CONTENTS

CHAPTER I

THEORY OF GENERAL TECHNIQUE

THEORY OF DISTILLATION

Vapour pressure . Calculation of the boiling point a t selected pressures . Superheating and bumping . Fractional distillation . The breaking up of azeotropic mixtures . Steam distillation. Distillation of a pair of i-iscible liquids Distillation with superheated steam .

PAGE 1 2 3 . 5 . 12 . 12 . 15

SOLUTIONS OF LIQUIDS IN LIQUIDS

Partially miscible liquids. Critical solution temperature . . 17 Influence of added substances upon the critical solution temperature 20

THEORY OF MELTING AND FREEZING

Melting point and vapour pressure . Effect of impurities upon the melting point . . System in which the solid phases consist of the pure components and

the components are completely miscible in the liquid phase . Construction of equilibrium diagrams System in which the two components form a compound possessing a

congruent melting point . System in which the two components form a compound with an

incongruent melting point . System in which the two components form a continuous series of

solid solutions . Mixed melting points . System in which the solid phases consist of the pure components and

the components are only partially miscible in the liquid state .

Theory of sublimation . . 37 Theory of the action of drying agents . . 39 Deliquescence and efflorescence . . 43 Extraction with solvents . . 44

. CHAPTER I1

EXPERIMENTAL TECHNIQUE .

11.1. Common laboratory apparatus . . 46 11.2. Cleaning and drying of glassware . . 53 11.3. Use of cork and rubber stoppers . . 55 11.4. Cutting and bending of gless tubing . . 57 11.5. Heating batha . . 67 11.6. Cooling baths . . 60 .

xi

CONTENTS

P Mechanioal agitation . Gm absorption traps . Calibration of thermometers . Experimental determination of the melting point. , Miscellaneous forma of melting point apparatus . Experimental determination of the boiling point . Typical msemblies of apparatus for distillation and refluxing . Fire hazards attending the distillation of idammable solvents . h t i o n a l distillation. Distillation with a fractionating column . Simple apparatus for fraotionation . Improved apparatus for fractional distillation . Still heeds for fractionating columns . Distillation under diminished pressure (" vacuum " distillation) . Fractional dbtillation under diminished pressure Water pumps . Oil pumps . Manometers and manostats . Refinements in the technique of distillation under diminished

pressure . Precision fractional distillation under diminished pressure . Molecular distillation . Purifioation of solid organic compounds by crystallisation. General

oomiderations . Experimental details for recrystallisation . Preparation of a fluted filter paper . Removal of traces of colouring matter and resinous products. Use

of decolouriaing oerbon . Difioulties encountered in recrystallisation . Filtration with suction . Drying of the recrystdlised material . Filtration of small quantities of material with suction . Miscellaneous apparatue for filtration with suction . Recrystallisation in en atmosphere of inert gm . Evaporation of the solvent . Drying of solid organic compounds . Drying of liquids or of solutions of organic compounds in organic

solvents . Technique of steam distillation . Modifications of the steam distillation apparatus . Teahnique of extraction with solvents . Extraation by ohernically active solvents . Continuous extraction of liquids or solids by solvents . Teohnique of sublimation Chromatographio adsorption . Purification of the common organic eolventa . Inorgmio reagente-gases Inorgmio reagents-liquids . Inorgenio reagenta-solids . Caloulation of yields . General instructions for work in the laboratory . Safety precautions . APPARATUS WITH IN'I'ERCHANGEABLE GROUND

GLASS JOINTS

'AGE 62 71 72 75 80 83 86 90 9 1 93 94

102 103 108 110 110 112

116 1 1

119 120 1

Interchangeable ground glass joints . . 206 Types of ground glass joints . . 210 Apparatus with interchangeable ground glass joints suitable for

general use in preparative organic chemistry . . 212 Electrio heating mantles (for use in fractional distillation, etc.) . 221

Apparatus for the

PREPARATION

Determination Fractional dist Purification of

n-Butyl chloride ( eec. -Butyl chloride iso-Butyl chloride n-Heryl ahloride (

1

1

CONTENTS . . .

