Patent GB-417388-A (GB)
Title: The manufacture of dyestuffs of the azine series
IPC: C09B17/00
Filed: 1933-04-01
Abstract: Azine dyes containing the grouping --CH2 CH2SO3H attached to nitrogen are prepared by using as reacting or condensing component at least once an aromatic amino ethane sulphonic acid of the general formula <FORM:0417388/IV/1> wherein R stands for hydrogen, alkyl, oxyalkyl, sulphoalkyl or aralkyl, in one of the following standard methods of preparation:--(1) oxidation together of one molar proportion of an aromatic m-diamine with one molar proportion of an aromatic p-diamine; (2) condensation of an aromatic m-diamine with an aromatic p-nitrosamine; (3) condensation of an alkyl or phenyl-b -naphthylamine or derivative thereof with an aromatic p-nitrosamine or with an aromatic p-diamine with simultaneous oxidation; (4) conversion of the isorosindulines prepared in accordance with the process; (3) into safranines by reacting with sulphite so as to introduce a 6-sulpho group and reacting the product with an aromatic amine whereby the 6-sulpho radicle is replaced; (5) oxidation together of 1 molar proportion of an aromatic p-diamine with 2 molar proportions of an aromatic monoamine.  Such dyes are also prepared by reacting azine dyes containing at least once an amino group having a replaceable hydrogen atom with a halogenethanesulphonic acid.  The products may be after-treated with sulphonating agents.  In examples: (1) 1,3-di-(phenylamino) naphthalene-8-sulphonic acid is oxidized with 4-aminoethylphenyltaurine to give a safranine dyeing wool reddish-blue shades; using 4-amino-oxyethylphenyltaurine (prepared by nitrosating oxyethylphenyltaurine and reducing the nitroso group with iron and acetic acid) or p-nitroso-di-(sulphoethyl)-aniline (prepared by nitrosating disulphoethylaniline) similar dyes are obtained; in the first two cases 1,3-di-(phenylamino)-naphthalene-8-sulphonic acid may be replaced by 1,3-di(m-tolylamino- or p-anisylamino-)-naphthalene - 8 - sulphonic acids; (2) diphenyl-m-phenylenediamine is condensed with p-nitroso-ethylphenyltaurine (prepared by nitrosating ethylphenyltaurine) to give a safranine which is rendered easily soluble in water by sulphonation to dye wool in bluish-violet shades; (3) phenyl-b -naphthylamine is condensed with p-nitroso-ethylphenyltaurine to a violet dyeing isorosinduline; by treatment with sodium bisulphite the 6-sulphonic acid derivative is formed and this sulpho group is replaced by condensation with 4-aminoethylphenyltaurine to give a safranine dyeing wool blue shades; (4) b -naphthyltaurine is oxidized with 4-aminodiethylaniline-3-sulphonic acid to give an isorosinduline which is treated with sodium bisulphite to give a 6-sulpho derivative and the latter converted to a eurhodine by condensation with 5-amino-2-ethyltoluidine; this product dyes wool blue shades, its affinity for the fibre being increased by sulphonation; the 4-amino-diethylaniline-3-sulphonic acid may be replaced by 4-amino-ethylbenzylaniline-2-sulphonic acid to give a similar product; (5) 4<1> - nitro - 4 - aminodiphenylamine - 2<1> - sulphonic acid is oxidized with ethylphenyltaurine to give an indamine which is converted to a safranine by oxidation with p-sulphanilic acid; it dyes wool blue shades, and gives a further product by acetylation; the p-sulphanilic acid may be replaced by p-aminosalicylic acid; (6) 4-amino-methylphenyltaurine, o-toluidine and aniline are oxidized together to give a safranine which dyes tanned cotton bluish-red; (7) methylphenyltaurine, 2,5-toluylenediamine and o-toluidine are oxidized together to give a similar safranine; (8) safranine FF extra is condensed with chlorethane sulphonic acid in presence of diethylaniline as acid-binding agent; (9) 3-diethylamino - phenylisorosinduline - 1 . 6 - disulphonic acid is condensed with p-amino-b -sulphoethylbenzylaniline whereby the 6-sulpho group is replaced to give a safranine dyeing greenish-blue shades; 3-(3<1>-sulphobenzyl)-ethylamino-phenylisorosinduline - 6 - sulphonic acid is similarly converted to a safranine; (10) a chlortolyl - b  - naphthylamine is oxidized with 4 - amino - diethylaniline - 3 - sulphonic acid, the resulting dye treated with sodium bisulphite to give a 6-sulpho derivative, and this converted to a safranine by condensation with 4-aminophenylbenzyltaurine; this dyes wool blue shades.  The products in general have a good solubility in water and dye in clear fast shades.  The Specification as open to inspection under Sect. 91 relates to the manufacture of the foregoing dyes by the application of methods known per se but this subject-matter does not appear in the Specification as accepted.