.8.7 Ion Cyclotron Resonance (ICR) 48 1.8.8 Crystal Structure Analysis 48

1.9 Classification of Organic Chemistry 49

vi Table of Contents

2 Aliphatic Compounds 51

2.1 Alkanes (Paraffins), C„H2n+2.. 51 2.1.1 Methane ".+ . . . 53 2.1.2 Ethane 54 2.1.3 Propane and Butanes 55 2.1.4 Pentanes and Higher Homologues 56 2.1.5 Conformations of Ethane 57

2.2 Alkenes (Olefins), CnH2n 59 2.2.1 Efhylene (Ethene) and Propene 60 2.2.2 Butenes and Higher Homologues 61 2.2.3 The C = C Double Bond 63 2.2.4 Cis-Trans Isomerism in Alkenes 64 2.2.5 Addition Reactions 67

2.3 Polymerisation of Alkenes and Vinyl Derivatives 73

2.3.1 Radical Induced Polymerisation 74 2.3.2 Ionic Polymerisation 75 2.3.3 Co-ordinative Polymerisation . . 75 2.3.4 Polymerisation of Alkenes . . . . 76 2.3.5 Polymerisation of Vinyl Deriva­

tives 79

2.4 The Chemistry of Mineral Oil (Petroleum) 82

2.4.1 Mineral Oil, Petroleum; Natural Gases; Oil Shale 82

2.4.2 Fuels from Mineral Oil 84 2.4.3 Fuel-oils from Coal 87

2.5 The Chemistry of Petroleum . 88

2.6 Alkynes (Acetylenes), CnH2n 2 . 88 2.6.1 Preparation 1 . . 90 2.6.2 The C = C Triple Bond 91 2.6.3 Addition Reactions 94 2.6.4 Reppe Syntheses 96

2.7 Hydrocarbons with Two or More C = C Double Bonds (Polyenes) 99

2.7.1 Allenes 99 2.7.2 Conjugated Dienes 100 2.7.3 1,2- and 1,4-Addition; Mesomer-

ism 101 2.7.4 Woodward-Hofflmann Rules . . . 104 2.7.5 Dienes with Isolated Double

Bonds 108

2.8 Monohydric Alcohols 109 2.8.1 Hydrogen Bonding (Hydrogen

Bridging) 110 2.8.2 Oxidation Products from Alco­

hols 112 2.8.3 Methanol (Methyl Alcohol,

Carbinol) 113

2.8.4 2.8.5 2.8.6 2.8.7

2.8.8 2.8.9 2.8.10

2.9 2.9.1 2.9.2

2.9.3 2.9.4 2.9.5 2.9.6 2.9.7

2.10 2.10.1

2.10.2 2.10.3 2.10.4 2.10.5

2.11 2.11.1 2.11.2

2.12 2.12.1 2.12.2

2.13 2.13.1 2.13.2 2.13.3

2.14

2.14.1 2.14.2

2.15 2.15.1 2.15.2

2.16 2.16.1

Ethanol (Ethyl Alcohol) 114 Propanols (Propyl Alcohols) . . 116 Butanols (Butyl Alcohols) 116 Pentanols (Pentyl or Amyl Alco­hols) 117 Optical Isomerism, Chirality . . 118 Higher Alcohols, C H ^ O H . . 121 Unsaturated Alcohols (Alkenols andAlkynols) 121 Halogen Derivatives of Alkanes 123 Alkyl Halides (Halogeno-alkanes) 123 Mechanism of Nucleophilic Sub­stitution at Saturated Carbon Atoms 126 Elimination Reactions 130 Phase Transfer Catalysts (PTC) 132 Fragmentation Reactions 133 Polyhalogenoalkanes 133 Fluorinated Hydrocarbons . . . . 135

Esters of Inorganic Acids . . . . 138 Esters of Sulphuric Acid. Alkyl Sulphates 138 Esters of Nitric Acid 139 Esters of Nitrous Acid 139 Esters of Phosphoric Acid . . . . 140 Esters of Boric Acid 140