Xll l

i I PAGE 11,58. Apparatus for the continuous extraction of solids or liquids by

i solvents . . 222 I II,59. Lubrication of ground glass joints . . 226

II,60. Typical essemblies . . 226 I

CHAPTER I11

PREPARATION AND REACTIONS O F ALIPHATIC COMPOUNDS

PRELIMINARY LABORATORY OPERATIONS

II1,l. Determination of melting points . . 229 II1,2. Mixed melting points . . 229 III,3. Determination of boiling points . . 230 . . . III,4. Fractional distillation . . 231 III,5. Purification of solid organio compounds by recrystalliaation . . 232

SATURATED ALIPHATIC HYDROCARBONS

III,6. Reactions and characterisation of saturated aliphatic hydrocarbons 234 , . 122 III,7. n-Octane (Wurtz reaction) . . 236

111.8. n-Hexane (hydrocarbon from Qrignard reagent) . . 237 . . . III,9. n-Octane (Ckmmensen reduction OJ a ketone) . . 238 ous products. Use . 127 . . . ETHYLENIC HYDROCARBONS (ALKENES)

. . a i . . . II1,lO. Amylene . 239 II1, l l . Reactions and characteriaation of ethylenic hydrooarbons . . 241 III,12. cycloHexene . . 243

1' ACETYLENIC HYDROCARBONS (ALKYNES)

. . . III,13. Acetylene . . 246 oompounds in organic '!

. . . . 139 4 ALIPHATIC ALCOHOLS 247 . . . . 146 L i

III,14. n-Amy1 alcohol (from ethyl n-valerate) . . 249 111,15. Tetramethylene glycol ( 1 : 4-butanediol) . . 260 III,16. n-Heptyl alcohol (from n-heptaldehyde) . 261 111.17. cycloHexylcarbino1 (from cyclohexyl chloridej : . 262 111.18. n-Hexyl alcohol (from n-butyl bromide) . . 263

* 111.19. n-Nonyl alcohol (from n-bptyl bromide) . . 254 III,20. Methyl n-amyl carbinol (from methyl n-amyl ketone) . . 264

4 111,21. Methyl n-butyl carbinol (from methyl n-butyl ketone) . . 266 III,22. Methyl ieo-propyl carbiiol . . 266 III,23. Di-n-butyl oarbinol (from n-butyl bsomide) . . 266 III,24. Dimethyl n-butyl carbinol. . . 257 III,25. Triethyl oarbinol . . 268 III,26. Dimethyl n-propyl carbiiol . . 269 111.27. Reactions and characterisation of aliphatic alcohols . . 260

AIXYL HALIDES 270

I III,28. n-Butyl ohloride (ZnCl, - HCl nzethod) . . 272 III,29. aec.-Butyl chloride (ZnCl, - HCl method) . . 273

1 III,30. ko-Butyl chloride (SOCl, - Pyridine method) . 1

. 274 1 111.31. n-Hexyl ohloride (SOCZ, method) . . 274

distillation. etc.) . 221

xiv CONTENTS

II1,76. n-Hepteldoxime . 111.77. Pinacol and pinaoolone III,78. Diacetone alcohol . 111,79. Mesityl oxide . .

III,80. ko-Butyrio acid . III,82. n-Butyl n-but III,83. n-Valeric acid III,84. dl-Methylethyl III,85. Reactions and c

ACID CHLORIDES 0

III,86. Acetyl chloride . III,87. n-Butyryl chloride III,88. Reactions andcharao

ACID ANHYDRIDES

PAGE . 275 . 276 . 277 . 277 . 280 . 281 . 284 . 285 . 285 . 288 . 289

cycloHexyl chloride (HC1 - CaC1, method) . tert.-Butyl chloride (HCZ method) . isoPropy1 bromide (HBr method) . n-Butyl bromide (HBr - H,SO4 method) . n-Butyl bromide (KBr - H,SO, method) . n-Butyl bromide (red P - Br, method) . 1 : 4-Diiodobutane (KI - H,PO, methd) . isoPropyl iodide (HI method) . n-Butyl iodide (red P and I, method) . n-Hexyl fluoride . Reactions and characterisation of alkyl halides .

POLYHALOGEN COMPOUNDS

III,43. Chloroform . III,44. Bromoform . III,45. Iodoform III,46. Methylene bromide . III,47. Methylene iodide . III,48. 1 : 2 : 3-Tribromopropane

ESTERS OF INORGANIC ACIDS Acetio anhydride . Keten . . . n-Caproio anhydride ; Succinic anhydride . Maleio anhydride . Reactions and o h

n-Butyl sulphite . n-Butyl phosphate . n-Butyl borate . n-Propyl thiocyanate . n-Amy1 nitrite . 1-Nitro-n-butane (AgNO, method) . - - Nitromethane

n-Butyl acetate . t&.-Butyl -tab .

