CONTENTS

CHAPTER 1 ORGANIC SYNTHESIS

1.1 1.2 1.3 1.4 1.5 INTRODUCTION STRUCTURE OF THE TARGET MOLECULE REACTION MECHANISM AND THE METHODOLOGY OF SYNTHESIS REACTION MECHANISM AND THE STRATEGY OF SYNTHESIS CONCLUSION

1
1 2 10 17 23 23

REFERENCES

CHAPTER 2 EXPERIMENTAL TECHNIQUES

2.1 GENERAL INSTRUCTIONS FOR SAFE WORKING IN ORGANIC CHEMICAL LABORATORIES 2.2 PLANNING OF EXPERIMENTS AND RECORDING OF RESULTS 2.3 HAZARDS IN ORGANIC CHEMISTRY LABORATORIES 2.3.1 Introduction 34 2.3.2 Explosion and fire hazards 35 2.3.3 Reactive inorganic reagents 42 2.3.4 Hazards due to toxic chemicals 44 2.3.5 Electrical safety 51 2.3.6 Ultraviolet radiation 52 APPARATUS AND REACTION PROCEDURES 2.4 INTERCHANGEABLE GROUND GLASS JOINTS 2.5 TYPES OF GROUND GLASS JOINTS 2.6 CARE AND MAINTENANCE OF GROUND GLASS JOINTS 2.7 APPARATUS WITH INTERCHANGEABLE GROUND GLASS JOINTS SUITABLE FOR GENERAL USE IN PREPARATIVE ORGANIC CHEMISTRY 2.8 OTHER TYPES OF INTERCHANGEABLE JOINTS AND STOPCOCKS 2.9 THE USE OF CORKS AND RUBBER STOPPERS 2.10 CUTTING AND BENDING OF GLASS TUBING

26
26 31 34

52 52 55 57 58 63 64 65
V

CONTENTS

2.11 2.12 2.13 2.14 2.15

GENERAL LABORATORY APPARATUS COOLING OF REACTION MIXTURES HEATING OF REACTION MIXTURES MECHANICAL AGITATION TYPICAL GROUND GLASS JOINT ASSEMBLIES FOR STANDARD REACTION PROCEDURES 2.16 PRECAUTIONS FOR UNATTENDED REACTIONS 2.17 APPARATUS FOR SPECIAL REACTION TECHNIQUES 2.17.1 Catalytic hydrogenation 87 2.17.2 Reactions under pressure 97 2.17.3 Uncatalysed and catalysed vapour phase reactions 99 2.17.4 Ozonolysis 103 2.17.5 Organic photochemistry 106 2.17.6 Electrolytic (anodic) syntheses 115 2.17.7 Liquid ammonia techniques 116 2.17.8 Reactions involving air-sensitive compounds 120 ISOLATION AND PURIFICATION PROCESSES 2.18 GENERAL CONSIDERATIONS 2.19 FILTRATION TECHNIQUES 2.20 RECRYSTALLISATION TECHNIQUES 2.21 SUBLIMATION TECHNIQUES - FREEZE DRYING 2.22 SOLVENT EXTRACTION 2.23 DRYING OF LIQUIDS OR OF SOLUTIONS OF ORGANIC COMPOUNDS IN ORGANIC SOLVENTS 2.24 DISTILLATION AT ATMOSPHERIC PRESSURE 2.25 STEAM DISTILLATION 2.26 FRACTIONAL DISTILLATION AT ATMOSPHERIC PRESSURE 2.27 DISTILLATION UNDER DIMINISHED PRESSURE CVACUUM' DISTILLATION) 2.28 HIGH VACUUM DISTILLATION - MOLECULAR DISTILLATION 2.29 VACUUM PUMPS 2.30 MANOMETERS, VACUSTATS, VACUUM GAUGES AND MANOSTATS 2.31 CHROMATOGRAPHY 2.32 STORAGE OF SAMPLES DETERMINATION OF 2.33 MELTING POINT 2.34 DETERMINATION 2.35 DETERMINATION 2.36 DETERMINATION 2.37 DETERMINATION REFERENCES
VI

66 70 71 73 80 86 87

131 131 133 135 153 156 165 169 171 173 181 186 191 193 197 234 236 236 241 243 244 249 250

