AdministratorText Box547 ROD V.3 Pt.A

C O N T E N T S

Chapter I I . Mononuclear Hydrocarbons: Benzene and its Homologues

I . Sources of the Hydrocarbons . . . . . . . . . . . . . . . . . . 81 Formation of Aromatic from Aliphatic Hydrocarbons . . . . . . . . 84

2. Reactions of the Hydrocarbons. . . . . . . . . . . . . . . . . . . a. Additive Reactions. . . . . . . . . . . . . . . . . . . . . .

(i) Hydrogenation, 85 - (ii) Addition of Halogens, 85 - (iii) Ozone, 86 - (iv) Hypochlorous Acid. 86 - (v) Polynitro Compounds and Quinones, 86 - (vi) Diazoacetic Ester. 86

b. Oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . c. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . d. Nuclear Substitution Reactions . . . . . . . . . . . . . . . .

(i) Halogenation, 90 - (ii) Nitration, 91 - (iii) Sulphonation, 93 - (iv) Friedel- Crafts Reaction. 94 - (v) Other Substitution Reactions, gg

3 . Individual Hydrocarbons . . . . . . . . . . . . . . . . . . . . a. Benzene. . . . . . . . . . . . . . . . . . . . . . . . . . . IOO b. Homologues of Benzene ; Alkylbenzenes . . . . . . . . . . . . . 102

(i) Preparation, 102 - (ii) Reactions of the Side Chain, 105 - (iii) Individual Alkylbenzenes. 106

ChaPter I I I . Halogen-, Nitro-, Nitroso-, and

Hydroxylamino-Derivatives of Benzene and its Homologues

I . Halogen Derivatives of Benzene and its Homologues . . . . . . . . a. Nuclear Halogen Derivatives . . . . . . . . . . . . . . . . .

General Methods of Preparation, I 13 - Properties and Reactions, I I 3 (i) Halogeno-benzenes, I 15 - (ii) Iodosobenzene, Iodoxybenzene and their Derivatives, 118 - (iii) Mixed Halogeno-benzenes, 120 - (iv) Halogen Derivatives of Alkylbenzenes, 12 I

b. Alkylbenzenes with Halogen in the Side Chain . . . . . . . . . . Preparation, I 24 (i) Benzyl Halides, 125 - (ii) Halogenophenylethanes, 128 - (iii) Benzylidene Halides ; Benzotrihalides, I 28

2. Nitro Derivatives of Benzene and its Homologues . . . . . . . . . a. Nuclear Nitro Compounds. . . . . . . . . . . . . . . . . . .

Methods of Preparation. 130 - Properties and Reactions, 130 (i) Mono- to Tetra-nitrobenzenes, 133 - (ii) Mono- to Tetra-nitrotoluenes, 135 - (iii) Nitro Derivatives of Higher Homologues, 138

b. Halogen Derivatives of Nuclear Nitro Compounds . . . . . . . . (i) Halogen in the Nucleus, 139 - (ii) Halogen in the Side Chain. 143

c. Side Chain Nitro Compounds : Arylnitroparaffins . . . . . . . . . 3 . Nitroso Derivatives of Benzene and its Homologues. . . . . . . . . 4. N-Arylhydroxylamines . . . . . . . . . . . . . . . . . . . . .

Chapter IV. Aromut*

Benzene and i

I . Nuclear Monoamino Derivatives of E a. Primary Amines . . . . . . . .

Methods of Formation, 159 - Propert the Amino Group, 161 - Reactions ol (i) Aniline, 162 - (ii) Toluidines, 165 - 4 166 - (iv) Homologues of Aniline.Hal

b. Secondary and Tertiary Amines . Methods of Formation, 169 - Separati Amines. 170 (i) Monoalkylarylamines, 171 - (ii) Dia Ammonium Com~ounds. 175 - Iivl Alkylarylamines Gith ~ubsti&en& id 1

I. . arylamines. Condensation Products of I 78 - (vii) Dl- and Tri-arylammes, 18

b - c. Arylamides of Inorganic Acids . . (i) Thionylarylamines, 182 - (ii) Aryls of Phosphorus Acids, 183 - (iv) Oths

d . Arylamides of Monobasic Fatty A e. Arylamides of Hydroxy- and Ketc f. Derivatives of Carbonic Acid . .