Reaotione end

ALIPHATIC ETHERS

Diethyl ether . Di-n-butyl ether . Ethyl n-hexyl ether cycbHexy1 ethyl ether . Reactions and characterisation of aliphatic ethers

ALIPHATIC ALDEHYDES

n-Buty-raldehyde . n-Hexaldehyde (catalyst method) . n-Hexaldehyde (ethyl orthoformate ntethod) . n-Hexaldehyde (from n-amyl cyanide) . Acetaldehyde (from paraldehyde) . Formaldehyde . Hexamethylenetetramine (hexamine) . Acetal (acetaldehyde diethylacetal) . Reactions and characterisation of acetals . Reaotions and characterisation of aliphatic aldehydes

ALIPHATIC KETONES

Methyl n-hexyl ketone . Diethyl ketone . cycloPentanone . Reactions and characterisation of aliphatic ketones Acetone oyanohydrii .

CONTENTS I

PAGE . 276 . 276 . 277 . 277 . 280 . 281 . 284 . 286 . 286 . 288 . 289

PAGE II1,76. n-Heptaldoxime . . 348 III,77. Pinacol and pinacolone . . 349 III,78. Diacetone alcohol . . 361 III,79. Mesityl oxide . . 363

SATURATED ALIPHATIC RIONOBASIC ACIDS 364

III,80. iso-Butyric acid . .. . . 366 III,81. n-Heptoic acid . . 366 III,82. n-Butyl n-butyrate . . 367 III,83. n-Valeric acid (hydrolysis of n-buy1 cyanide) . . 367 III,84. dl-Methylethylacetic acid (carbonation of a Gignard reagent) . . 368 III,85. Reactions and characterisation of aliphatic carboxylic acids . . . 360

ACID CHLORIDES O F ALIPHATIC CARBOXYLIC ACIDS 367

III,86. Acetyl chloride . . 367 III,87. n-Butyryl chloride . . 368

I III,88. Reactions and characterisation of acid 'chlorides oialiphatic acids . 369

ACID ANHYDRIDES OF ALIPHATIC CARBOXYLIC ACIDS 371

L III,89. Acetio anhydride . . 372 III,90. Keten . . 372 I 1 1 9 1 n-Caproio anhydride. . . 374 III,92. Succinic anhydride . . 376 III,93. Maleic anhydride . . 376 III,94. Reactions and oharacterisation of acid anhydrides '(aliphatio) . 376

ALIPHATIC ESTERS

II,95. n-Butyl acetate . :II,96. te7t.-Butyl acetate . :II,97. n-Butyl formate . :II,98. cycloHexy1 acetate . :II,99. Diethyl adipate (azeotropic mixture method) . ;II,100. Diethyl adipate (benzene &hod) . :II,101. n-Propyl n-valerate . [II,102. ieo-Propyl lactate (ion mchange reAn catalyst method) . ;II,103. Diethyl maleate (silver sd t method) . [II,104. Ethyl n-valerate (from n-butyl cyanide) . . . . [II,105. Ethyl vinylacetate ( a d chlmide method) . [II,106. Reactions and characterktion of aliphatic esters .

ALIPHATIC AMIDES

111,107. Acetamide (from ammonium ace&& or from acetic acid) . 111,108. Acetamide (from ethyl acetate) . 111,109. n-Caproamide . 111,110. Reactions and characterktion of aliphatic amides .

ALIPHATIC CYANIDES (NITRILES)

II1,l 11. Acetonitrile . 111,112. n-Amy1 oyanide (n-capronitrile) . . 111,113. n-Butyl cyanide (n-valeronitrile) . 111,114. Trimethylene dicyanide (glutaronitrile) . 111,115. Reectione and characterisation of aliphatic cymnides (nitrilesl

ONOBASIC ACIDS

. . .

. . .

. . . TS AND SOAPS

. . .

. . . C COMPOUNDS

CONTENTS xvii 'AGE

413 PAGE SOME ALIPHATIC DICARBOXYLIC ACLDS 489

111,157. Malonio acid . . 490 111,158. Glutaric acid (from trimethylene dicyanide) . . 491 111,159. Pimelic acid (from benzoyl pipedim) . . 492 111,160. Glutario acid (from cyclopentanone) . . 493 111,161. Adipioacid . . 494 111,162. a-Dimethylaucoinio acid . . 496