Ethers 141 Preparation 141 Properties 142

Alkanethiols (Mercaptans)... 144 Preparation 144 Properties and Uses 145

Dialkyl Sulphides (Thioethers) 146 Preparation 146 Properties 146 Sulphoxides and Sulphones . . . 147

Aliphatic Sulphonic Acids, Sulphonyl Chlorides, Sulphinic and Sulphenic Acids 148 Alkanesulphonic Acids 149 Alkanesulphonyl Chlorides, Alkanesulphinic and Alkane-sulphenic Acids . 149

Nitroalkanes 150 Preparation 152 Properties 153

Aliphatic Amines 155 Monoamines 155

Table of Contents vii

2.16.2 Optical Activity in Compounds with 3- and 4-Co-ordinate Nitro-gen Atoms 164

2.16.3 Unsaturated Amines (Enamines) 165 2.16.4 Diamines 166

2.17 Aliphatic Diazo-Compounds, Diazirines and Diazlridines . . 166

2.17.1 Diazo-compounds 166 2.17.2 Diazirines and Diaziridines . . . 168

2.18 Aliphatic Hydrazines and Azides 169

2.18.1 Hydrazines 169 2.18.2 Azides 171

2.19 Organic Compounds Containing some other Non-metals 171

2.19.1 Organophosphorus Compounds 171 2.19.2 Organo-arsenic Compounds . . . 176 2.19.3 Organosilicon Compounds . . . . 177 2.19.4 Organoboron Compounds . . . . 179

2.20 Organometallic Compounds . 182 2.20.1 Alkali Metal Compounds 183 2.20.2 Organomagnesium Compounds 184 2.20.3 Organozinc Compounds 186 2.20.4 Organotitanium Compounds . . . 187 2.20.5 Organomercury Compounds . . . 188 2.20.6 Organoaluminium Compounds . 189 2.20.7 Organotin Compounds 190 2.20.8 Organolead Compounds 190

2.21 Aliphatic Aldehydes (Alkanals) 191 2.21.1 General Methods of Preparation 191 2.21.2 Tests for Aldehydes 192 2.21.3 The C = 0 Double Bond 193 2.21.4 Addition Reactions of Aldehydes 194 2.21.5 Enantiotopy and Prochirality . . 196 2.21.6 Addition and Substitution Reac­

tions of Aldehydes 196 2.21.7 Condensation Reactions of

Aldehydes 197 2.21.8 Formaldehyde (Methanal) 201 2.21.9 Acetaldehyde (Ethanal) 203 2.21.10 Propionaldehyde (Propanal) . . . 204 2.21.11 Halogenoaldehydes 204 2.21.12 Unsaturated Aldehydes (Alke­

nais and Alkynals) 205 2.21.13 Directed Aldol Reaction 207

2.22 Aliphatic Ketones (Alkanones) 207 2.22.1 General Methods of Preparation 208 2.22.2 Addition and Condensation

Reactions 210 2.22.3 Reduction Products from Ketones 214 2.22.4 Pinacol-Pinacolone Rearrange-

ment 216

2.22.5 Wagner-Meerwein Rearrange-ment 217

2.22.6 Acetone (Propanone) 217 2.22.7 Butanone (Ethyl methyl ketone) 219 2.22.8 Halogenoketones 219 2.22.9 Unsaturated Ketones 220 2.22.10 Photochemistry of Carbonyl

Compounds 221

2.23 Tabular Comparison of the Properties of the Aldehydes and Ketones 226

2.24

2.24.1 2.24.2 2.24.3 2.24.4 2.24.5 2.24.6 2.24.7 2.24.8

2.25

2.25.1 2.25.2 2.25.3 2.25.4

2.25.5

2.25.6

2.26 2.26.1 2.26.2 2.26.3

2.27

2.27.1 2.27.2 2.27.3

2.28

2.28.1 2.28.2 2.28.3 2.28.4 2.28.5 2.28.6 2.28.7

Saturated Aliphatic Monocarboxylic Acids (Alkanoic Acids, Fatty Acids) 229 General Methods of Preparation 229 Acidity of the Carboxyl Group . 231 Formic Acid (Methanoic Acid) 233 Acetic Acid (Ethanole Acid) . . 235 Propionic Acid (Propanoic Acid) 236 Butyric Acids (Butanoic Acids) 236 Pentanoic Acids (Valerie Acids) 237 Higher Carboxylic Acids 237

