Patent GB-475942-A (GB)
Title: Improved manufacture of solid diazonium salts
Filed: 1936-05-28
Abstract: Solid diazonium salts are manufactured by separating a diazonium alkyl sulphate of an aminodiaryl ether in solid form from a solution of such a salt or from a solution of a corresponding mineral acid diazonium compound after addition of an alkylsulphuric acid or a salt thereof, either directly or after neutralizing the excess of mineral acid, by cooling or salting out or both.  In examples: (1) 1-amino-2-(4<1>-chlorophenoxy)-5-chlorobenzene is diazotized, and ammonium sulphate and sodium methyl sulphate are added; the sodium methyl sulphate may be replaced by other alkyl sulphates, e.g. sodium n- or iso-butyl sulphate, and the amine by 1-amino-2-phenoxy - 4 : 5 - dichlorobenzene; (2) sodium ethyl sulphate is employed in the process of (1); (3) 1-amino-2-phenoxy-5-chlorobenzene is diazotized by means of nitrosylsulphuric acid, the diazo solution is mixed with sodium methyl sulphate solution, and Glauber's salt is added; the amine may be replaced by 1 - amino - 2 - (4<1> - methylphenoxy) - 5 - chlorobenzene, and the sodium methyl sulphate by sodium ethylsulphate; (4) 1-amino-2-(naphthyl-2<1> - hydroxy) - 4 - chlorobenzene is diazotized, and sulphuric acid, sodium methyl sulphate and ammonium sulphate are added; 1-amino-2-phenoxy-4-chlorobenzene may be similarly treated; (5) 1-amino-2-(4<1>-chlorophenoxy)-5-chlorobenzene is diazotized in the presence of ethylsulphuric acid, and ammonium sulphate is added; (6) 1-amino-2-(2<1>-chlorophenoxy)-benzene is diazotized by means of nitrososulphuric acid, the diazo solution is mixed with Glauber's salt, and sodium methyl sulphate is added, followed by ammonium sulphate; the sodium methylsulphate may be replaced by sodium ethyl sulphate, and the amine by 1 - amino - 2 - (2<1> - chlorophenoxy) - 5 - chlorobenzene; (7) 1 - amino - 2 - (2<1> : 5<1> - dichlorophenoxy)-5-methylbenzene is diazotized by means of nitrososulphuric acid, and sodium methyl or ethyl sulphate and Glauber's salt are added; (8) 1-amino-2-phenoxy-4-acetylamino-5-chlorobenzene is diazotized, and sulphuric acid, sodium methyl sulphate and Glauber's salt are added; the sodium methyl sulphate may be replaced by a salt of ethylsulphuric acid; (9) 1-amino-4-(4<1>-chlorophenoxy)-benzene is diazotized, and sodium methyl sulphate and Glauber's salt are added; 1 - amino - 4 - phenoxy - 3 - chlorobenzene may be similarly treated; (10) 1 - amino - 4 - phenoxybenzene is diazotized, the diazo solution is mixed with a solution of sodium ethyl sulphate, and ammonium sulphate is added.  The following additional starting materials are specified: 1 - amino - 2 - phenoxy - 4 - nitrobenzene, 1 - amino - 4 - phenoxy - 3 : 5 - dichlorobenzene, 1 - amino - 4 - phenoxy - 2 - nitrobenzene, 1 - amino - 4 - phenoxy - 2 - chloro - 5 - methylbenzene, 1 - amino - 4 - (2<1> : 4<1> - dinitrophenoxy)-benzene, and also the compounds the manufacture of which is indicated below.  Aminodiaryl ethers.--The following compounds are obtainable by reducing the corresponding nitro compounds, produced by condensing the appropriate nitrochloro aromatic compounds with the appropriate sodium or potassium phenolates: 1 - amino - 2 - (naphthyl-2<1> - hydroxy)- 4 - chlorobenzene, 1 - amino - 2 - (2<1> : 5<1> - dichlorophenoxy) - 5 - methylbenzene, 1 - amino - 2 - phenoxy - 4 - acetylamino - 5 - chlorobenzene, 1 - amino - 4 - phenoxy - 3 - chlorobenzene, 1 - amino - 2 - phenoxy - 3 - chlorobenzene, 1 - amino - 2 - (4<1> - methoxyphenoxy) - 5 - methoxybenzene, 1 - amino - 2 - (4<1> - methoxyphenoxy) - 5 - trifluoromethylbenzene, 1 - amino - 2 - (2<1> - methyl - 5<1> - chlorophenoxy) - 5 - chlorobenzene, 1 - amino - 2 - phenoxy-5-acetylbenzene, 1-amino-2-phenoxy-5-benzoylbenzene, 1 - amino - 2 - phenoxy - 5 - phenylsulphonylbenzene, 1 - amino - 2 - (5<1> : 6<1> : 7<1> : 8<1> - tetrahydronaphthyl - 2<1> - hydroxy) - 5 - chlorobenzene, 1 - amino - 2 - phenoxy - 4 - methoxy - 5 - chlorobenzene, 1 - amino - 3 - (4<1> - methoxyphenoxy) - 4 - nitrobenzene, 1 - amino - 4 - (3<1> - methylphenoxy) - 3 - methylbenzene, 1 - amino - 4 - phenoxy - 3 : 5 - dichlorobenzene, 1 - amino - 4 - phenoxy - 2 - nitrobenzene, 1 - amino - 4 - phenoxy - 3 - trifluoromethylbenzene, 1 - amino - 4 - phenoxy - 2 - chloro - 5 - methylbenzene, 1 - amino - 4 - (2<1> : 4<1> - dinitrophenoxy) - benzene, 1 - amino - 4 - (2<1> : 4<1> : 5<1> - trichlorophenoxy) - 3 - chloro benzene, and 1-amino-4-(4<1>-chlorophenoxy)-naphthalene. Specification 324,090, [Class 2 (iii)], is referred to. 1-Amino-2-phenoxy-5-bromobenzene is obtainable by condensing 1-nitro-2 : 5-dibromobenzene with sodium phenolate and reducing. 