Patent GB-422195-A (GB)
Title: Water soluble diazoimino compounds and their application
Filed: 1933-06-30
Abstract: Diazoimino compounds are made by reacting a diazotized aromatic amine containing no solubilizing group with a pyrrolidine compound containing one or more solubilizing groups.  Diazotized amines of the benzene, azobenzene, diphenyl, diphenylamine, naphthalene, anthraquinone or carbazole series may be used and they may be substituted by alkyl, alkoxy, halogen, nitro or benzoyl amino groups. In examples, diazoimino compounds from the following components are described: (1)--(3) 2 : 5-dichloraniline and pyrrolidine-a -carboxylic acid (proline), pyrrolidine-a -sulphonic acid or 4-hydroxypyrrolidine-2-carboxylic acid (oxyproline); (4) m-nitro-p-toluidine and proline.  The diazo compounds of 4-nitro- and 4-chlor-2-aminoanisole, 4-nitro- and 5-chlor-2-toluidine, 0- and m-chloraniline, 4-chlor-2-nitraniline, 0-nitraniline, dianisidine, a -naphthylamine, 1-amino-4-benzoylamino-2 : 5-dimethoxybenzene, 4-amino-6-benzoylamino-1 : 3-dimethylbenzene, 4 - aminoazobenzene, a - aminoanthraquinone, 2-nitro-5-methylbenzeneazocresidine, 3-amino-carbazole and 4 : 4<1>-diaminodiphenylamine are also specified.  Azo dyes, forming on the material.--The above diazoimino compounds are used in the "one bath" process of dyeing or printing ice-colours on the fibre in which the diazoimino compound and the coupling component are applied to the material and the colour developed by acid treatment.  In examples: (5) cotton is printed with a paste containing the diazoimino compound from diazotized 2 : 5-dichloraniline and proline and the o-anisidide of 2 : 3-oxynaphthoic acid, dried and developed in an acetic formic acid bath containing Glauber's salt; (6) a mixture of the sodium salt of the diazoimino compound obtained by the action of diazotized 2 : 5-dichloraniline or pyrrolidine-a -sulphonic acid and the sodium salt of the anilide of 2 : 3-oxynaphthoic acid (obtained by evaporation of the mixed aqueous solutions) is made into a paste, printed on cotton and the colour developed by exposure to steam containing acetic acid vapours.  Other arylides of 2 : 3-oxynaphthoic acid may be used and also acetoacetic arylides, e.g. diacetoacetyl-o-tolidine, a -and b -naphthol, arylides of hydroxy-carbazole-and hydroxynaphthocarbazole - o - carboxylic acids, 1-phenyl-3-methyl-5-pyrazolone, arylides of hydroxyanthracene- and hydroxyphenanthrene-o-carboxylic acids and arylides of 3 - hydroxydiphenylamine - 4 - carboxylic acid. Specifications 306,844 and 308,660, [both in Class 15 (ii)], are referred to.  The Specification as open to inspection under Sect. 91 comprises also diazoimino compounds derived from piperidine derivatives and their use in forming azo dyes on the fibre.  In examples, diazoimino compounds from the following compounds are described: (1) 2 : 5 dichloraniline and piperidine-b - or a -carboxylic acid or piperidine-q -sulphonic acid; (2) 4-nitro-2 - aminoanisole or m - nitro - p - toluidine and piperidine-a -carboxylic acid; (3) aminoazobenzene and piperidine - b  - carboxylic acid. Diazoimino compounds from the following components are also specified: o- and m-chloraniline, m-nitraniline, 4-chlor-2-nitraniline, 4-chlor-2-anisidine, 5-nitro-2-anisidine, 1-amino-4-benzoylamino-2 : 5-diethoxybenzene, N-(p-aminobenzoyl)-aniline, dianisidine, a -amino-anthraquinone, 2 - nitro - 4 - methylbenzeneazocresidine, 4 : 4<1> - diaminodiphenylamine, o-ethoxybenzeneazo-a -naphthylamine, 3-amino-carbazole and a  - naphthylamine; polycarboxylic and polysulphonic acids of piperidine and ring alkylated piperidine carboxylic and sulphonic acids.  In an example of the dyeing process: (4) a mixture of the diazoimino compound from diazotized 2 : 5-dichloraniline and piperidine-a -carboxylic acid and the 2 : 5-dimethoxyanilide of 2 : 3-oxynaphthoic acid obtained by evaporation of the mixed solutions is made into a paste and applied as above.  In a further example: (5) cotton is padded with the anilide of 2 : 3-oxynaphthoic acid and developed with a solution prepared from the diazoimino compound from diazotized 3-nitro-4-aminotoluene and pyrrolidine-a -carboxylic acid, acetic acid and aluminium sulphate. Other pyrrolidine derivatives specified are the b -carboxylic acid, di- and poly-carboxylic acids, di- and poly-sulphonic acids, ring alkylated pyrrolidine-carboxylic and sulphonic acids, e.g. 4 : 5-dimethylpyrrolidine-2-carboxylic acid, polyhydroxypyrrolidine carboxylic and sulphonic acids.  Piperidine-b -carboxylic acid may be prepared by the catalytic hydrogenation of pyridine-b -carboxylic acid.  Piperidine-a -carboxylic acid is made by oxidizing a -picoline to a -picolinic acid and reduction with sodium and alcohol.  This subject-matter does not appear in the Specification as accepted.