Unsaturated Aliphatic Monocarboxylic Acids (Alkenoic Acids) 238 General Methods of Preparation 238 Acrylic Acid (Propenoic Acid) . 239 Acrylonitrile 240 Unsaturated Carboxylic Acids with Four Carbon Atoms 241 Oleic Acid (Octadec-9-enoic Acid) 243 Polyunsaturated Monocarboxylic Acids 243

Fats, Oils and Waxes 244 Fats and Oils 244 Production of Fats 245 Waxes 246

Soaps and Synthetic Detergents 246 Anionic Surfactants 247 Cationic Surfactants 249 Non-ionic Surfactants 250

Derivatives of Aliphatic Monocarboxylic Acids 250 Acyl Halides (Acid Halides) . . 250 Acid Anhydrides 253 Ketenes 255 Esters of Carboxylic Acids . . . . 256 Ortho-esters 260 Amides 260 Thioamides 263

viii Table of Contents

2.28.8 Hydrocyanic Acid and Nitriles (Cyanides) 264

2.28.9 Hydroxamic Acids 267 2.28.10 Iminoesters, Amidines and

Amidrazones 268 2.28.11 Acid Hydrazides and Acid

Azides 269

2.29 Substituted Aliphatic Monocarboxylic Acids 269

2.29.1 Halogenocarboxylic Acids . . . . 269 2.29.2 D- and L-Configuration on

Asymmetrie Carbon Atoms which are Stereogenic Centres 272

2.29.3 Absolute Configuration at Asymmetrie Carbon Atoms. The Cahn-Ingold-Prelog (CIP) (RS) System 274

2.29.4 Hydroxy-acids 278 2.29.5 Lactones 280 2.29.6 CommonerHydroxyacids . . . . 281 2.29.7 Amino acids 283 2.29.8 The Most Important Aliphatic

Amino acids 289

2.30 Aliphatic Aldehydo- and Keto-aeids 291

2.30.1 Aldehydo-acids 291 2.30.2 a-Keto-acids 292 2.30.3 ß-Keto-acids 293 2.30.4 Keto-enol Tautomerism (Oxo-

enol Tautomerism) 293 2.30.5 Preparation of Acetoacetic

Esters 295 2.30.6 Syntheses using Acetoacetic

Esters 296 2.30.7 y-Keto-acids 299

2.31 Polyhydric Alcohols 300 2.31.1 Dihydric Alcohols (Glycols, 1,2-

Diols) 300 2.31.2 Trihydric Alcohols 308 2.31.3 Tetrahydric Alcohols 314 2.31.4 Pentahydric Alcohols (Pentitols) 314 2.31.5 Hexahydric Alcohols (Hexitols) 315

