GB448182A - Manufacture of dyestuff-sulphonic acids - Google Patents

Abstract

Oxazine dyestuff-sulphonic acids are made by treating a 1 : 4 benzoquinone derivative of the general formula <FORM:0448182/IV/1> wherein R and R1 stand for sulphonated diarylamine radicals which may be substituted at the nitrogen atom and X and X1 stand for hydrogen, alkyl, aryl or halogen, with sulphuric acid, chlorosulphonic acid, or fuming sulphuric acid, if desired in the presence of an organic or inorganic oxidizing agent, such as chloranil, benzoquinone, pyrolusite, permanganate, lead peroxide, or hydrogen peroxide. Sometimes the product is heated with dilute acid, for instance, after condensing with oleum. The parent materials are made by condensing in water or alcohol 1 : 4 benzoquinone or a substitution product such as toluquinone, chloranil, tetrabromoquinone, or 2 : 6 di-chloroquinone, with an amino-sulphonic acid of a di-arylamine. Amino-sulphonic acids of diarylamines are made by reacting a halogen-nitro-sulphonic acid, or a halogen-nitro compound, of the benzene or naphthalene series with an organic amino-compound, or a sulphonic acid thereof, in water or alcohol in presence of an acid binding agent and copper or a copper salt, and reducing the nitro group. Organic amino-compounds specified are aniline, acetanilide, methylaniline, a toluidine, a xylidine, an aminodiphenylamine, a naphthylamine, 2-amino-5 : 6 : 7 : 8-tetrahydronaphthalene, an amino-carbazole, aminofluorene, aminopyrene, aminochrysene or a derivative or substitution product thereof. The dyestuffs dye animal, vegetable and viscose artificial silk fibres. In examples, the products obtained by condensing chloranil and the following substances are heated with oleum: (1) 4-aminodiphenylamine-2-sulphonic acid; (2) 4 - amino - 4<1> - methoxy - diphenylamine - 2 - sulphonic acid; (5) 4-aminodiphenylamine-4<1>-sulphonic acid; (6) 4-aminophenyl-b -naphthylamine-2-sulphonic acid; (7) 4 : 4<1>-diamino-3<1> - 5<1> - dichloro - diphenylamine - 2 - sulphonic acid; (8) 4-amino-4<1>-nitrodiphenylamine-2<1>-sulphonic acid; (9) 4 - amino - 4<1> - carboxydiphenylamine-2-sulphonic acid; (10) 4-amino-4<1>-methyldiphenylamine-2-sulphonic acid; (11) 4 - amino - 4<1> - acetylaminodiphenylamine - 2 - sulphonic acid; (12) 4-amino-4<1>-chlorodiphenylamine-2-sulphonic acid; (13) 4-amino-3<1> : 4<1>-dichlorodiphenylamine-2-sulphonic acid; and (14) 4 - amino - 3<1> - chlorodiphenylamine - 2 - sulphonic acid. The starting materials of examples 3 and 4 are made from 4-aminodiphenylamine-2-sulphonic acid and benzoquinone and tetrabromoquinone respectively. 4-Aminodiphenylamine-4<1>-sulphonic is made by baking 4-amino-diphenylamine sulphate at 180 DEG C. Specifications 313,094, [Class 2 (iii)], and 367,389 are referred to.