vogel's textbook of practical organic chemistry 5th ed. (furnis b.s. et all, longman 1989)

Download Vogel's Textbook of Practical Organic Chemistry 5th Ed. (Furnis B.S. Et All, Longman 1989)

If you can't read please download the document

Post on 17-Nov-2014

135 views

Category:

Documents

24 download

Embed Size (px)

TRANSCRIPT

CONTENTS

CHAPTER 1 ORGANIC SYNTHESIS1.1 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

11 2 10 17 23 23

REFERENCES

CHAPTER 2 EXPERIMENTAL TECHNIQUES2.1 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

2626 31 34

52 52 55 57 58 63 64 65V

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 REFERENCESVI

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 ALKENESStructure 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 ALKYNESStructure 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 ALCOHOLSStructure 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 550Vlll

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 616IX

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 COMPOUNDSStructure 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 CARBOHYDRATESStructure 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 DERIVATIVESStructure 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