ALIPHATIC SULPHUR COMPOUNDS 496

111,163. n-Hexyl mercaptan (n-hexyl thiol) . . 497 111,164. Di-n-propyl sulphide . . 497 111,165. Diethyl disulphide . . 498 111,166. Potassium ethyl xanthate . . 499 111,167. Ethyl 5-ethyl xanthate . . 499 111,168. Reactions and characterisation of mercaptane (thiols) . . 600

RESOLUTION O F A RACEMIC COMPOUND

III,1 C Q netermination of the rotatory power . 503 II1,I ,rcdution of see.-octyl alcohol (dl-2-octanol) into its optioally

-;ive components (d- and 1-2-octanol) . . 605

. REPARATION AND REACTIONS OF AROMATIC COMPOUNDS

AROMATIC HYDROCARBONS 608

IV. n-Butylbenzene ( Wurtz - Fittig synthesis) . . 611 IV ho-Propylbenzene (cumene) . . 612 I\ tert.-Butylbenzene . . 613 IT Diphenylmethane . . 613 J 1. Triphenylmethane . . 616

. . Ethylbenzene . 616 1 V ,7. n-Propylbenzene . . 616 IV,8. n-Amylbenzene . . 617 IV,9. Characterisation of aromatic hydrocarbons . . 618

\

2 NITRATION O F AROMATIC HYDROCARBONS

IV, 10. Nitrobenzene IV,11. a-Nitronaphthalene . IV,12. m-Dinitrobenzene . IV,13. 2 : 4-Dinitrotoluene . IV.14. p-Bromonitrobenzene . IV,15. 2 : 2'-Dinitrodiphenyl . IV,16A. Reactions and oharacteriaation of aromatic nitro compounds IV,16B. Reactions and characterisation of aliphatio nitro compounds

I HALOGENATION O F AROMATIC HYDROCARBONS 633

IV,17. Chlorobenzene . 635 I IV, 1 8. Bromobenzene . 636

IV, 19. m-Bromonitrobenzene . . 637

I

xviii CONTENTS

a-Bromonaphthalene . Iodobenzene . Benzyl ohloride (chhinrrtion of toluene) . Benzyl chloride (chlwomethylation of benzene) . Iodobenzene dichloride . Iodosobenzene Iodoxybenzene . Diphenyliodonium iodide . Reactions and characterisation of halogenated aromatic

aarbona .

SULPHONATION O F AROMATIC HYDROCARBONS 64 8

IV.29. Sodium benzenesulphonate . . 649 IV.30. Sodium p-toluenesulphonate . . 660 IV.31. Sodium p-naphthalenesulphonate . . 661 IV.32. p-Toluenesulphonio acid . . 662 IV.33. Reactions and characterisation of aromatic sulphonic acids . . 662 IV,33A. Reactions and characterisation of aromatic sulphonamides . . 668

AROMATIC AMINES AND T H E I R SIMPLE DERIVATIVES 669

IV.34. Aniline . . 663 IV.35. f3-Phenylethylamine . . 666 IV.36. a-Phenylethylamine . . 667 IV.37. a-Naphthylamine . . 668 IV.38. P-Naphthylamine . . 668 I V.39. Benzylemine (Qabriel8yntheeis) . . 669 IV.40. Pure methylaniline from commercial methylaniline . . 670 IV.41. Benzylaniline . . 672 IV.42. Dimethylaniline . . 672 IV.43. p-Nitrosodimethylaniline . . 673 IV.44. m-Nitroaniline . 674

ACETYLATION O F AROMATIC AMINES

BENZOYLATION O F AROMATIC AMINES 68%

IV.52. Benzanilide (Schotten - Baumunn remiion) . . 682 IV.53. Benzanilide . . 683 IV.54. Hippuric acid (benzoyl glycine) . . 684

SULPHONATION O F AROMATIC AMINES 686

IV.55. Sulphanilic acid . . 686 IV.56. Naphthionio acid . . ' . 686 IV.57. Orthanilio acid . . 687 IV .5 8. Metanilio acid . 689

Solid phenyldiazoni Iodobenzene . .

Methyl orange. . Orange I1 (f3-naphthol Methyl red . . Diazohobenzene . p-Amino-azobmme.

INTERMEDIA

Benzidine . >TION OF DIAZO

Thiocarbdde

Reaotiona and

CONTENTS xix

PAGE 690

. 697 . 698 . 600 . 602 . 606 . 606

. 607

. 607 . 609 . 612 . 613

DIAZONIUM SALTS Solid phenyldiazonium chloride . Iodobenzene . p-Chlorotoluene . p-Bromotoluene (Sandmyer reaction) . m-Bromotoluene . o-Bromotoluene (Oattemnn reaction) . Benzenesulphinic acid . p-Tolunitrile (p-tolyl cyanide) . Fluorobenzene o-Dinitrobenzene . Phenol (from aniline) .