2.32 Aliphatic Hydroxy-aldehydes and Hydroxy-ketones 316

2.32.1 Hydroxy-aldehydes 316 2.32.2 Hydroxy-ketones (Keto-alcohols) 318

2.33 Aliphatic Dialdehydes, Ketoaldehydes and Diketones 319

2.33.1 Dialdehydes 319 2.33.2 Ketoaldehydes 320 2.33.3 Diketones 321

2.34 Saturated Aliphatic Dicarboxylic Acids 323

2.34.1 Oxalic Acid 325 2.34.2 Malonic Acid 326 2.34.3 Succinic Acid 330 2.34.4 Higher Dicarboxylic Acids . . . . 332

2.35 Unsaturated Aliphatic Dicarboxylic Acids 334

2.35.1 Ethylenedicarboxylic Acids (Maleic and Fumaric Acids) . . . 334

2.35.2 Diels-Alder Reaction 336 2.35.3 Acetylenedicarboxylic Acid . . . 340

2.36 Aliphatic Hydroxy-dicarboxylic and -tricarboxylic Acids . . . . 340

2.36.1 Hydroxymalonic Acid (Tartronic Acid) 340

2.36.2 Malic Acid (Hydroxysuccinic Acid) 341

2.36.3 Waiden Inversion 342 2.36.4 Asymmetrie Synthesis, Stereo-

selective Synthesis, Asymmetrie Induction 344

2.36.5 Tartaric Acid (Dihydroxy-succinic Acid) 346

2.36.6 Methods for the Resolution of Racemic Forms 347

2.36.7 Citric Acid 349

2.37 Aliphatic Ketodicarboxylic Acids 350

2.37.1 Mesoxalic Acid (Oxomalonic Acid) 350

2.37.2 Oxaloacetic Acid 350

2.38 Carbonic Acid Derivatives . . . 351 2.38.1 Halogen Derivatives of Carbonic

Acid 352 2.38.2 Esters of Carbonic Acid 352 2.38.3 Amides of Carbonic Acid 353 2.38.4 Amides of Orthocarbonic Acid 359

2.39

2.39.1 2.39.2 2.39.3 2.39.4

2.40 2.40.1 2.40.2 2.40.3 2.40.4 2.40.5

Thio-derivatives of Carbonic Acid 359 Carbon Disulphide 360 Thiourea 361 Thiosemicarbazide 362 3-Thiocarbazide (Thiocarbono-hydrazide) 363

Cyanic Acid and its Derivatives 363 Cyanogen Halides 364 Cyanate Esters 365 Isocyanate Esters 366 Cyanamides 367 Carbodijmides 369

Table of Contents ix

2.41 Thiocyanic Acid and its Derivatives 369

2.41.1 Preparation 369 2.41.2 Thiocyanate and Isothiocyanate

Esters 370

2.42 Dicyanogen and Di(thiocyanogen) 371

2.42.1 Dicyanogen 371 2.42.2 Di(thiocyanogen) 372

2.43 Carbon Monoxide and its Derivatives 373

2.43.1 Carbon Monoxide 373 2.43.2 Alkyl Isocyanides (Isonitriles) . 374

2.44 Carbenes and Nitriles as Reactive Intermediates 376

2.44.1 Carbenes 376 2.44.2 Nitrenes 378

2.45 Organic Transition-Metal Complexes 380

2.45.1 The Eighteen Electron Rule . . . 380 2.45.2 Back Bonding . 381 2.45.3 Oxidative Addition and Reduc-

tive Elimination 382 2.45.4 Wacfer-Hoechst Process 383 2.45.5 Oxo-synthesis 383

3 Alicyclic Compounds 385

3.1 Small-Ring Compounds 387 3.1.1 Cyclopropane 387 3.1.2 The Stereochemistry of Carbo-

cyclic Compounds 389 3.1.3 Cyclopropene 389 3.1.4 Cyclobutane and its Derivatives 390

3.2 Common Ring Compounds . . 394 3.2.1 Cyclopentane and its Derivatives 394 3.2.2 Cyclohexane and its Derivatives 398 3.2.3 Cycloheptane and its Derivatives 404

3.3 Medium-Sized Rings 406 3.3.1 Cyclooctatetraene 406

3.3.2 Cyclooctane, Cyclooctene . . . . 408 3.3.3 Cyclododecatriene 409

3.4 Large Rings 409 3.4.1 Preparation 409

3.5 Bi- and Poly-cyclic Hydrocarbons 411

3.5.1 Spiro-alkanes (Spiranes) 411 3.5.2 Condensed Rings 411 3.5.3 Bridged-ring Compounds 413 3.5.4 Ring-systems Related to Diamond 415 3.5.5 Small Bi- and Poly-cyclic Sys­

tems 416

4 Carbohydrates 423

4.1 4.1.1 4.1.2 4.1.3

4.1.4

4.1.5

4.1.6

4.1.7 4.1.8 4.1.9

Monosaccharides 424 Configuration of Sugars 424 Reactions of Monosaccharides . 426 Interconversion of Monosac­charides 431 Test Reactions for Monosac­charides 432 Syntheses, Chain Lengthening and Chain Shortening of Mono­saccharides 432 The Ring Structure of Mono­saccharides 435 Glycosides 439 Pentoses, C5H|0O5 441 Hexoses, C6H,2Q6 441