PHYSICAL CONSTANTS - MIXED MELTING POINTS OF BOILING POINT OF MOLECULAR WEIGHT OF OPTICAL ROTATORY POWER OF REFRACTIVE INDEX

CONTENTS

CHAPTER 3 SPECTROSCOPIC METHODS AND THE INTERPRETATION OF SPECTRA Introduction 254 The electromagnetic spectrum 255 3.1 INFRARED SPECTROSCOPY Instrumental features of infrared spectrophotometers 258 Determination of infrared spectra 259 Sample preparation 260 Features of an infrared spectrum 268 Interpretation of an infrared spectrum 271 Characteristic group frequencies 273 3.2 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY Features of the nuclear magnetic resonance spectrum 319 The chemical shift 324 Spin-spin splitting 338 Protons attached to heteroatoms 348 Simplification of 1H spectra 350 Interpretation of the p.m.r. spectrum 359 Further information from 13C-spectra 360 3.3 MASS SPECTROMETRY The mass spectrum 362 Appearance of the mass spectrum 372 Interpretation of the mass spectrum 373 Mass spectra of classes of organic compounds 373 14 ULTRAVIOLET-VISIBLE SPECTROSCOPY Instrumental features of ultraviolet-visible spectrophotometers 384 Determination of ultraviolet-visible spectra 384 Laws of light absorption 385 Solvents for ultraviolet spectroscopy 386 Solution preparation 386 Optical cells and their care 387 Features of an ultraviolet-visible spectrum 388 REFERENCES

254

256

316

361

383

393

CHAPTER 4 SOLVENTS AND REAGENTS 4.1 THE PURIFICATION OF COMMON ORGANIC SOLVENTS Saturated aliphatic hydrocarbons 397 Aromatic hydrocarbons 398 Halogenated hydrocarbons 399 Aliphatic alcohols 400 Ethers 404 Ketones 407 Esters 409

395 395

Vll

CONTENTS

Nitrogen-containing solvents 409 Sulphur-containing solvents 411 Phosphorus-containing solvents 412

4.2 THE PREPARATION AND PURIFICATION OF REAGENTS REFERENCES

413 468

CHAPTER 5 ALIPHATIC COMPOUNDS 5.1 ALKANES

470 470

Structure 470 Summary of preparative methods and of retrosynthetic strategies 471 Spectroscopic features 472 5.1.1 T h e catalytic hydrogenation and chemical reduction o f alkenes 472 5.1.2 T h e hydrolysis o f alkylmagnesium halides and the hydrogenolysis o f a l k y l halides and o f a l k y l methane- or toluene-p-sulphonates 474 5.1.3 T h e reduction o f aldehydes and ketones 476 5.1.4 Coupling reactions (a) using organometallic compounds, and (b) at the anode 477

5.2 ALKENES
Structure 484 Summary of preparative methods and of retrosynthetic strategies 485 Spectroscopic features 486 5.2.1 1,2-Elimination processes (-elimination) 486 5.2.2 T h e partial hydrogenation o f alkynes 493 5.2.3 W i t t i g and related reactions 495 5.2.4 Selected rearrangements o f alkynes to allenes 504

484

5.3 ALKYNES
Structure 507 Summary of preparative methods and of retrosynthetic strategies 508 Spectroscopic features 508 5.3.1 T h e dehydrogenation o f vic- and gem-dihalides 509 5.3.2 T h e oxidation o f dihydrazones o f 1,2-diketones 512 5.3.3 A l k y l a t i o n o f a terminal alkyne 513 5.3.4 Coupling reactions leading to diynes 515

507

5.4 ALIPHATIC ALCOHOLS

Structure 517 Summary of preparative methods and of retrosynthetic strategies 517 Spectroscopic features 519 5.4.1 T h e reduction o f aldehydes, ketones and esters 519 5.4.2 T h e interaction o f carbonyl-containing compounds with organometallic reagents 531 5.4.3 T h e hydroboration-oxidation o f alkenes 542 5.4.4 T h e oxymercuration demercuration o f alkenes 545 5.4.5 T h e hydroxylation o f alkenes 547 5.4.6 Methods for the protection o f the hydroxyl group 550
Vlll

