Patent GB-481019-A (GB)
Title: Process of dyeing and manufacture of intermediates therefor
Filed: 1936-08-27
Abstract: Diazoimino compounds are manufactured by reacting a diazotized arylamine or arylene diamine, e.g. of the benzene, diphenyl, naphthalene, anthracene, azobenzene, diphenylether, diphenylamine or carbazole series, which is free from sulphonic or carboxylic groups but may carry other substituents, e.g. alkyl, alkoxy, nitro, acylamino, sulphonamide or trifluoromethyl groups or halogen atoms, with a watersoluble secondary aliphatic amino compound containing a furfuryl or tetrahydrofurfuryl radicle, preferably in the presence of acidbinding agents, e.g. alkali hydroxides, carbonates, bicarbonates or acetates.  In examples, the following compounds are reacted in the presence of sodium carbonate: (1) diazotized 4 - chloro - 2 - aminotoluene and furfurylaminoacetic acid; (2) the same diazo compound and tetrahydrofurfurylaminoacetic acid; (3) diazotized 4 - chloro - 2 - aminoanisole and furfurylaminoacetic acid; (4) the diazo compound of (1) and 1-(furfurylamino) - ethane - 2 - sulphonic acid; (5) the diazo compound of (1) and b -hydroxyethylfurfurylamine. Dyeing and printing compositions; azo dyes, forming upon the material; printing.-Dyeing and printing compositions comprise one or more of the diazoimino compounds described above and one or more ice-colour coupling components, e.g. arylamides of hydroxyarylcarboxylic acids such as the anilides, halogenanilides, toluidides, substituted toluidides, etherified hydroxyanilides, naphthylamides and substituted naphthylamides of 2 : 3- hydroxynaphthoic acids, 2 - hydroxycarbazole - 3 - carboxylic acid, 7 - hydroxy - a  - naphthocarbazole - 6 - carboxylic acid, hydroxyindolecarboxylic acids, hydroxydiphenylaminecarboxylic acids, and hydroxyphenanthrenecarboxylic acids, acylacetyl arylamides such as acetoacetyl, benzoylacetyl and terephthaloyl-bis-acetyl derivatives of primary arylamines and diamines, a - and b -naphthols, acylnaphthols such as 4-benzoyl- or 4-acetyl-1-naphthol, arylalkylpyrazolones or dihydroxyquinolines.  The 2 : 3-hydroxynaphthoic arylides may be employed in the form of free phenolic compounds or as salts, preferably of alkali metals.  Dyeing or printing assistants may be incorporated in the mixtures, which may be in the form of dry powders, aqueous pastes, aqueous solutions or solutions in organic solvents, especially water-miscible solvents such as methanol, ethyl alcohol, ethylene glycol or its alkyl ethers, or diethylene glycol.  Textile materials are dyed or printed by applying these compositions and developing the colour by the action of acid, e.g. by the action of steam and a mild volatile acid, by immersion in a boiling saturated salt solution containing a weak acid, e.g. acetic, phthalic, oxalic or citric acid, or by incorporating in the composition material of a non-acidic nature yielding acid on heating, e.g. sodium chloracetate, diethanolamine sulphate or formamide.  In examples: (6) the product of (1) above is ground with 2 : 3-hydroxynaphthoic o-toluidide; cotton is printed with a paste containing this mixture together with the substance known under the Registered Trade Mark " Cellosolve," caustic soda solution, sulphonated castor oil and starch tragacanth thickener, and a red print is developed by exposure to the vapours from a boiling solution of acetic and formic acids; (7) the product of (2) above is mixed with diacetoacetyl-o-tolidine; cotton is printed with this mixture by the process of (6), yielding a yellow print; (8) the product of (3) above is mixed with 2 : 3 - hydroxynaphthoic - o - anisidide; cotton is printed with this mixture by the process of (6), yielding a bluish red print; (9) the diazoimino compound from diazotized 4-chloro-2-aminoanisole and tetrahydrofurfurylaminoacetic acid is dissolved, together with acetoacetyl-p-phenetidine, in aqueous alcoholic caustic soda; cotton is printed with a paste containing this solution and starch tragacanth thickener, and a yellow print is developed as in (6); (10) the diazoimino compound and coupling component of (9) are mixed dry and the mixture is dissolved in aqueous caustic soda; cotton is padded in this solution and a yellow dyeing is developed as in (6).  A table shows the shades obtained with further compositions, the following additional components being specified: diazo components: 4-nitro-2-aminoanisole, dianisidine, 4 - carbomethoxyamino - 2 : 5 - dimethoxyaniline, 3 - chloraniline, 5 - nitro - 2 - aminoanisole, 2 : 5 - dichloraniline, 4 - ethoxy - 41 - amino - 21 : 51 - dimethoxyazobenzene, 4-benzoylamino-2 : 5-diethoxyaniline, aniline, 41-ethoxy-4-aminodiphenylamine, 3-benzoylamino - 4 - methoxyaniline, 4 - benzoylamino - 2 - methoxy - 5 - methylaniline; coupling components: 2 : 3-hydroxynaphthoic acid o-phenetidide, m-xylidide, m-nitranilide, anilide and a -naphthylamide, 2-hydroxyanthracene-3-carboxylic acid o-toluidide, diacetoacetyl-o-tolidine sulphone and 2-hydroxycarbazole-3-carboxylic acid p-chloranilide.  Furane compounds suitable for use in the preparation of the diazoimino compounds are obtainable by reacting a furfurylamine with a halogenated aliphatic carboxylic or sulphonic acid, e.g. a halogenated acetic, propionic or butyric acid.  Thus furfurylaminoacetic acid and its tetrahydro-derivative may be prepared, in admixture with small amounts of tertiary amino acids, by reacting an aqueous solution of furfurylamine (prepared by hydrogenation of furfurol in ammonia) or tetrahydrofurfurylamine (prepared by hydrogenation of furfurylamine) with sodium chloracetate in the presence of an acid-binding agent, e.g. sodium carbonate.  b -Hydroxyethylfurfurylamine is obtainable by reacting furfurylamine with ethylene chlorhydrin in the presence of an acid-binding agent.