4.1.10 Reactions of the Hydroxy Groups 442 4.1.11 Deoxysugars 444 4.1.12 Aminosugars 444 4.1.13 Sugar Mercaptals and Thiosugars 446 4.1.14 L(+)-Ascorbic Acid (Vitamin C) 448

4.2 Oligosaccharides 451 4.2.1 Disaccharides 451 4.2.2 Trisaccharides 456 4.2.3 Pseudo-oligosaccharides 457

4.3 Polysaccharides (Glycans) . . . 457 4.3.1 Starch (Amylum) 458 4.3.2 Glycogen 461 4.3.3 Inulin 461 4.3.4 Chitin 461

x Table of Contents

4.3.5 Pectins 461 4.3.6 Cellulose 462 4.3.7 Hemicelluloses 463 4.3.8 Cellulose Ethers 464

4.3.9 Cellulose Nitrates 464 4.3.10 Cellulose-based Synthetic Fibres

(Half-synthetic Fibres) 464

5 Aromatic Compounds. Derivatives of Benzene 467

5.1 Arenes. Aromatic Hydrocarbons 472

5.1.1 Benzene 473 5.1.2 Homologues of Benzene. Alkyl-

benzenes 474 5.1.3 Toluene 476 5.1.4 Ethylbenzene 477 5.1.5 Xylenes 477 5.1.6 Trimethylbenzenes 477 5.1.7 Cumene 477

5.2 Halogen Derivatives of Arenes 478 5.2.1 Addition of Halogens to the

Benzene Ring 478 5.2.2 Halogenobenzenes 479 5.2.3 Mechanisms of Further Elec-

trophilic Substitution in the Benzene Ring 482

5.2.4 Side-chain Halogenation of Alkylbenzenes .„,-

5.3 Nitro-arenes. Aromatic Nitro-compounds 486

5.3.1 Nitrobenzenes 487 5.3.2 Nitrotoluenes 490

5.4 Arenesulphonic Acids 490 5.4.1 Preparation 490 5.4.2 Derivatives of Arenesulphonic

Acids 492

5.5 Phenols 495 5.5.1 Monohydric Phenols 495 5.5.2 Alkyl Phenyl Ethers (Phenol

Ethers) 497 5.5.3 Halogenophenols 500 5.5.4 Phenolsulphonic Acids 501 5.5.5 Nitrophenols 501 5.5.6 Nitrosophenols 504 5.5.7 Homologues of Phenol 505 5.5.8 Dihydric Phenols 507 5.5.9 Cyclophanes and Catenanes . . . 510 5.5.10 Trihydric Phenols 513