517

CMTERTS

5.5 ALIPHATIC HALIDES 553 Structure 553 Summary of preparative methods and of retrosynthetic strategies 554 Spectroscopic features 554 5.5.1 Preparation of alkyl chlorides from alcohols 555 5.5.2 Preparation of alkyl bromides from alcohols 559 5.5.3 Preparation of alkyl iodides from alcohols 566 5.5.4 Displacement reactions involving a halogen atom 570 5.5.5 Displacement reactions involving a methanesulphonyloxy group 572 5.5.6 Displacement reactions involving the amino group 574 5.5.7 Addition of hydrogen halides or halogens to alkenes 574 5.5.8 The replacement of reactive allylic hydrogen atoms by bromine 577 5.6 ALIPHATIC ETHERS 579 Structure 579 Summary of preparative methods and of retrosynthetic strategies 580 Spectroscopic features 580 5.6.1 The formation of ethers from alcohols under acidic conditions 581 5.6.2 The interaction of an alcohol with a halogen compound under basic conditions 583 5.7 ALIPHATIC ALDEHYDES 585 Structure 585 Summary of preparative methods and of retrosynthetic strategies 585 Spectroscopic features 587 5.7.1 The controlled oxidation or dehydrogenation of primary alcohols 587 5.7.2 The oxidative cleavage of 1,2-diols 590 5.7.3 The ozonolysis of suitably substituted alkenes 592 5.7.4 The reduction of nitriles, carboxylic acids and carboxylic acid chlorides 594 5.7.5 Methods based upon alkyl halides 596 5.7.6 The hydrolysis and decarboxylation of ,-epoxy esters (glycidic esters) 598 5.7.7 The oxidative hydrolysis of nitronate salts derived from primary nitroalkanes 599 5.7.8 Methods for the alkylation of the carbon chain 600

5.8 ALIPHATIC KETONES

604

Structure 604 Summary of preparative methods and of retrosynthetic strategies 605 Spectroscopic features 606 5.8.1 The oxidation of secondary alcohols 607 5.8.2 The hydration of alkynes 612 5.8.3 The thermal decarboxylation of acids over a metal oxide catalyst 612 5.8.4 The interaction of organometallic compounds with carboxylic acid chlorides and N,N-dimethylcarboxainides 616
IX

CONTENTS

5.8.5 The hydrolysis and decarboxylation of -keto esters and the hydrolysis of -diketones 619 5.8.6 The acid-catalysed rearrangement of 1,2-diols 623 5.8.7 The oxidative hydrolysis of nitronate salts from secondary nitroalkanes 623 5.8.8 Methods for the protection of the carbonyl group in aldehydes and ketones 623

5.9 DICARBONYL COMPOUNDS

Structure 626 5.9.1 1,2-Dicarbonyl compounds 627 5.9.2 1,3-Dicarbonyl compounds 632 5.9.3 1,4-Dicarbonyl compounds 635

626

5.10 CARBOHYDRATES
Structure 637 5.10.1 Carbohydrate interconversions 5.10.2 Carbohydrate intercon versions 5.10.3 Carbohydrate interconversions 5.10.4 Carbohydrate interconversions 5.10.5 Carbohydrate interconversions 642 644 651 658 660

637

5.11 ALIPHATIC CARBOXYLIC ACIDS

664

Structure 664 Summary of preparative methods and of retrosynthetic strategies 664 Spectroscopic features 666 5.11.1 Oxidative methods 667 5.11.2 Hydrolysis of alkyl cyanides 671 5.11.3 Carboxylation of Grignard reagents 673 5.11.4 The Arndt-Eistert method 675 5.11.5 Electrolytic (anodic) coupling 677 5.11.6 Methods utilising diethyl malonate 680 5.11.7 The synthesis of optically active carboxylic acids 687 5.11.8 Methods for the protection of the carboxyl group 690

5.12 CARBOXYLIC ACID DERIVATIVES

Structure 691 Summary of retrosynthetic strategies 692 Spectroscopic features 692 5.12.1 Acylhalides 692 5.12.2 Acid anhydrides 693 5.12.3 Esters 695 5.12.4 Acid amides 708 5.13