(i) Derivatives of Carbamic Acid, 1% - (iii) Derivatives of Phenylisourea, I of Hydroxylamine and Hydrazine, Dithio-carbamic Acids, 194 - (vi) Ar Arylisothioureas, 196 - (vln) Phenylt! amine and Hydrazine, 197 - (k) C HOGGARTH). 197- (x) AryltsoCyanate (xii) Phenylcyanamide and its Derh

g. Arylamides of Dicarboxylic Acids h. Phenylamino Derivatives of Fat$ 1. Phenylamino Derivatives of F a r j . Phenylamino Derivatives of Aliph

2. Nuclear Halogen Derivatives of Anil a. Monohalogen-substituted Anilined b. Di-, Tri- and Poly-halogen-substil c. Halogen Derivatives of N-Alkyh

3. Nuclear Nitroso Derivatives of A d L 4. Nuclear Nitro Derivatives of Anilind

a. Nitroanilines. . . . . . . . . b. Nitro Derivatives of Homologues

5. Sulphonic Acids of Aniline and its E 6. Amines with More than One Nuclea

r a. Diamines . . . . . . . . . . b. Tri- and Poly-amines . . . . .

C O N T E N T S

Chapter V . Sulphonic Acids, Sulphinic Acids

and SulPhenyl Compounds of the Benzene Series

. . . . . . . . . . . . . . . . . . . . . . . . I. Sulphonic Acids 2 30 . . . . . a. Nuclear Sulphonic Acids of Benzene and its Homologues 230

General Methods of Formation, 230 - General Properties and Reactions, 230 - Replacement of the Sulphonyl Group, 231 - Reduction to Sulphinic Acids and Thiols, 233 - Preparation of Sulphonyl Halides, 233 - Properties and Reactions of Sulphonyl Halides, 234 (i) Monosulphonic Acids, 234 - (ii) Halogen-substituted Benzenesulphonic Acids, 237 - Nitro-substituted Sulphonic Acids, 238 - (iv) Di- and Tri- sulphonic Acids, 239 - (v) Aryl Selenonic Acids, 240

b. Acids with the Sulphonic Group in the Side Chain . . . . . . . . 240 2. Sulphinic Acids . . . . . . . . . . . . . . . . . . . . . . . . 241 3. Sulphenic Acid Derivatives . . . . . . . . . . . . . . . . . . . 244

. . . . . . . . . . . . . . . . . . . . . . 4. Thiosulphonic Acids 246

Chapter PI . Nitrogen Derivatives of Anilines:

Nitrosamznes; Nitramines; Diazo, Azo, Azoxy and Hydrazo Conzfiounds

I. Phenylnitrosamines . . . . . . . . . . . . . . . . . . . . . . 249 2. Phenylnitramines. . . . . . . . . . . . . . . . . . . . . . . . 252 3. Diazo Compounds . . . . . . . . . . . . . . . . . . . . . 256

a. Methods of Formation and Properties. . . . . . . . . . . . . . 258 (i) Diazonium Salts, 258 [General, 258 - History and Constitution. 259 - Diazotisation of Amines: Theory, 259; Monoamines, 260; Diamines, 262 - Properties of Diazonium Salts; Stability: Solid Diazonium Salts, 264; Stabi- lity in Aqueous Media, 265; Diazo-oxides or Quinonediazides, 266; Diazo- imines or Irninoquinonediazides, 267; Individual Diazonium Salts: from Monoamines, 268; from Diamines, 2711 - (ii) Diazohydroxides and Di- azotates, 272 [Isomerism of Aromatic Diazo Compounds, 272 - History and Constitution, 273 - Formation of n-Diazohydroxides and Diazotates, 274 - Formation of iso-Diazohydroxides and Diazotates, 276 - Diazobenzene- sulphonic Acids, 2781 - (iii) Diazo Ethers, 279 - (iv) Diazomercaptans, Diazosulphides and Diazothioethers, 280 - (v) Diazosulphonates, 280 - (vi) Diazo-sulphinates and -sulphones, 282 - (vii) Diazocyanides, 283

b. General Reactions of Diazo Compounds . . . . . . . . . . . . . 284 (i) With Retention of Diazo Nitrogen, 284- (ii) With Loss of Diazo Nitrogen, 286 peplacement of Diazo Group by Hydrogen and by Various Groups, 287- Reductive Replacement of the Diazo Nitrogen. Formation of Symmetrical Diaryls, 296 - Non-reductive Methods of Replacement of Diazo Nitrogen, 297 - Arylation of Quinones and of Unsaturated Compounds, 2981