5.6 Benzoquinones 514 5.6.1 The Most Important Benzo­

quinones 515 5.6.2 Redox Reactions of p-Quinones 517

5.6.3 1,4-Addition Reactions of p-Quinones 518

5.6.4 Quinoid Dyestuffs 520

5.7 Aryl Alcohols and Arylalkylamines 522

5.7.1 Aryl Alcohols 522 5.7.2 Arylalkylamines 524

5.8 Aromatic Aldehydes and Ketones. Aryl Aldehydes and Aryl Ketones 528

5.8.1 Benzaldehyde 529 5.8.2 Homologues of Benzaldehyde . 535 5.8.3 Phenol and Phenol-ether

Aldehydes 536 5.8.4 Vanillin 538 5.8.5 Aryl Ketones 539

5.9 Arenecarboxylic Acids 545 5.9.1 Arenemonocarboxylic Acids . . 545 5.9.2 Arylaliphatic Monocarboxylic

Acids (Arylalkanoic Acids) . . . 553 5.9.3 Unsaturated Arylaliphatic Mono­

carboxylic Acids 555 5.9.4 Arenedicarboxylic Acids 557

5.10 Reduction Products from Aryl Nitro-compounds 562

5.10.1 Reduction in Solution in Mineral Acid 563

5.10.2 Reduction in Weakly Acidic or Neutral Solution 563

5.10.3 Reduction in Alkaline Solution 565

5.11 Arylamines 569 5.11.1 Aniline 569 5.11.2 Derivatives of Aniline 571 5.11.3 Nitroanilines 572 5.11.4 Anilinesulphonic Acids 574 5.11.5 Arsenic Derivatives of Aniline . 576 5.11.6 N-Alkylanilines (Alkylarylamines) 577 5.11.7 Secondary and Tertiary Amines

having only Aryl Substituents . 578 5.11.8 Phenylenediamines 579

5.12 Aryl Diazo-compounds 580 5.12.1 Diazonium Salts 580 5.12.2 Diazotates 582

Table of Contents xi

5.13 Reactions of Arenediazonium Salts 582

5.13.1 Reactions Involving Loss of the Diazo-group 583

5.13.2 Reactions in which the Nitrogen of the Diazo-group is Retained . 586

5.13.3 Coupling Reactions 587

5.14 Azo Dyestuffs 590 5.14.1 Structure and Colour 590 5.14.2 Dyestuff Technology 594 5.14.3 Basic Azo-dyestuffs 595 5.14.4 Acid Azo-dyestuffs 596 5.14.5 Direct Dyestuffs (Substantive

Dyestuffs) 596 5.14.6 Naphthol-AS-Dyestuffs 597 5.14.7 Reactive Dyestuffs 599 5.14.8 Disperse Dyestuffs 599 5.14.9 Metal-complex Azo-dyestuffs . 600 5.14.10 Diazotype Printing and Related

Copying Processes 601

5.15 Biphenyl and Arylmethanes . 602 5.15.1 Biphenyl 602 5.15.2 Diphenylmethane 603 5.15.3 Triphenylmethane 604

5.16 Triphenylmethane Dyestuffs . 606 5.16.1 Aminotriphenylmethane Dye­

stuffs 606 5.16.2 Hydroxytriphenylmethane Dye­

stuffs 608 5.16.3 Phthaleins 609

5.17 Arylethanes 610

5.18 5.18.1 5.18.2 5.18.3 5.18.4

5.19

5.19.1 5.19.2 5.19.3 5.19.4

5.20

5.20.1 5.20.2 5.20.3 5.20.4 5.20.5 5.20.6 5.20.7

5.21 5.21.1 5.21.2 5.21.3 5.21.4 5.21.5 5.21.6 5.21.7

Free Radicals 612 Carbon Radicals 612 Nitrogen Radicals 613 Aroxyls (Phenoxy Radicals) . . . 615 Radical-ions 615

Phenyl Derivatives of Unsaturated Hydrocarbons . . 616 Arylalkenes 617 Arylakynes 619 Cumulenes 620 Allenic Isomerism (Molecular Asymmetry) 621

Condensed Aromatic Ring-Systems 623 Indene 623 Fluorene 625 Naphthalene 625 Acenaphthene 634 Anthracene 634 Phenanthrene 641 Polycyclic Arenes 644

Nonbenzenoid Aromatics . . . . 647 Cyclopentadienides 647 Aromatic Complexes 648 Tropylium Salts 650 Tropone '. 651 Tropolone and its Derivatives . 652 Azulenes 653 Hückel's Rule 655

6 Isoprenoids (Terpenes and Steroids) 66]

6.1 Acyclic Monoterpenes 662 6.1.1 Monoterpene Hydrocarbons . . . 662 6.1.2 Monoterpene Alcohols 662 6.1.3 Monoterpene Aldehydes and

