Patent GB-408590-A (GB)
Title: Improvements in the manufacture and production of azo dyestuffs
IPC: C09B45/16
Filed: 1932-09-29
Abstract: Azo dyes, soluble chromium compounds of.--Complex chromium compounds of azo dyes are obtained by treating with an agent yielding chromium a compound of the general formula <FORM:0408590/IV/1> wherein A is an alkyl, cycloalkyl, aryl or acyl radicle, X is a benzene or naphthalene radicle, Y is the radicle of a coupling component, Z is hydrogen or an alkyl, cycloalkyl, aralkyl or aryl radicle, n is a whole number, and the O--A and --N=N-- substituents are attached to X in o-- position, the treatment being affected under such conditions that the radicle A is replaced by hydrogen, i.e. effected in presence of water at 100--150 DEG  C. (cf. Specification 296,819).  The products are of good levelling power and give dyeings and printings especially fast to light and washing on animal fibres such as wool, silk and leather.  The radicle X may be further substituted, e.g. by alkoxy, alkyl, halogen or nitro groups.  When A is an acyl radicle, the chroming is preferably effected under alkaline conditions. Suitable chroming agents are chromium fluoride, formate or sulphate, chromium alum or alkaline chromites.  The following examples are specified.  (1) The dyestuff 2-aminoanisol-4-sulphodiethylamide --> 2 - naphthol - 6 : 8 - disulphonic acid is heated under pressure for 3 hours at 135 DEG  C. with an aqueous solution of chromium sulphate or formate and the product is separated by evaporation to dryness or by addition of hydrochloric or sulphuric acid to the solution; it dyes wool level bluish bordeaux red shades, fast to light and washing. (2) Chromium compounds giving similar shades are obtainable by replacing the diazo component by 2-aminoanisol-4-sulphonamides in which the amido group is substituted by one ethyl, by one or two methyl or by two phenyl groups; the use as diazo component of 5-chlor-2-aminoanisol-4-sulphonamide or the use as coupling component of 2 : 8-naphtholsulphonic acid gives similar products. A table is also given showing the shades obtainable on wool with the following dyestuffs and their complex chromium compounds : --5-chloro-2-aminoanisol-4-sulphonamide or 4 - chloro - 2 - aminoanisol - 5 - sulphonamide --> 1 - (3<1> - sulpho)phenyl - 3 - methyl - 5 - pyrazolone, 2 - aminoanisol - 4 - sulphon--amide --> 2 : 4 - dihydroxyquinoline - 6 - sulphonic acid, 5 - methoxy - 2 - aminoanisol 4 - sulphonamide, 4 - chloro - 2 - aminoanisol - 5 - sulphodiethylamide or 4 - methoxy - 2 - aminoanisol - 5 - sulphodiethylamide --> 2 - naphthol - 3 : 6 - disulphonic acid, 4 - chloro - 2 - aminoanisol - 5 - sulphodiethylamide or 4 - methoxy - 2 - aminoanisol - 5 - sulphonamide --> 2 - naphthol - 6 : 8 - disulphonic acid, 4 - chloro - 2 - aminoanisol - 5 - sulphonamide --> 2 : 4 - naphtholsulphonic acid, 5 - methoxy - 2 - aminoanisol - 4 - sulphonamide --> 2 : 8 - dihydroxynaphthalene - 6 - sulphonic acid, 2 - aminoanisol - 4 - sulphodiethylamide --> 8 - hydroxyquinoline - 5 - sulphonic acid, 1 - amino - 2 - methoxynaphthalene - 6 -sulphodiethylamide --> 1 - naphthol - 4 : 8 - disulphonic acid, 1 - naphthol - 8 - sulphonamide - 3 - sulphonic acid or 1 - naphthol - 4 - sulphodiethylamide - 8 - sulphonic acid.  Samples of the chromium compounds of the following dyestuffs have been furnished under Sect. 2 (5) of the Acts:--(a) 2 - aminoanisol - 4 - sulphocyclohexylamide --> 2 : 6 : 8 - naphtholdisulphonic acid; (b) 2 - aminoanisol - 4 - sulphobenzylamide --> 2 : 6 : 8 - naphtholdisulphonic acid; (c) 2 - aminoanisol - 4 - sulphodiphenylamide --> 2 : 6 : 8 - naphtholdisulphonic acid.  2 - Aminoanisol - 4 - sulphodiethylamide is obtained by reducing the nitro group of the product of reaction of diethylamine on the chloride of 2-nitroanisol-4-sulphonic acid.  2 - Aminoanisol - 4 - sulphodiphenylamide is similarly obtained with replacement of the diethylamine by diphenylamine.  5 - Chloro - 2 - aminoanisol - 4 - sulphonamide is obtained by removing the acetyl group by saponification from the product of reaction of ammonia on 5-chloro-2-acetylaminoanisol-4-sulphochloride which is obtained by the action of chlorosulphonic acid on acetylated 5-chloro-2-aminoanisol.  4 - Chloro - 2 - aminoanisol - 5 - sulphonamide is similarly obtained from 4-chloro-2-aminoanisol. 4-Chloro-2-aminoanisol-5-sulphodiethylamide is similarly obtained with replacement of the ammonia by diethylamine. 5-Methoxy-2-aminoanisol-4-sulphonamide is obtained by removing the acetyl group by saponification from the product of reaction of ammonia on 1 : 5-dimethoxy-2-acetylaminobenzene-4-sulphochloride which is obtained by the action of chlorosulphonic acid on acetylated 1 : 5-dimethoxy-2-aminobenzene. 4-Methoxy-2-aminoanisol-5-sulphonamide is similarly obtained from 1 : 4-dimethoxy-2-aminobenzene. 4-Methoxy-2-aminoanisol-5-sulphodiethylamide is similarly obtained with replacement of the ammonia by diethylamine.  2 - Aminoanisol - 4 - sulphocyclohexylamide is obtained by reaction of cyclohexylamine on 2-aminoanisol-4-sulphochloride.  2 : 4-Dihydroxyquinoline-6-sulphonic acid is obtained by sulphonating anthranilic acid with fuming sulphuric acid at 100--150 DEG  C., acetylating the resulting 2-amino-5-sulphobenzoic acid and melting the product with caustic alkali at above 200 DEG  C. 1-Naphthol-4-sulphodiethylamide-8-sulphonic acid is obtained by converting 1 : 4-naphtholsulphonic acid or its toluenesulphonic acid ester into the diethylamide by way of the sulphochloride and sulphonating the product.  Reference has been directed by the Comptroller to Specification 296,819, [Class 2 (iii)].