691

ALIPHATIC NITRILES 710 Summary of preparative methods and of retrosynthetic strategies 710 Spectroscopic features 711 5.13.1 Displacement with cyanide ion on an alkyl halide 711 5.13.2 Displacement with cyanide ion on an arylsulphonylhydrazone 712 5.13.3 Dehydration of amides and aldoximes 715

CONTENTS

5.13.4 Cyanoethylation procedures and the -alkylation of nitriles 717 5.14 SUBSTITUTED CARBOXYLIC ACIDS AND THEIR DERIVATIVES
Structure 719

719

Spectroscopic features 720 5.14.1 Halogeno acids 720 5.14.2 Hydroxy acids and lactones 725 5.14.3 Keto acids and esters 735 5.14.4 Amino acids and peptides 746

5.15 NITROALKANES

763

Structure 763 Summary of preparative methods and of retrosynthetic strategies 764 Spectroscopic features 764 5.15.1 The displacement of a halogen by a nitrite ion in an alkyl halide 764 5.15.2 The oxidation of oximes and amines 765 5.15.3 C-Alkylation of nitroalkanes and other homologation procedures 768

5.16 ALIPHATIC AMINES

769

Structure 769 Summary of preparative methods and of retrosynthetic strategies 770 Spectroscopic features 771 5.16.1 The reduction of alkyl azides, alkyl cyanides and amides 771 5.16.2 The reduction of nitro compounds and oximes 774 5.16.3 The reductive alkylation of ammonia or amines 776 5.16.4 The alkylation of ammonia and its derivatives 779 5.16.5 Imine and enamine formation 782 5.16.6 Molecular rearrangements of the Hofmann type 783 5.16.7 Methods for the protection of the amino and imino groups 784 5.17 ALIPHATIC SULPHUR COMPOUNDS Structure 786 Spectroscopic features 787 5.17.1 Thiols and thioacetals 787 5.17.2 Dialkyl sulphides (thioethers) and trialkylsulphonium salts 789 5.17.3 Sulphoxides and sulphones 791 5.17.4 O,S-Dialkyl dithiocarbonates (xanthate esters) 792 5.18 UNSATURATED COMPOUNDS 5.18.1 Unsaturated alcohols 794 5.18.2 Unsaturated carbonyl compounds 798 5.18.3 Unsaturated acids and esters 820 RESOLUTION OF RACEMATES 786

794

5.19

809 816

REFERENCES

XI

CONTENTS

CHAPTER 6 AROMATIC COMPOUNDS

6.1 AROMATIC HYDROCARBONS Structure 824 Spectroscopic features 825 6.1.1 Alkylbenzenes 826 6.1.2 D i - and triarylmethanes 833 6.1.3 Biphenyl systems 835 6.1.4 Condensed polycyclic systems 839 6.1.5 Some non-benzenoid systems 847

824
824

6.2 AROMATIC NITRO COMPOUNDS 850 Summary of preparative methods and of retrosynthetic strategies 850 Spectroscopic features 851 6.2.1 Direct nitration 851 6.2.2 The oxidation of amines 857 6.2.3 The replacement of a diazo group by a nitro group 858 6.3 AROMATIC HALOGEN COMPOUNDS 858 Structure 858 Summary of preparative methods and of retrosynthetic strategies 858 Spectroscopic features 859 6.3.1 Direct halogenation 860 6.3.2 Chloromethylation 865 6.3.3 The replacement of a diazo group by a halogen 867 6.3.4 The replacement of a hydroxyl group by a halogen 867 6.3.5 Methods leading to polyvalent iodine compounds 868 6.4 AROMATIC SULPHONIC ACIDS AND THEIR DERIVATIVES 872 Structure 872 Summary of preparative methods and of retrosynthetic strategies 872 Spectroscopic features 873 6.4.1 Direct sulphonation 873 6.4.2 The preparation of arylsulphonyl chlorides 877 6.4.3 The preparation of arylsulphonamides 879 6.4.4 The preparation of arylsulphonate esters 883 6.4.5 Reduction products from arylsuphonyl chlorides 887