Monoterpene Ketones 663

6.2 Monocyclic Monoterpenes . . . 664 6.2.1 p-Menthane 664 6.2.2 Unsaturated Monoterpene Hydro­

carbons 664 6.2.3 Monoterpene Alcohols and

Monoterpene Thiols 665 6.2.4 Monoterpene Ketones 666

6.3 Bicyclic Monoterpenes 667 6.3.1 Carane Group 668 6.3.2 Pinane Group 668

6.3.3 Bornane Group 669

6.4 Sesquiterpenes 672 6.4.1 Acyclic Sesquiterpenes 672 6.4.2 Monocyclic Sesquiterpenes . . . 673 6.4.3 Bicyclic Sesquiterpenes 673 6.4.4 Tricyclic Sesquiterpenes 674

6.5 Diterpenes 674 6.5.1 Acyclic Dieterpenes 674 6.5.2 Monocyclic Diterpenes 675 6.5.3 Tricyclic Diterpenes 675 6.5.4 Tetracyclic Diterpenes 677

6.6 Triterpenes (Squalenoids) . . . 677

6.7 Tetraterpenes 678 6.7.1 Carotenoids (Polyene Pigments) 679

xii Table of Contents

6.8 Polyprenes 681 6.8.1 Polyprenols 681 6.8.2 Natural Rubber 681 6.8.3 Synthetic Elastomers 682 6.8.4 Gutta-percha 684

6.9 Sterols 687

6.10 Bile Acids 689

6.11 Steroid Vitamins 690

6.12 Steroid Hormones (Sex Hormones and Adrenal Hormones) 691

6.12.1 Male Sex Hormones (Androgens) 692

6.12.2 Female Sex Hormones [Oestrogens (Estrogens) and Gestagens] 692

6.12.3 Corticoids 695

6.13 Cardiotonic (Cardiac-active) Steroids 697

6.13.1 Cardenolides 697 6.13.2 Bufadienolides 698

6.14 Steroid Sapogenins 698

6.15 Steroid Alkaloids 699

7 Heterocyclic Compounds 701

7.1

7.1.1 7.1.2 7.1.3 7.1.4

7.2

7.2.1 7.2.2 7.2.3 7.2.4 7.2.5

7.3

7.3.1 7.3.2

7.4

7.4.1 7.4.2 7.4.3 7.4.4

7.5

7.5.1 7.5.2 7.5.3 7.5.4 7.5.5

Five-membered Rings with One Hetero-atom 704 Pyrroles 704 Porphin Pigments 708 Furans 716 Thiophenes 719

Benzopyrroles, Benzofurans and Benzothiophenes 722 Indoles 722 Indolizines 729 Coumarones 730 Thianaphthenes 731 Tricyclic Condensed Systems . . 731

Five-membered Rings Containing Two Nitrogen Atoms 732 Pyrazoles 733 Imidazoles 739

Five-membered Rings with Two Different Hetero-atoms . 743 Oxazoles 744 Isoxazoles 746 Thiazoles 747 Isothiazoles 752

Five-Membered Rings Containing Three or More Heteroatoms 753 Triazoles 753 Tetrazoles 756 Pentazoles 758 Sydnones, Mesoionic Compounds 759 Thiadiazoles 760

