Patent GB-691410-A (GB)
Title: Process for the preparation of diazoamino compounds and water-insoluble azodyestuffs on fibres
Inventor: LANTZ ROBERT
Filed: 1951-03-16
Abstract: The invention comprises diazo-amino compounds of the formula <FORM:0691410/IV (b)/1> where R is alkyl or aryl, R1 is a benzene nucleus, R2 is an aliphatic, aryl, aralkyl or alicyclic radical, R3 is hydrogen or an aliphatic radical, and A is a cation conferring solubility in water; R2 and R3 may form a saturated heterocyclic ring with the nitrogen atom.  These are made by reacting a diazo compound of the formula <FORM:0691410/IV (b)/2> with a primary or secondary amine HNR2R3.  Preferably the diazo compound does not contain any solubilizing group other than the N-sulphonic group shown.  Suitable diazo compounds are prepared as in Specification 611,320 by diazotization of the appropriate diamine derivatives.  The reaction with the amine HNR2R3 takes place in a neutral or alkaline aqueous medium, with or without a miscible solvent such as alcohol.  In the examples diazoamino compounds are prepared from (1) N-p-anisyl-4-diazobenzene-sulphamic acid and diethylamine, piperidine or morpholine; (2) N-phenyl-4-diazobenzenesulphamic acid and piperidine, dimethylamine, diethylamine, morpholine or dibutylamine; (3) N-phenyl-4-diazobenzenesulphamic acid and methylaniline, aniline or o-toluidine; and (4) N-methyl-4-diazobenzenesulphamic acid and diethylamine.  Other specified reactants are N-p-tolyl-, N-o-tolyl- and N-o-anisyl-4-diazobenzenesulphamic acids, N-phenyl-3-methoxy-4-diazobenzene-sulphamic acid, N-methyl-3-diazo-6-methylbenzenesulphamic acid, methylamine, ethylamine, cyclohexylamine and N - methylcyclohexylamine.ALSO:Textile fibres, especially of natural or regenerated cellulose, are coloured with insoluble azo dyestuffs by applying thereto a diazoamino compound of the formula <FORM:0691410/IV (c)/1> in conjunction with a coupling component, and then reducing the pH to effect coupling and elimination of the N-sulphonic group; R is alkyl or aryl, R1 is a benzene nucleus, R2 is an aliphatic, aryl, aralkyl or alicyclic radical, R3 is hydrogen or an aliphatic radical and A is a cation conferring solubility in water; R2 and R3 may form a saturated heterocyclic ring with the nitrogen atom.  The coupling and elimination reactions may take place successively by lowering the pH in two stages.  The components may be mixed to form a liquid or paste together with a non-volatile base (e.g. caustic soda) or a volatile base (e.g. diethylethanolamine). In the latter case a salt of a volatile base may be added, which releases acid on subsequent steaming; otherwise acid dipping or acid steaming is necessary to develop the colour.  Other ingredients may be added to the composition, e.g. thickeners, solvents, surface-active agents, wetting agents, dispersing agents, hygroscopic agents or products which protect the dyestuff against prolonged steaming. In the examples: (1) cotton is printed with the diazoamino compound from N - p - anisyl - 4 - diazobenzenesulphamic acid and diethylamine, 2 : 3-oxynaphthoic anilide, caustic soda and starch; the colour is developed by steaming with acetic or formic acid; (2) as in (1) using the diazoamino compound from N - phenyl - 4 - diazobenzenesulphamic acid and piperidine; (3) as in (1) with after-treatment in sulphuric acid and sodium sulphate; (4) cotton is printed with the diazoamino compound from N-p-anisyl-4-diazobenzenesulphamic acid and diethylamine, 2 : 3-oxynaphthoic anilide, ethoxyethanol, diethylethanolamine and starch; the colour is developed by steaming, followed by treatment with sulphuric acid and sodium sulphate; (5) as in (4) with the addition of ammonium sulphate to the paste; no acid treatment is necessary.  Other suitable compounds are arylides and arylene - diamides of 2 : 3 - oxynaphthoic, 2 : 3 - oxyanthroic, 2 : 3 - oxycarbazole - carboxylic, 2 : 3 - oxybenzocarbazolecarboxylic, 3 : 2 - oxydibenzofuran - carboxylic and acylacetic acids.  R may also be methyl, o-tolyl, o-anisyl or p-tolyl and R1 may carry methyl or methoxy substituents and may be a m-phenylene residue.  Other primary and secondary amine residues are specified for -NR2R3.