6.5 AROMATIC AMINES

888

Structure 888 Summary of preparative methods and of restrosynthetic strategies 889 Spectroscopic features 890 6.5.1 The reduction of nitro compounds 892 6.5.2 Molecular rearrangements of the Hofmann type 897 6.5.3 The replacement of halogen by an amino group 900 6.5.4 The replacement of a phenolic hydroxy! group by an amino group 900 6.5.5 Alkylation and reductive alkylation procedures 901 6.5.6 Some methods for the protection of the amino and imino groups 906
Xll

COMTEIITS

6.6 SUBSTITUTION PRODUCTS OF AROMATIC AMINES 6.6.1 Nuclear substitution products 906 6.6.2 Acylated amines and their substitution reactions 916 6.7 FORMATION OF DIAZONIUM SALTS AND THEIR USES 6.7.1 Reactions involving replacement of the diazo group 922 6.7.2 Coupling reactions 946

906

920

6.8 MISCELLANEOUS AROMATIC NITROGEN COMPOUNDS 953 6.8.1 Intermediate products in the reduction of nitro compounds 953 6.8.2 Arylhydrazines 959 6.8.3 Arylureas and related compounds 963

6.9 PHENOLS AND PHENYL ETHERS

Summary of preparative methods and of retrosynthetic strategies 968 Spectroscopic features 969 6.9.1 Methods for the introduction of a hydroxy! group into an aromatic ring 970 6.9.2 Substitution reactions of phenols 975 6.9.3 Formation of phenyl ethers 984 6.9.4 Some methods for the protection of the phenolic hydroxy! group 988

968

6.10 AROMATIC ALDEHYDES 989 Summary of preparative methods and of retrosynthetic strategies 989 Spectroscopic features 990 6.10.1 Aromatic formylation reactions 990 6.10.2 Reactions involving modification of aromatic ring substituents 999 6.11 AROMATIC KETONES AND QUINONES Summary of preparative methods and of retrosynthetic strategies for aromatic ketones 1005 Spectroscopic features 1005 6.11.1 Friedel-Crafts-type acylation processes 1006 6.11.2 Synthesis of aromatic ketones from carboxylic acid derivatives 1008 6.11.3 Quinones 1019 6.12 SOME REACTIONS OF AROMATIC CARBONYL COMPOUNDS 6.12.1 The Cannizzaro reaction 1028 6.12.2 The Claisen-Schmidt and related reactions 1032 6.12.3 The Perkin and Doebner reactions 1036 6.12.4 The synthesis of diphenylpolyenes 1041 6.12.5 The benzoin condensation 1043 6.12.6 Oxime formation 1047 6.12.7 Some reactions of alkyl aryl ketones 1050 6.12.8 Methods for the protection of the aromatic carbonyl group 1056 1005

1028

6.13 AROMATIC CARBOXYLIC ACIDS 1056 Summary of preparative methods and of retrosynthetic strategies 1056 Spectroscopic features 1057
Xlll

CONTENTS

6.13.1 6.13.2 6.13.3 6.13.4 6.13.5

Oxidative methods 1057 The hydrolysis of nitriles 1062 Carboxylation of the aromatic ring system 1067 Nuclear nitration of aromatic carboxylic acids and esters 1071 Some methods for the protection of the carboxyl group 1072 1073

6.14 AROMATIC CARBOXYLIC ACID DERIVATIVES

Structure 1073

Spectroscopic features 1073 6.14.1 Acidhalides 1073 6.14.2 Acid anhydrides 1074 6.14.3 Esters 1076 6.14.4 Acid amides 1080

6.15 AROMATIC NITRILES

1081

Summary of preparative methods and of retrosynthetic strategies 1081 6.15.1 The Sandmeyer procedure 1081 6.15.2 The displacement of halogen by cyanide in an aryl halide 1082 6.15.3 The dehydration of amides and aldoximes 1082 REFERENCES 1085

CHAPTER 7 SELECTED ALICYCLIC COMPOUNDS 7.1 INTRAMOLECULAR NUCLEOPHILIC DISPLACEMENT REACTIONS 7.2 INTRAMOLECULAR ADDITION REACTIONS OF CARBANIONS TO A CARBONYL GROUP 7.3 INSERTION REACTIONS 7.4 RING EXPANSION AND RING CONTRACTION REACTIONS 7.5 REDUCTION OF AROMATIC COMPOUNDS 7.6 CYCLOADDITION REACTIONS REFERENCES