4. Diazoamino Compounds (or Triazea . . . . . . . . (or Pentazdiens)

. . . . . History and Constitution a. Triazens (Diazoamino Compounds) b. Pentazdiens (Bisdiazoamino Comp

5. Diazohydroxyamino Compoun

d

s, ~ r i i 6. Aryl Azides . . . . . . . . . . . 7. Azoxy Compounds . . . . . . . . 8. Azo Compounds . . . . . . . . :

a. General Methods of Formation . . (i) Reduction of Nitro, Nitroso and tion of Amines and Hydrazines, 320- Reactions, 320

b. The Diazo-coupling Reaction . . (i) Coupling with Amines, 322 - (ii) Ethers, 323 - (iii) Coupling with Subst Methine or Methyl Group, 323 - (iv) : 326

. . . . c. Properties and Reactions (i) General Properties, 328 - (ii) Reac (iii) Reactions of the Aromatic Nuclei

. . . d. Azobenzene and Derivatives (i) Azobenzene, 333 - (ii) Polyazo Co pounds. 335

. . . . . e. Mixed Azo Compounds . . . . . . g. Hydrazine Derivatives . . . . . . a. Aromatic Hydrazines

General Methods of Formation, 345 (i) Monophenylhydrazines; Hydrazim hydrazines, 347 - (iii) Triphenylh] hydrazines, 348 Properties and Reactions, 348 (i) Oxidation, 349 - (ii) Reduction, 351 Semidine Rearrangements, 351 - (iv) with Aldehydes and Ketones, 354 - ( pounds, 354 - (vii) Formation of Hetc Individual Compounds, 355 (i) Monophenylhydrazines, 355 - ( benzenes, 357 - (iii) as-Diarylhydmzh

b. Mixed Aliphatic-Aromatic Hydrazi Methods of Formation, 358 (i) Alkyl Derivatives of MonophenylJq of Diphenylhydrazines, 359 Individual Compounds, 359

c. Phenylhydrazones and Osazones . Methods of Formation, 360 - Reactia

d. Phenylhydrazine Derivatives of In e. Phenylhydrazides of Monocarboxy

Methods of Formation, 366 - Format Hydrazides, 367

f. Phenylhydrazine Derivatives of C;u . . . . . . . . . . . . Acids

g. Phenylhydrazine Uerivatives of l3

XIV C O N T E N T S

h. Phenylhydrazidines (Amidrazones), Nitrazones, Phenylhydrazoald- oximes, Phenylazoaldoximes (Nitrosazones), Formazyl Compounds . 373 (i) Phenylhydrazidines or Phenylamidrazones, 373 - (ii) Nitrohydrazones or Nitrazones, 374 - (iii) Phenylhydrazoaldoximes and Benzeneazoaldoximes or Nitrosazones, 375 - (iv) Formazyl Compounds, 376

i. Nitroso Derivatives of Phenylhydrazines; Triazans, Tetrazens and . . . . . . . . . . . . . . . . . . . . . . . . . . Tetrazans 378

Chapter V I I . Aromatic Metal and Metalloid Compounds

. . . . . . . . . . . . . . . . . . . . . . . . . . Introduction I. Aromatic Compounds of Elements of Group I . . . . . . . . . . . 2. Aromatic Compounds of Elements of Group 2 . . . . . . . . . . .

a. The Alkaline Earth Metals. . . . . . . . . . . . . . . . . . . b. Typical Elements and B Sub-group, Be, Mg, Zn, Cd, Hg. . . . . .

(i) Magnesium, 386 - (ii) Mercury, 387 . . . . . . . . . . . 3. Aromatic Compounds of Elements of Group 3

(i) Boron, 389 - (ii) Aluminium, 390 - (iii) Gallium, 391 - (iv) Indium, 391 - (v) Thallium, 391

4. Aromatic Compounds of Elements of Group 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . a. Silicon

b. Germanium, Tin and Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Aromatic Compounds of the Transition Elements.

a. Chromium, Manganese, Cobalt. . . . . . . . . . . . . . . . . b. Copper, Silver, Gold . . . . . . . . . . . . . . . . . . . . . c. Metal Derivatives of Cyclopentadiene. . . . . . . . . . . . . .