7.6 Six-membered Ring Hetero-cycles with One Heteroatom . 760

7.6.1 Pyridines 761 7.6.2 Pyrans 770

7.7 Benzo-derivatives of Pyridine and y-Pyrone 772

7.7.1 Quinolines 772 7.7.2 Benzoquinolines 775 7.7.3 Isoquinolines 777 7.7.4 Chromans 778

7.8 Six-membered Rings with Two Hetero-atoms 781

7.8.1 Pyridazines 781 -7.8.2 Pyrimidines 782

7.8.3 Pyrazines 785 7.8.4 Benzodiazines 786 7.8.5 Phenazines, Phenoxazines, Di-

benzo-p-dioxins and Pheno-thiazines 788

7.9 Six-membered Rings Containing Three Heteroatoms 792

7.9.1 Triazines 792 7.9.2 Oxathiazines 793

7.10 Benzo-annelated Seven-membered Rings Containing One or Two Hetero-atoms . . . 794

7.10.1 Benzazepines 794 7.10.2 Benzodiazepines 794

7.11 Bicyclic Heterocyclic Systems 795 -7.11.1 Purines 795 7.11.2 Pterins 799 7.11.3 Flavins (Isoalloxazines) 801

Table of Contents xiii

7.11.4 1,4-Diketopyrrolo[3,4-c]pyrroles (DPP) 801 Bicyclic Amidines 802

Alkaloids 802 Alkaloids Based on Tetrahy-dropyrrole, Pyridine and Piperidine 802

7.11.5

7.12 7.12.1

7.12.2 Alkaloids Based on Tropane . . 805 7.12.3 Alkaloids Based on Quinolizidine 809 7.12.4 Alkaloids Based on Quinoline . 809 7.12.5 Alkaloids Based on Isoquinoline 811 7.12.6 Alkaloids Based on Indole 815

8 Amino Acids, Peptides and Proteins 819

8.1 Amino acids as Protein Building Blocks 820

8.1.1 Aliphatic Amino acids 820 8.1.2 Aryl Amino acids 824 8.1.3 Heterocyclic Amino acids . . . . 825 8.1.4 Industrial Sources of Amino

Acids 826

8.2 Peptides 827 8.2.1 Synthesis of Peptides 827

8.2.2 Amino-acid Analysis of Peptides 832 8.2.3 Sequence Analysis of Peptides . 833 8.2.4 Naturally Occurring Peptides . . 834

8.3 Properties and Structure of Proteins 838

8.3.1 Fibrous Proteins 839 8.3.2 Globular Proteins (Sphero-

proteins) 842 8.3.3 Conjugated Proteins 843

9 The Chemistrv and Function of Nucleic Acids 849

9.1 Structural Units of Nucleic Acids 849

9.1.1 Nucleosides 850 9.1.2 Nucleotides 851

9.2 The Structure of Nucleic Acids 852

9.2.1 Sequence Analysis of DNA . . . 856

9.3 Synthesis of Nucleic Acid Sequences 856

9.3.1 Diester Method 857 9.3.2 Triester Method 858 9.3.3 Sticky-end Method 859

9.4 Viruses 860

9.5 Function of Nucleic Acids . . . 862 9.5.1 The Genetic Code 863 9.5.2 Mutations 864 9.5.3 Transcription of DNA 866 9.5.4 Translation 867 9.5.5 RNA Enzymes (Ribozymes) . . 869 9.5.6 Control of Gene-Expression . . . 872 9.5.7 Gene Analysis (DNA Diagnosis) 873

9.6 Genetic Engineering and Biosynthesis 875

9.6.1 Modifikation of Plasmids 876 9.6.2 Cloning 877 9.6.3 Biosynthesis of Hormones . . . . 879

10 Enzymes 883

10.1 Oxidoreductases 884 10.1.1 Pyridine Nucleotides 885 10.1.2 Flavin Enzymes 886 10.1.3 CellHaemins 888

10.2 Transferases 889 10.2.1 Phosphotransferases 889 10.2.2 Acyltransferases 890 10.2.3 Aminotransferases 890

xiv Table of Contents

10.2.4 Methyl-and Formyl-transferases 891

10.3 Hydrolases 892 10.3.1 Ester Hydrolases 893 10.3.2 Glycoside Hydrolases (Glycosi-

dases) 893 10.3.3 Peptide Hydrolases 894

10.4 Lyases 895 10.4.1 C-C-Lyases 895 10.4.2 C-O-Lyases 897

10.5 Isomerases 897

10.6 Ligases (Synthetases) 898

11 Metabolie Processes 899

11.1 Photosynthetic Cycle 899

11.2 Enzymatic Build-up and Breakdown of Carbohydrates 902

11.2.1 Alcoholic Fermentation 902

11.2.2 Glycolysis (Degradation of Sugars in Living Organisms) 905

11.2.3 Citric Acid Cycle 907

Appendix: Haxardotts Suftstances and Cardsogenk Materials. Named Reacttons and Concc

::M^>£J**^,

^S^^^f^i m^ & Subject Index 962