1087 1087 1092 1106 1111 1114 1117 1126

CHAPTER 8 SELECTED HETEROCYCLIC COMPOUNDS

1127

8.1 THREE-MEMBERED HETEROCYCLES 1127 8.1.1 Intramolecular cyclisation of a 1,2-bifunctional compound 1128 8.1.2 Insertion of a methylene group into a carbon heteroatom double bond 1131 8.1.3 Insertion of a heteroatom into a carbon-carbon double bond 1132 8.1.4 Heteroatom exchange 1137 8.2 FOUR-MEMBERED HETEROCYCLES 8.2.1 Cyclisation reactions 1138 8.2.2 Cycloaddition reactions 1141
XIV

1138

CONTENTS

8.3 FIVE-MEMBERED HETEROCYCLES 1144 8.3.1 Pyrroles, furans, thiophenes and pyrazolones from dicarbonyl compounds 1146 8.3.2 Hydantoins from urea, and thiazoles from thiourea or thioamides 1151 8.3.3 Oxazolones (and aziactones) from -amino acids 1155 8.3.4 Indoles, benzofurans and benzothiophenes 1156 8.3.5 Benzimidazoles and benzotriazole from o-phenylene diamine 1162 8.4 SIX-MEMBERED HETEROCYCLES 8.4.1 Pyridines and pyrylium salts 1165 8.4.2 Pyrones and pyridones 1172 8.4.3 Barbituric acid and barbiturates 1174 8.4.4 Quinolines, isoquinolines and quinoxalines 1180 8.4.5 Coumarins and chromones 1190 REFERENCES 1164

1194

CHAPTER 9 INVESTIGATION AND CHARACTERISATION OF ORGANIC COMPOUNDS

9.1 9.2 9.3 9.4 9.5 PHYSICAL CONSTANTS THE STUDY OF SOLUBILITY BEHAVIOUR DETECTION OF ELEMENTS PRESENT SPECTROSCOPIC INFORMATION FUNCTIONAL GROUP IDENTIFICATION 9.5.1 Acidic compounds 1211 9.5.2 Basic compounds 1215 9.5.3 Neutral compounds 1218

1196
1197 1198 1204 1210 1211

9.6 PREPARATION OF DERIVATIVES 9.6.1 Saturated aliphatic hydrocarbons 1235 9.6.2 Unsaturated aliphatic hydrocarbons 1235 9.6.3 Aromatic hydrocarbons 1238 9.6.4 Alcohols and polyhydric alcohols 1241 9.6.5 Carbohydrates 1245 9.6.6 Phenols 1248 9.6.7 Enols 1251 9.6.8 Aliphatic halogen compounds 1251 9.6.9 Aromatic halogen compounds 1253 9.6.10 Aliphatic ethers 1254 9.6.11 Aromatic ethers 1255 9.6.12 Acetals 1257 9.6.13 Aldehydes and ketones 1257 9.6.14 Quinones 1261 9.6.15 Carboxylic acids 1261 9.6.16 Carboxylic acid chlorides and anhydrides 1265 9.6.17 Esters 1266

1234

xv

CONTENTS

9.6.18 9.6.19 9.6.20 9.6.21 9.6.22 9.6.23 9.6.24 9.6.25 9.6.26 9.6.27

Primary amides 1270 Substituted amides 1271 Nitriles 1271 Primary and secondary amines 1273 Tertiary amines 1278 -Amino acids 1279 Nitrocompounds 1281 Thiols 1283 Sulphonic acids 1284 Sulphonamides 1286 1287

9.7 SEPARATION OF MIXTURES OF ORGANIC COMPOUNDS 9.7.1 Introduction 1287 9.7.2 Preliminary examination of a mixture 1290 9.7.3 Separation of water-insoluble mixtures 1292 9.7.4 Separation of water-soluble mixtures 1295