6. Aromatic Compounds of Elements of Group 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . a. Phosphorus

. . . . . . . . . . . . . . . . . . . . . . . . . . . b. Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . c. Antimony.

. . . . . . . . . . . . . . . . . . . . . . . . . . d. Bismuth 7. Aromatic Compounds of Elements of Group 6 . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . a. Selenium

. . . . . . . . . . . . . . . . . . . . . . . . . . b. Tellurium . . . . . . . . . . . . . . . . . . . . . . . . . Bibliography

Chapter V I I I . Nuclear Hydroxy Derivatives of Benzene and

its Homologues. Phenols

. . . . . . . . . . . . . . . . . . . . . . I. Monohydric Phenols 4 I 3 . . . . . . . . . . . . . . . . . . . Methods of Formation. -. 413 . . . . . . . . . . . . . . . . . . . Properties and Reactions 415

Reactions of the Hydroxyl Group, 415 - Nuclear Substitution, 416

I C O N T I

. . . a. Phenol and its Homologues b. Functional Derivatives of Phenols

(i) Phenyl Alkyl Ethers, 423 - (ii) U Alkyl Ethers with Substituents in tl Ethers, 429 - (v) Esters of Phenols, 421 429 - Esters of Phenols with Carboxyb

c. Thiophenols and their Derivatives (i) Thiophenols, 432 - (ii) Thioethers' Thiophenols and their Derivatives, 437

d . Halogenophenols . . . . . . . . i e. Nitrophenols. . . . . . . . . . .

Nitro Derivatives of Homologues of PC . . . . . . . . f . Nitrosophenols.

. . . . . . . . . g. Aminophenols ' . . . . . h. Phenolsulphonic Acids

. . . . . . . . 2. Dihydric Phenols. Methods of Formation. . . . . . Reactions and Properties . . . .

. . . . . . . . a. o-Dihydric Phenols (i) Catechol and its Derivatives, 465 [Cy Catechol Esters of Inorganic and Orga Nitro Derivatives of Catechol, 469 - (iii) Thio Derivatives of Catechol, 470

. . . . . . . b. m-Dihydric Phenols (i) Resorcinol and its Derivatives, 470, Nitro Derivatives, 472 - (iv) Homolot Derivatives, 474

. . . . . . . c. p-Dihydric Phenols : (i) Hydroquinone and its Derivatives, - (iii) Homologues of Hydroquinone, qj 4 78

d . Amino Derivatives of Dihydric Phe! . . . . . . . . . 3. Trihydric Phenols

a. I : 2 : 3-Trihydroxybenzene . . . . . . . . . . b. I : z : 4-Trihydroxybenzene . . . . . c . I : 3 :5-Trihydroxybenzene

4. Tetra-, Penta- and Hexa-hydric Phenci . . . . . . . a. Tetrahydric Phenols

b. Pentahydric and Hexahydric Phena

Chapter IX. A ~ I

Alcohols, Aldehydes and KeW

I. Aralkylamines of the Benzene Series . . . . . . . Methods of Formation

a. Phenylalkylamines and their Hornoh b. Nuclear-substituted Aralkylamines . c . Benzyl Derivatives of Hydroxylamiz

XVI C O N T E N T S

d. Benzyl Derivatives of Hydrazine . . . . . . . . . . . . . . . . e. Diazo Compounds, Triazens and Azides Related to Benzylamine . .

. . 2. Monohydric Alcohols of the Benzene Series and their Derivatives. . . . . . . . . . . . . . . . . . . . . Methods of Formation

. . . . . . . . . . . . . a. Phenyl Alcohols and their Homologues b. Functional Derivatives of the Alcohols . . . . . . . . . . . . . c. Sulphur Derivatives of the Alcohols . . . . . . . . . . . . . .

. . . . . . . . . . . . . . d. Nuclear-substituted Benzyl Alcohols . . . . . . . . . . . . . . . 3. Monoaldehydes of the Benzene Series

. . . . . . . . . . . . . . . . . . . . Methods of Formation Aromatic Aldehydes, 506 - Methods Applicable to both Aromatic and Aryl- substituted Fatty Aldehydes, 508 - Special Methods for Aryl-substituted Aliphatic Aldehydes, 51 I

. . . . . . . . . . . . . . . . . . . . . a. Aromatic Aldehydes General Properties and Reactions. 51 I - (i) Benzaldehyde and its Homolo- gues, 513 - (ii) Functional Derivatives of Benzaldehyde, 515 - (iii) Halo- genobenzaldehydes, 521 - (iv) Nitrobenzaldehydes, 521 - (v) Hydroxyl- amino-, Nitroso-, Azoxy- and Azo-benzaldehydes, 523 - (vi) Aminobenz- aldehydes, 524 - (vii) Benzaldehydesulphonic Acids, 527

b. Aryl-substituted Fatty Aldehydes . . . . . . . . . . . . . . . 4. Monoketones of the Benzene Series . . . . . . . . . . . . . . . . .

