Patent GB-499587-A (GB)
Title: Process for the manufacture of dyeings according to the chrome printing process
IPC: C09B17/04
Filed: 1937-06-25
Abstract: Dyeings are produced by the chromium printing process, using dyestuffs of the naphthophenosafranine series which contain at least one hydroxycarboxylic acid grouping and solubilizing groups and are of the general formula <FORM:0499587/IV/1> in which at least one hydroxycarboxylic acid grouping and two sulphonic acid groups must be present in the molecule (e.g. in the nuclei I, II, III or IV or in R1 and R2), R1 is a secondar or tertiary amino group, the substituents of which may be alkyl, aralkyl, hydroaryl, aryl or substitution products thereof, and R2 is hydrogen or any radicle such as free or substituted hydroxy or amino groups.  The nucleus I may be naphthyl or any other aromatic, hydroaromatic, or aliphatic radicle, in addition to phenyl.  The nuclei I, II, III and IV may be further substituted, especially by halogen in nucleus I.  The term " hydroxycarboxylic acid grouping " comprises any grouping of a hydroxy and a carboxylic group capable of forming a chromium lake, preferably salicylic and o-hydroxynaphthoic acid groupings, and suitable printing processes are machine printing, film printing, hand printing, spray printing, relief printing, especially on cotton, regenerated cellulose, linen, wool, silk and mixed fabrics, and also on naphtholized materials, i.e. materials which have been impregnated with a solution of sodium naphtholate and dried.  Dyestuffs which, when printed on cotton with a chromium mordant, yield blue, reddish-blue, greenish-blue, or violet shades are obtained by (1) alkaline oxidation of 1,3-diphenylaminonaphthalene-8-sulphonic acid with 51-sulpho-41 (or 21)-hydroxy-31-carboxy-4-aminodiphenylamine 2-sulphonic acid; (2) by reacting 5-sulpho-3-amino-2-hydroxybenzoic acid with (a) 3-diethyl-isorosinduline-1 : 6-disulphonic acid, (b) 11 : 13-dichloro-3-diethylisorosinduline-1.6-disulphonic acid, (c) 11-methyl-13-hydroxy-14-carboxy-3-diethylisorosinduline-1 : 6-disulphonic acid, (d) 8-carboxy-9-hydroxy-3-diethylisorosinduline-1 : 6 - disulphonic acid, (e) 11 : 15 - dimethyl - 3-diethylisorosinduline-6-sulphonic acid, (f) 11 : 13-dichloro - 3 - sulphoethylbutylisorosinduline - 6-sulphonic acid, (g) 1-chloro-3-diethylisorosinduline-6.9-disulphonic acid; (3) by reacting 51-sulpho-41-hydroxy-31-carboxy-4-amino diphenylamine-2-sulphonic acid with (a) 11-methyl - 3 - diethylrosinduline - 1.6 - disulphonic acid, (b) 11.13-dichloro-3-diethylisorosinduline-1,6-disulphonic acid, (c) 3-(31-sulphobenzyl)-ethyl - isorosinduline - 6 - sulphonic acid, (d) 3-methylcyclohexylisorosinduline-6,9-disulphonic acid, (e) 3 - diethylrosinduline - 1,6 - disulphonic acid hexahydrogenated in the nucleus I, (f) a 3 - diethylisorosinduline - 1.6 - disulphonic acid containing instead of the nucleus I a b -naphthyl radical, a b -sulphoethyl radical, an ethyl radical, or a b -phenylethyl radical; (4) by reacting 3-diethylrosinduline-1.6.12-trisulphonic acid with 21-hydroxy-31-carboxy-4-aminodiphenylamine-2 -sulphonic acid; (5) by heating 12-carboxy-13-hydroxy-3-diethyl-isorosinduline-1,6-disulphonic acid with 1-amino-4-ethylamino-5-methylbenzene followed by sulphonation; (6) by oxidation of the isorosinduline from vic-m-xylyl-b -naphthylamine and p-nitrosodiethylaniline with 5-aminosalicylic acid, followed by disulphonation. 51-Sulpho-41-hydroxy-31-carboxy-4-amino -diphenylamine-2-sulphonic acid is obtained by condensing 4-nitro-1-chlorbenzene-2-sulphonic acid with 5-amino-3-sulpho-2-hydroxybenzoic acid, followed by reduction.  51-Sulpho-31-carboxy-21-hydroxy-4-amino -diphenylamine-2-sulphonic acid is obtained by condensing 4-nitro-1-chlorobenzene-2-sulphonic acid with 5-sulpho-3-amino-2-hydroxybenzoic acid, followed by reduction. 21-Hydroxy-31-carboxy-4-aminodiphenylamine-2-sulphonic acid is obtained by condensing 4-nitro-1-chlorbenzene-2-sulphonic acid with 3-amino - 2 - hydroxybenzoic acid, followed by reduction.  The 3 - diethylisorosinduline - 1,6-disulphonic acids used in the examples are obtained by oxidizing condensation of 1-amino-4-diethyl-aminobenzene-2-sulphonic acid by means of sodium dichromate with various aryl- (or hydroaryl-) b -naphthylamines, followed by introduction of the 6-sulphonic group by reaction with sodium bisulphite (see Specification 14962/98, [Class 2]).  11.15 - Dimethyl - 3 - diethyl - isorosinduline-6-sulphonic acid is obtained by condensing 21.61-dimethylphenyl-b -naphthylamine with p-nitro-sodiethylaniline, followed by reaction with sodium bisulphite.  11.13 - Dichloro - 3 - (b  - sulphoethyl) - butyl-isorosinduline-6-sulphonic acid is obtained by condensing 21.41 - dichlorphenyl - b  - naphthylamine with N-butyl-p-nitrosophenyl-taurine, followed by reaction with sodium bisulphite.  3 - (31 - Sulphobenzyl)ethylisorosinduline - 6-sulphonic acid is obtained by condensing N-ethyl-(31-sulphobenzyl)-p-nitrosoaniline with phenyl-b -naphthylamine and reaction with sodium bisulphite.  3 - Methylcyclohexylisorosinduline - 6.9 - disulphonic acid is obtained by condensing 2-phenyl-aminonaphthalene-7-sulphonic acid with N-methyl - cyclohexyl - p - nitrosoaniline and reaction with sodium bisulphite.  1 - Chloro - 3 - diethylisorosinduline-6.9-disulphonic acid is obtained by condensing 2-phenyl-aminonaphthalene-7-sulphonic acid with p-nitroso - m - chlorodiethylaniline, and reaction with sodium bisulphite.  A 3-diethylisorosinduline-6-sulphonic acid containing a b -sulphoethyl group in place of the nucleus I is obtained by condensing b -naphthyltaurine with p-nitrosodiethylaniline and reaction with sodium bisulphite. Specifications 4880/95 and 24410/97, [both in Class 2], also are referred to.