1-Amino-2-phenoxy-5-nitrobenzene is obtainable by condensing 1-nitro-2-chloro-5-acetylaminobenzene with potassium phenolate, saponifying, diazotizing, introducing a nitrile group by the Sandmeyer reaction, and reducing.  1 - Amino - 2 - phenoxybenzene - 5 - carboxylic acid phenyl ester is obtainable by condensing 1-nitro-2-chlorobenzene-5-carboxylic acid with sodium phenolate, transforming the product by way of the acid chloride into the phenyl ester, and reducing.  1 - Amino - 2 - (2<1> ; 4<1> - dichlorophenoxy)-benzene-5-carboxylic acid anilide is obtainable by condensing 1 - nitro - 2 - chlorobenzene - 5 - carboxylic acid with the sodium salt of 1-hydroxy-2 : 4-dichlorobenzene, condensing the product with aniline, and reducing.  1 - Amino - 2 - phenoxybenzene - 5 - carboxylic acid diethylamide is obtainable by condensing 1 - nitro - 2 - phenoxybenzene - 5 - carboxylic acid chloride with diethylamine and reducing.  1 - Amino - 2 - phenoxy - 5 - dimethylaminosulphonylbenzene is obtainable by condensing 1-nitro-2-chlorobenzene-5-sulphonic acid with sodium phenolate, condensing the product by way of the sulphochloride with dimethylamine, and reducing.  1 - Amino - 4 - phenoxy - 2 - dimethylaminosulphonylbenzene is obtainable similarly from 1-nitro-4-chlorobenzene-2-sulphonic acid.  1 - Amino - 2 - (4<1> - ethoxycarbonylphenoxy)-5-chlorobenzene is obtainable by condensing 1-nitro - 2 : 5 - dichlorobenzene with p-hydroxybenzoic acid ethyl ester and reducing.  1 - Amino - 2 - phenoxy - 4 - methoxy-5-chlorobenzene is obtainable from 1 : 2-dinitro-4 : 5-dichlorobenzene by replacing the 2-nitro group by phenoxy by means of potassium phenolate, replacing the 4-chlorine atom by methoxy by means of potassium methylate, and reducing.  1 - Amino - 2 - phenoxy - 4 - nitro - 5 - methoxybenzene is obtainable by condensing 1-nitro-2-chloro - 5 - methoxybenzene with potassium phenolate, reducing, acetylating, nitrating and saponifying.  1 - Amino - 2 - phenoxy - 4 - benzoylamino - 5-ethoxybenzene is obtainable by nitrating 1-acetylamino - 2 - ethoxy - 5 - chlorobenzene, condensing the product with potassium phenolate, saponifying, benzoylating and reducing.  1 - Amino - 2 - phenoxy - 4 - ethylsulphonylbenzene is obtainable by condensing 1-nitro-2-chlorobenzene-4-sulphonic acid with sodium phenolate, transforming the product to the sulphochloride, reducing to the sulphinic acid, ethylating and reducing.  1-Amino-3-phenoxy-4 : 6-dichlorobenzene is obtainable by condensing 1-acetylamino-2 : 5-dichloro-4-nitrobenzene with potassium phenolate, reducing, diazotizing, introducing chlorine by the Sandmeyer reaction, and saponifying.  1 - Amino-3-phenoxy-4-chloro-6-methoxybenzene is obtainable by diazotizing 1-amino-2-phenoxy-4-nitro-5-methoxybenzene, introducing chlorine by the Sandmeyer reaction, and reducing.  1-Amino-2 : 4-diphenoxy-5-chlorobenzene is obtainable by condensing 1-nitro-2 : 4 : 5-trichlorobenzene with 2 mols. of potassium phenolate and reducing.  1 - Amino - 2 : 4 - di - (4<1> - chlorophenoxy) - 5-methoxybenzene is obtainable by diazotizing 1 - amino - 2 - methoxy - 4 - nitro - 5 - chlorobenzene, introducing chlorine by the Sandmeyer reaction, condensing the product with 2 mols. of potassium 4-chlorophenolate and reducing.  1 - Amino - 4 - phenoxy - 3 - chloronaphthalene is obtainable by diazotizing 1-amino-2-chloro-4-nitronaphthalene, introducing chlorine by the Sandmeyer reaction, condensing the product with potassium phenolate, and reducing.