Methods of Formation . . . . . . . . . . . . . . . . . . . . General Methods, 529 - Special Methods for the Preparation of Alkyl Aryl Ketones, 530 - Special Methods for the Preparation of Aryl-substituted Aliphatic Ketones, 530

a. Alkyl Aryl Ketones. . . . . . . . . . . . . . . . . . . . . . b. Nuclear-substituted Acetophenones . . . . . . . . . . . . . . .

(i) Halogenoacetophenones, 536 - (ii) Nitroacetophenones, 537 - (iii) Aminoacatophenones, 537

c. Monoaryl Derivatives of Dialkyl Ketones . . . . . . . . . . . . d. Monoaryl Ketens . . . . . . . . . . . . . . . . . . . . . .

Chapter X . Monocarboxylic Acids of the Benzew Series I

CONTE

. . . . . . . . . . . . . . . . . I. Aromatic Monocarboxylic Acids 541 . . . . . . . . . . . . . . . . . . . Methods of Formation : 541

a. Benzoic Acid and its Homologues . . . . . . . . . . . . . . . 543 . . . . b. Functional Derivatives of Aromatic Monocarboxylic Acids. 545

(i) Esters, 546 - (ii) Aroyl Halides and Mixed Anhydrides with Inorganic Oxy-acids, 547 - (iii) Acid Anhydrides, 548 - (iv) Aroyl Peroxides and Peracids, 548 - (v) Thio- and Dithio-acids, 549 - (vi) Aromatic Amides, 551 - (vii) Benzoyl Derivatives of Amino-acids, 552 - (viii) Aroyl Hydra- . zmes, 556 - (ix) Aroyl Azides, 557 - (x) Nitriles, Aryl Cyanides, 557 - (xi) Amidohalides, Iminohalides and Hydrazidohalides, 561 - (xii) Imino- ethers, 563 - (xiii) Thioamides and Imino-thioethers, 563 - (xiv) Amidines, 564 - (xv) Hydrazidines or Amidrazones, 566 - (xvi) Hydroxamic Acid,

. . . c. Substituted Benzoic Acids. (i) Halogen-substituted Benzoic Acids, 5 Acids, 573 - (iii) Nitrobenzoic Acids, 57 (v) Aminobenzoic Acids, 576 [Anthrani Nuclear-substituted Anthranilic Acids, Compounds from Anthranilic Acid and benzoic Acids, 586 -Diazo-, Azoxy- and Acids. 5881 - (vi) Sulphobenzoic Acids,

2 . Aryl-substituted Saturated Fatty Acid Methods of Formation . . . . .

a. Aryl Fatty Acids. . . . . . . . b. Nitriles of the Aryl Fatty Acids . c. Substituted Aryl Fatty Acids . .

F

will contain chapters coveri

and Hydroximic Acid Halides, 566 - (xvii) Nitrolic and Nitrosolic Acids, I 568 - (xviii) Nitrile Oxides, 569 - (xix) Amidoximes and Related Com- pounds, 570 - (xx) Ottho-acid Derivatives, 571 ,

Quinones, by Z. E. JOLLES

Hydroxy-alcohols, -aldehydes, -ketones Benzene Derivatives to Polycarboxy R. F. GARWOOD

Benzenoid Compounds with Two or More W. J . HICKINBOTTOM, R. F. GARWO(

Benzenoid Compounds with Unsaturated and M. P. ANSELL

Phenylbenzenes and Derivatives; Diphen HICKINBOTTOM

Triphenylmethane; Di-, Tri- and Poly-pht Alkanes and their Derivatives by S.

Pseudo-aromatic Compounds, by R. A. R

Indene, Naphthalene and other Bicyclic by J. VAN ALPHEN and E. H. RODD

Anthracene and Phenanthrene and their S. COFFEY

Other Condensed Ring Compounds and 1 G. M. BADGER