HYDROCARBONS 64 8

. . . . 649

. . . . 660

. . . . 661 . 662

1 ~ 1 7 0 . m-~itrophenol .. IV,71. Toluene (from p-tohidine) . IV,72. 8ym.-Tribromobenzene . IV,73. 3 : 3'-Dimethyldiphenyl . I V,74. Diphenio acid (from anthranilic acid) . IV,75. Phenylareonic acid .

SOME AZO DYESTUFFS 620

Phenyl-azo-P-naphthol . . 622 Chrysoidine . . 623 Methyl orange . . 624 Orange I1 (P-naphthol orange) . . 626 Methyl red . . 626 Diazoaminobenzene . . 626 p-Amino-azobenzene. . : . 627

'ES

INTERMEDIATE PRODUCTS I N T H E REDUCTION OF NITRO COMPOUNDS 628

8-Phenylhydroxylamine . . 629 Nitroeobenzene . . 630 Azoxybenzene . . 631 Azobenzene . . 631 Hydrazobenzene (sym.-diphenylhydrazine) . . 632 Benzidine . . 633

REDUCTION OF DIAZONIUM COMPOUNDS. ARYL HYDRAZINES 636

AROMATIC DIAMINES 640

MISCELLANEOUS COMPOUNDS DERIVED FROM PRIMARY AMINES

IV,94. Thiocarbdde (m.-diphenylt.hiouree) . . 642 IV,95. Phenyl iso-thiooyanate (from thiocarbanilide) . . 642 IV,96. Phenyl k-thiocyamte (from aniline) . . 643 I V,97. Phenylurea (cya?tatc method) . . 644 I V,98. Phenylurea (urea method) . . 646 IV,99. p-Iodoeniline . . 647 IV,100. Reeotioxw and charactarhtion of aromatio mines . . 648

IV, 149. p-Benzoquinone (" quin IV,150. 1 : 2-Naphthoquinone IV,151. Quinhydrone . . IV,152. Reectione and c h m

CONTENTS

PHENOLS p-Cmol . p-Naphthol . Phenyl acetate. . Anisole . Phenyl n-butyl ether . Reeotione and characterisation of aromatic ethers o-Propiophenol and p-propiophenol . o- and p-nitrophenols . 2 : 4-Dinitrophenol . Piorio mid (2 : 4 : 6-trinitrophenol) . p-Bromophenol . o-Bromophenol . p-Iodophenol . Raeotions and charmteriaation of phenols .

IV,174. Phenylpropiolic aoid , IV ,175. Reeotions and chmtr

AB IV,176. Methyl benzoate . IV,177. Methyl doylate . IV,178. Benzyleoetete . IV,179. Ethyl phenybetete IV, 1 80. Phenyl cinnamate . IV,181. Phenyl benzmte . IV,182. Ethyl a-naphthoate . IV,183. FLeactione and chard

AROW

IV,184. p-Nitrobenzoyl chlorh IV,185. Benzoyl chloride .

AROW

IV,186. p-Chlorobemoio enhg IV,187. Reectione and charaa

ARO IV,188. Benzamide . IV,189. Memurg w d e IV,190. O - T o l d d e . IV,191. Remtione and cham IV,192. Reeotione and aha

(ammatio mylad

AROMATIC ALDEHYDES IV,115. Benzaldehyde . IV,116. p-Bromobenzaldehyde . IV,117. p-Nibrobenzaldehyde . IV,118. p-Tolualdehyde . lV,119. p-Naphthnldehyde . IV,120. a-Naphthaldehyde (Sommht reaction) . IV,121. Meeitaldehyde . IV,122. Salioylaldehyde .

