GB447899A - Manufacture of dyestuff-sulphonic acids - Google Patents

Abstract

Dioxazine dyestuff sulphonic acids are made by treating a diarylamino 1 : 4-benzoquinone derivative, prepared from a sulphonated primary aromatic arylamine containing more than two nuclei of the following formula <FORM:0447899/IV/1> wherein R and R<1> stand for a sulphonated aromatic monovalent radical containing more than two nuclei and X and X<1> for hydrogen, alkyl, aryl, or halogen, with concentrated sulphuric acid, chlorosulphonic acid, or fuming sulphuric acid or an alkaline condensing agent such as ammonia, sodium carbonate, or caustic soda solution, preferably in the presence of an organic or inorganic oxidizing agent such as chloranil, benzoquinone, pyrolusite, permanganate, lead peroxide, or hydrogen peroxide. Suitable monovalent radicals specified are those of carbazole, diphenylene-oxide or dioxide, acenaphthene, fluorene, anthracene, phenanthrene, phenanthridone, fluoranthene, chrysene, pyrene, benzanthracene, benzofluorene, benzodiphenyleneoxide, benzophenanthrene, retene, and perylene. The 1 : 4-benzoquinone derivatives of the above formula are made by causing chloranil or another 1 : 4-benzoquinone such as 1 : 4-benzoquinone itself or toluquinone, to condense with an aminosulphonic acid. The dyestuffs obtained dye animal, vegetable and viscose fibres. In examples, the following diarylamino-benzoquinones are treated with concentrated or fuming sulphuric acid: (1) 2 : 5 - di - (N - ethylcarbazolyl - 3<1>-amino - 6<1>-sulphonic acid)-3 : 6-dichloro-1 : 4-benzoquinone; (2) 2 : 5-di-(N-methylcarbazolyl-3<1>-amino-6<1>-sulphonic acid) - 3 : 6 - dichloro - 1 : 4 - benzoquinone, using pyrolusite; (4) 2 : 5-di(chrysenyl-2<1>-amino-8<1>-sulphonic acid)-3 : 6-dichloro-1 : 4-benzoquinone; (5) 2 : 5-di(carbazolyl-3<1>-amino-4<1>-sulphonic acid)-3 : 6-dichloro-1 : 4-benzoquinone; (6) 2 : 5-di-(fluorenyl-2<1>-amino-disulphonic acid)-3 : 6-dichloro-1 : 4-benzoquinone, using pyrolusite; and (7) 2 : 5-di-(2<1>-amino-diphenylenoxide - 6<1> - sulphonic acid) - 3 : 6-dichloro-1 : 4-benzoquinone. In example 3, 2 : 5-di-(N-ethylcarbazolyl-3<1>-amino - 6<1>-sulphonic acid) p - 3 : 6-dichloro-1 : 4-benzoquinone is treated with caustic soda and potassium permanganate. 3-Amino-(N)-ethylcarbazole-6-sulphonic acid is made by nitration of N-ethylcarbazole, sulphonation of the 3-nitro compound so obtained and reduction of the product. 2-Aminofluorenedisulphonic acid is obtained by nitration of fluorene to give 2-nitro-fluorene, sulphonation of the product to give a disulphonic acid and reduction. 2 - Aminochrysene - 8 - sulphonic acid and 2-aminodiphenyleneoxide - 6 - sulphonic acid are obtained from chrysene and diphenyleneoxide respectively by nitration to the 2-nitro compounds, sulphonation and reduction. Specifications 313,094, [Class 2 (iii)], 367,389, and 408,456 are referred to.