CHAPTER 10 PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS

Tables of derivatives 1298 Index to tables 1298

1298

APPENDICES
1. 2. 3. 4. 5. 6. 7. THE LITERATURE OF ORGANIC CHEMISTRY INFRARED CORRELATION TABLES NUCLEAR MAGNETIC RESONANCE CORRELATION TABLES MASS SPECTROMETRY CORRELATION TABLES USEFUL SOLVENT CHARACTERISTICS: HAZARD SYMBOLS COMMON SYNTHONS AND THEIR REAGENT EQUIVALENTS SELECTION OF MANUFACTURERS AND SUPPLIERS OF LABORATORY APPARATUS, EQUIPMENT AND CHEMICALS 1401 1412 1423 1435 1442 1447 1451

Table of atomic weights 1454 Index 1455 Reference data 1511 Abbreviations 1513

XVI

CHAPTER 10

PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS

TABLES OF DERIVATIVES
The tables in this chapter contain lists of the more common members of the various classes of organic compounds arranged, as far as possible, in the order of increasing boiling points or melting points, together with the melting points of selected derivatives. Some of the tables are subdivided: thus in Table 10.6, Phenols, the additional sub-headings are Halogeno-phenols and itro-phenols. This subdivision renders the tables less cumbersome and facilitates their use. In describing compounds in the literature, the range of a certain number of degrees is usually recorded for the boiling point or the melting point; the highest point of the boiling point or the melting point range is listed in the tables and the value is given to the nearest whole degree. For those compounds the author has purified or prepared, the actual observed boiling point or melting point is recorded. Densities are given for a temperature of 20 C referred to water at 4 C unless otherwise indicated. Refractive indices are recorded for the sodium D line at 20 C. It must be remembered that the value obtained for a melting point depends upon the observer and upon the method which was used in the determination: this often accounts for the slightly different values found in the literature for the same compound. Reference should be made to Section 2.3.4, p. 44, for those classes of compounds which are potentially carcinogenic; those marked C should be handled with great caution; some are subject to legal control in Great Britain or the U S A or both. INDEX TO TABLES
Table Table Table Table Table Table Table Table Table Table Table Table 1298 10.1. 10.2. 10.3. 10.4. 10.5. 10.6. 10.7. 10.8. 10.9. 10.10. 10.11. 10.12. Saturated aliphatic hydrocarbons Unsaturated aliphatic hydrocarbons Aromatic hydrocarbons Aliphatic alcohols Aromatic alcohols Phenols Enols Polyhydric alcohols Carbohydrates (sugars) Aliphatic halogen compounds Aromatic halogen compounds Aliphatic ethers 1300 1301 1302 1304 1308 1310 1314 1314 1315 1316 1322 1327

TABLES OF DERIVATIVES

11

Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table Table

10.13. 10.14. 10.15. 10.16. 10.17. 10.18. 10.19. 10.20. 10.21. 10.22. 10.23. 10.24. 10.25. 10.26. 10.27. 10.28. 10.29. 10.30. 10.31. 10.32. 10.33. 10.34. 10.35. 10.36. 10.37. 10.38. 10.39. 10.40. 10.41. 10.42. 10.43. 10.44. 10.45. 10.46.

Aromatic ethers Acetals Aliphatic aldehydes Aromatic aldehydes Aliphatic ketones Aromatic ketones Quinones Aliphatic carboxylic acids Aromatic carboxylic acids Acid chlorides (aliphatic) Acid anhydrides (aliphatic) Acid chlorides and acid anhydrides of aromatic acids Aliphatic esters Aromatic esters Primary aliphatic amides Primary aromatic amides Substituted aromatic amides Aliphatic nitriles (cyanides) Aromatic nitriles Primary and secondary aliphatic amines Primary aromatic amines Secondary aromatic amines Tertiary amines Amino acids Aromatic nitro compounds Aliphatic nitro compounds Thiols Sulphonic acids Aromatic sulphonamides Imides Nitroso, azo, azoxy and hydrazo compounds Miscellaneous sulphur compounds Miscellaneous phosphorus compounds Esters of inorganic acids

1328 1330 1332 1334 1336 1338 1342 1342 1346 1350 1350 1351 1352 1357 1361 1363 1364 1366 1369 1370 1372 1378 1380 1384 1386 1387 1387 1388 1392 1393 1393 1395 1397 1398

1299