CONDENSATION REACTIONS OF AROMATIC ALDEHYDES 706

IV,123. Benzyl aloohol and benzoic mid (Cannizzaro reaction) . . 711 IV,124. Cinnamio acid . . 712 IV,125. Benzoin . . 714 IV,126. Bend . . 714 IV.127. Benzilio aoid . . 716 IV,128. Benzahetone . . 716 IV,129. P-Nitrostyrene . . . 717 IV, 130. Benzelacetophenone (chalcone) . . 718 IV,131. Ethyl oinnamate . . 718 IV,132. P-Piperonylaarylio acid (3 : 4-methylenediogycinnamic mid) . . 719 IV,133. a- and p-Benzaldoximee . . 719 IV,134. Hydrobendde . . 720 IV,135. Reaotione and characterisation of aromatio aldehydes . . 720

AROMATIC KETONES

Aoetophenone Butyrophenone . p-Bromoacetophenone . Bemophenone . Benzylacetophenone . Methyl benzyl ketone . Phloroeoetophenone . a-Tetralone . o-Benzoylbenzoio acid . Anthraquinone . Anthrone . Benzophenone oxime and Beokmann mamaugement Reeotions and chareoterisation of arometio ketones

CONTENTS xxi

PAGE 746

IV.149. p-Benzoquinone (" quinone ") . . 746 IV.150. 1 : 2-Naphthoquinone . . 746 IV.151. Quinhydrone . . 747 IV.152. Reections and characterhation of quinones . . 747

AROMATIC CARBOXYLIC ACIDS 761

IV.153. Benzoic acid . . 766 IV.154. p-Nitrobenzoio acid . 767 1V.155. 2 : 4 : 6-Trinitrobenzoic acid . . 768 IV, 156. 2 : 4-Ditrophenylacetic acid . . 768 IV, 157. o-Chlorobenzoio acid . 768 1V,158. Terephthelio wid . . 760 IV, 159. o-Toluio mid . . 760 IV,l60. Phenyleoetio acid (from be7azyl cyanide) . . 761 1V.161. p-Nitrophenylaoetio acid . . 763 IV, 162. p-Aminophenylacetic acid . . 764 IV.163. a-Naphthoio acid . . 764 IV.164. P-Naphthoio acid . . 766 IV.165. Diphenic acid (from. phnadhrene) . . 768 IV, 166. Hydrooinnamio acid . . 788 IV,167. m-Nitrobenzoio acid . . 769 IV,168. 3 : 6-Dinitrobenzoic acid . . 770 IV,169. Homophthalio acid . . 771 IV,170. Anthranilic acid . . 773 IV, 17 1. Diphenylecetio wid . . 773 IV, 172. Mandelio acid . . 774 IV.173. Salioylio acid . . 774 IV, 174. Phenylpropiolic acid . . 776 IV.175. Reactions and charaoterisation of aromatic carboxylic acids . . 777

AROMATIC ESTERS IV.176. Methyl benzoate . IV.177. Methyl salioylate . IV, 178. Benzyl acetate . IV.179. Ethyl phenylacetate . IV,180. Phenyl cinnamata . IV,181. Phenyl benzoate . IV.182. Ethyl a-naphthoata . IV.183. Reactions and characterisation of aromatic eaters

AROMATIC ACID CHLORIDES 791

IV.184. p-Nitrobenzoyl chloride . . 791 IV.185. Benzoyl ohloride . . 792

AROMATIC ACID ANHYDRIDES 784

IV,186. p-Chlorobenzoio anhydride . .' 794 IV.187. Reactione and oharacterisation of acid ohlorides of aromatic acids . 796

AROMATIC ACID AMIDES 797

IV,188. Benzamide . . 797 IV.189. Memury benzamide . . 797 IV,190. o-Toluemide . , 798 IV,191. Reactions and characterisetion of primary aromatic amides . . 798 IV.192. Reactions and chamtarhation of substituted aromatio amidea

(womatio acylated baeea) . . 801

xxii CONTENTS

AROMATIC NITRILES PAGE

803

IV,193. Benzonitrile . . 803 IV,194. Veratronitrile . . 804 IV.195. Reactions and characterisation of aromatic nitriles . . 805

SOME AROMATIC PEROXIDES AND PER-ACIDS

IV,196. Benzoyl peroxide . . 807 IV,197. p-Nitrobenzoyl peroxide . . 808 IV.198. Perbenzoic acid (benzoyl hydrogen peroxide) . . 808 IV,199. Monoperphthalio acid . . 810

AROMATIC ALCOHOLS 81 1

IV,200. p-Tolyl carbinol (p-methyl benzyl alcohol) . . 812 IV.201. Benzhydrol (diphenylcarbinol) . . 812 IV.202. Triphenylcarbinol . . 813 IV,203. Triphenylchloromethane . . 816 IV,204. P-Phenylethyl alcohol . . 816 IV.205. Reactions and characterisation of aromatic alcohols . . 817

COMPOUNDS DERIVED FROM AROMATIC SULPHONIC ACIDS 820

IV,206. Benzenesulphonyl chloride . . 822 IV,207. p-Toluenesulphonyl chloride . . 822 IV ,208. Dichloramine-T and chloramine-T . . 823 IV,209. Saccharin . . 824 IV,210. n-Butyl p-toluenesulphonate . . 825 IV,211. Sodium p-toluenesulphinate . . 826 IV,212. Thiophenol . . 827

CHAPTER V

SOME HETEROCYCLIC AND ALICYCLIC COMPOUNDS

Quinoline . Quinaldine . Furfuryl alcohol and furoic acid . 2-Furfuralacetone . Furylacrylic acid . Furoin . Furil . 2-Methylthiophene . 2 : 6-Dimethylthiophene . 2-Acetylthiophene . . Pyrrole . 2 : 6-Dimethylpyrrole . 2 : 4-Dimethyl-3 : 6-dicarbethoxypyrrole Succinimide . 2-Arninothiazole . 2 : 4-Dimethylthiazole . 2 : 6-Dimethylpyrazole . 6 : 6-Dimethy1hydanto.h . 4-Ethylpyridine (~%mpyridine) .

Nicotinic acid Ethyl nicotinata . P-CyanopJrridine . Uramil . . . 2-Phenylindole . Benzimidazole .

Acetylacetone .

~ 1 ; 1 9 . VI.20. V1,21. VI.22. VI,23.

It VI.24. VI.25.

VI, 1. v1,2. + VI.3.

Ring enlargement cyclohexanone . "I

Dehydrogenation of hyd Preparation of palladia Oxidation with lead bt~

CONTENTS xxiii

PAGE n-Amylpyridines (front picolines) . . ' . 845 Picolinic acid . . 847 Nicotinic acid . 848 Ethyl nicotinate . . 849 P-Cyanopyridine . . 850 Ur amil . 850 2-~hen~lkdole ' : . 861 Benzimidazole . 853 4-Methylcoumarin . . 853 2-Hydroxylepidine (4-methylcarbostyril) . . 855 Phenylbenzoyldiazomethane . . 856 2-Carbethoxycyclopentanone . . 856 cycloButane- 1 : 1 -dicarboxylic [acid and cyclobutanecnrboxylio

acid . . 857 cycloPropanecarboxylic acid . . 859

CHAPTER VI

MISCELLANEOUS REACTIONS

Acetylacetone Benzoylacetone . Phenylglyoxal . Apparatus for reactions under pressure . Raney nickel (catalyst) . Copper - chromium oxide catalyst . Hexamethylene glycol (1 : 6-Hexanediol) . Ethyl P-phenyl-@-hydroxypropionste PP-Dirnethylglutaric acid . Reductions with lithium aluminium hydride . Reductions with potassium (or sodium) borohydride . Reductions with aluminium alkoxides The Oppenauer oxidation . Oxidation of unsaturated compounds with ozonized oxygen (ozono-

lysis) . . . Epoxidation and hydroxylation of ethylenic compounds . Reactions in liquid ammonia. Some acetylenic compounds . The Arndt-Eistert reaction . The Darzens glycidio eater condemtion . The Erlenmeyer azlaatone reaction . The Mannich reaction . The Michael reaction . Cyanoethylation . The Schmidt reaction or rearrangement . The Stobbe condensation . The Willgerodt reaction . The Wohl-Ziegler reaction. Applications of N-bromosuccinirnide Synthesis of unsymmetrical diaryls . Syntheses with organolithium compounds Syntheses with organosodium compounds . Syntheses with organocadmium compounds . Some electrolytic syntheses . The diene synthesis (Diels-Alder reaction) Some applications of chromatographic adsorption . Ring enlargement with diazomethane. cycloHeptanone from

cyclohexanone . Dehydrogenation of hydroaromatic compounds . Preparation of palladium catalysts for hydrogenation . Oxidation with lead tetra-acetate. n-Butyl glyoxylate .

xxiv CONTENTS

CHAPTER VII ORGANIC REAGENTS IN INORGANIC AND

ORGANIC CHEMISTRY PAGE

Dimethylglyoxime . . 963 Semicarbadde hydrochloride . . 954 Diphenylcarbazide . . 964 Diphenylcarbazone . . 966 Dithizone (diphenylthiocarbazone) . . 966 Cupferron . . 967 Salicylaldoxime . . 967 a-Benzoinoxime . . 968 a-Nitroso-P-naphthol . . 968 Ammonium mlt of aurin tricarboxylic acid (" aluminon ") . . 969 p-Nitrobenzene-azo-a-naphthol . , 960 p-Bromophenacyl bromide . . 960 p-Nitrobenzyl bromide . . 961 p-Phenylphenacyl bromide . . 962 5 : 6-Dimethyl-1 : 3-cyclohexanedione (dimethyldihydro-resorcinol) . 963 Xanthhydrol . . 964 1 : 3 : 6-Trinitrobenzene . . 966 S-Benzyl-bo-thiuronium chloride . . 966 3-Nitrophthalic anhydride . . 966 Diazomethane . . 967 3 : 4 : 6-Triiodobenzoyl chloride . 973 3 : 6-Dinitrobenzoyl chloride . . 974 1 : 2-ycloHexanedione-dioxime (nioxime) . . 974 Quinaldinic acid . . 976 Girard's reagents " T " and " P " . . 976 Pseudo-saccharin chloride . 978

CHAF'TER VIII DYESTUFFS, INDICATORS AND RELATED COMPOUNDS

VIII.1. Congo red . . 979 VIII.2. Indigo . . 980 VIII.3. Alizarin . . 981 V1114. Crystal violet . . 982 VIII.5. Copper phthalocyanine (Monastral Blue) . . 983 VIII,6. Phenolphthalein . . 984 VIII,7. Fluorescein and eosin . . 985 VIII,8. pp -Tetramethyldiaminodiphenylrnethane . . 987 V 1 1 9 o-Sulphobenzoic anhydride . . 987 VII1,lO. Sulphonephthaleins . . 989 VII1,ll. N-Phenylanthranilio acid . . 991 VIII,12. 1 : 10-Phenanthroline . . 991 VIII.13. 2 : 2'-Dipyridyl . . 992 VIII,14. Ninhydrin (indane-1 : 2 : 3-trione hydrate) . . 993

CHAPTER IX SOME PHYSIOLOGICALLY ACTIVE COMPOUNDS

IX,1. Aspirin (acetylsalicylic acid) . . 996 IX.2. Phenacetin . . 996 IX,3. Antipyriue . . 998 IX,4. Bromural (a-bromo-bo-vderylurea) . , 999 IX,5. Benzocaine (ethyl p-aminobenzoate) . . 1000 IX.6. Barbituric acid . . 1001

AJ. A12. A*3. k4- 6 5 - A,6. A,7. 68. k 9 . Atlo.

4 INDEX . . .

INDE

CONTENTS xxv

PAGE Diethylbarbituric acid (veronal) . . 1002

>-(p-~minobenzen&ulphonamido) pyridine (sdphapyridine) . . 1007 Sulphaguanidine . . 1009 2-Phenylquinoline-4-cerboxylic acid (atophan) . . 1010 2 : 2-&(p-Chloropheny1)-1 : 1 : 1-trichloroethane (D.D.T.) . . 1011 3-Indoleacetic acid . . 1012

CHAPTER X SYNTHETIC POLYMERS

Brief introduction to subject . Phenol-formaldehyde resin . Depolymehtion of methyl methacrylate resin . Formation of a glyptal resin . Thiokol A (polyethylene polysulphide) . Phenylethylene (styrene) . Polystyrene . Ethylenediamine - adipic mid polymer . Depolymerisation of a hexamethylenediamine - adipic *cid polymer

(Nylon " 66 ") . CHAPTER XI

QUALITATIVE ORGANIC ANALYSIS Bash of qualitative organic enalysia . Determination of physical constants . Qualitative analyeis for the elements . The solubilities of organic compounds. - . The solubility groups . Determination of the solubilities of organic compounds

-1 - Cless reactions (reactions for functional group) The preparation of derivatives . Qualitative analysis of mixtures of organic compounds

CHAPTER XI1 SEMIMICRO TECHNIQUE

Introduction and general considerations . . 1101 Some typical operations on the aemimicro scale . . 1102 Semimicro apparatus with interchangeable ground glees joints . 1109 Small-scale preparations . . 1110

APPENDIX LITERATURE OF ORGANIC CHEMISTRY

Beilstein's " Hendbuch " . . 1116 Original sources of chemical information . . 1127 Secondary sources of chemical information. Abstracting journtrla . 1127 Locating an organic compound . 1128 Selected reference worh on organic chemistry . . 1128 Laboratory accidents and first aid . . 1130 Applications of infrared and ultraviolet spectra to organic chemistry 1134 Densities and percentage compositions of various solutions . . 1151 Density and vapour pressure of water : 0' to 36' C. . . 1162 Atomic weights . . 1163