Patent GB-681642-A (GB)
Title: New derivatives of 4:4-diaminostilbene-2:2-disulphonic acid and their manufacture and use
IPC: C07D417/14
Filed: 1950-10-06
Abstract: The invention comprises compounds of the formula <FORM:0681642/IV (b)/1> and their salts; W is aryloxy or-SR, R being an aliphatic, aromatic or heterocyclic residue which may be substituted; X and Y are -NH2 or substituted amino; Z is chlorine, amino, substituted amino, aryloxy or -SR.  These are made by (1) condensing 2 mols. of cyanuric chloride in any order with 1 mol. of 4 : 41-diaminostilbene - 2 : 21 - disulphonic acid, 1-2 mols. of a phenol or a mercapto compound RSH (or alkali derivative of a phenol or RSH) and 2-3 mols. of ammonia or a primary or secondary amine; or (2) condensing 1 mol. of cyanuric chloride in any order with 1 mol. of 4-nitro-41-aminostilbene-2 : 21-disulphonic acid and 1-2 mols. of a phenol, mercaptan or amine as above, reducing the nitro group to an amino group and reacting a further mol. of cyanuric chloride in any order with 1 mol. of the aminostilbene so produced and 1-2 mols. of a phenol, mercaptan or amine as above; the 4-nitro group may be replaced by any other group convertible to amino, e.g. acylamino. Examples describe the preparation (as sodium salts) of the following derivatives of 4 : 41 - bis - (1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid, the numbering referring to the triazine rings:-2 : 21 - diphenoxy - 4 : 41 - di - oxyethylamino, 2 : 21 - di - o - chlorophenoxy - 4 : 41 - diethanolamino, 2 : 21 - di - p - methoxyphenoxy-4 : 41 - di - ethanolamino, 2 : 21 - diphenoxy-4 : 41 - di - ethylamino, 2 : 21 - diphenoxy - 4 4 : 41 - bis - dimethylamino, 2 : 21 - diphenoxy - 4 : 41 - dimorpholino, 2 : 21 - diphenoxy - 4 : 41 - bis - diethylaminoethylamino, 2 : 21 - di - o - chlorophenoxy - 4 : 41 - di - methylamino, 2 - o - tolyloxy - 4 - diethanolamino - 21 - methylamino - 41 - ethanolamino, 2 - o - tolyloxy - 4 - diethanol-amino - 21 : 41 - diamino, 2 : 21 - bis - diethanol-amino - 4 : 41 - di - hydroxyethylthio, 2 : 21 - diphenylthio - 4 : 41 - di - ethanolamino, 2 : 21 - di-p - xylylthio - 4 : 41 - dimorpholino, 2 : 21 - di-thiazolino - (2) - thio - 4 : 41 - di - ethanolamino, 2 : 21 - di - thiazolino - (2) - thio - 4 : 41 - dimorpholino, 2 - phenoxy - 4 - ethanolamino - 21 - ethylamino - 41 - o - anisidino, 2 - a  - naphthoxy - 4 - ethanolamino - 21 - ethylamino - 41 - o-anisidino, 2 - phenoxy - 4 - ethanolamino - 21 - chloro - 41 - diethanolamino, 2 - p - sulphophenoxy - 4 - ethylamino - 21 : 41 - di - o - chloranilino, 2 - benzthiazolyl - (2) - thio - 4 - ethanolamino - 21 : 41 - bis - diethanolamino and 2 - carboxymethylthio - 4 - ethanolamino - 21 : 41-bis-diethanolamino. Besides the above, the following substituent groups are mentioned :-SR : allylthio, amylthio, sulphoalkylthio, polyglycolthio, haloarylthio, alkoxyarylthio, acylaminoarylthio, dialkylaminoarylthio, carboxyarylthio and sulphoarylthio; aryloxy: m- and p-chlorophenoxy, 2 : 4-dichlorophenoxy, m- and p-tolyloxy, halotolyloxy, p-bromophenoxy, p-tert.-butylphenoxy, carboxyphenoxy, thymoxy, acylaminoaryloxy and dialkylaminoaryloxy; amino: propylamino, isopropylamino, butylamino, isobutylamino, allylamino, di-isobutylamino, dimethylaminoethylamino, sulphoethylamino, anilino, toluidino, naphthylamino, piperidino, pipecolino, pyrrolidino, tetrahydroquinolino, imidazolino, benzimidazolyl, thiazolyl-(2)-amino and tetrazolyl-(5)-amino. The invention includes water-soluble salts of these compounds with alkali metals, ammonia and amines.  4 - Amino - 41 - (substituted - 1 : 3 : 5 - triazinyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acids are made as follows, the numbering referring to the triazine ring:-2-methylamino-4-ethanolamino by condensing cyanuric chloride with 4-nitro-41-aminostilbene-2 : 21-disulphonic acid, reacting the product successively with methylamine and ethanolamine and reducing the nitro group; 2-ethylamino-4-o-anisidino similarly by using ethylamine and o-anisidine; 2-phenoxy-4-ethanolamino similarly by using phenol and ethanolamine; 2 : 4-di-o-chloranilino similarly by using 2 mols. of o-chloraniline.  4 - (2 - chloro - 4 - ethanolamino - 1 : 3 : 5 - triazyl - 6 - amino) - 41 - (2 - amino - 4 - diethanolamino - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid is made by reacting 4 - nitro - 41 - (2 : 4 - dichloro - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid with 1 mol. each of ammonia and diethanolamine, reducing the nitro group and condensing the product successively with 1 mol. each of cyanuric chloride and ethanolamine.ALSO:Stilbene derivatives of the formula <FORM:0681642/IV (c)/1> and salts thereof are used as fluorescent brightening agents; W is aryloxy or -SR, R being an aliphatic, aromatic or heterocyclic residue which may be substituted; X and Y are -NH2 or substituted amino; Z is chlorine, amino, substituted amino, aryloxy or -SR.  The compounds may be applied in aqueous solution to vegetable or animal fibres, such materials being white, dyed or printed.  They are also applicable to fibres or films of synthetic condensation and polymerization products, e.g. polyamides, or regenerated cellulose.  They may be applied in conjunction with washing and bleaching agents, e.g. soaps, salts of sulphonated 2-higher-alkyl-benzimidazoles, salts of monocarboxylic esters of 4-sulphophthalic acid with higher fatty alcohols, fatty alcohol sulphonates, or condensation products of higher fatty acids with aliphatic hydroxy- or amino - sulphonic acids.  In examples: (1) cotton is treated with an aqueous solution of the disodium salt of 4 : 41-bis-(2-phenoxy - 4 - ethanolamino - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid; (2) wool is treated with an aqueous solution of formic acid and the disodium salt of 4 : 41-bis-(2 - phenoxy - 4 - ethylamino - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid; (3) a washing agent for textiles comprises a solution of the sodium salts of 2-heptadecyl-N-benzyl-benzimidazole disulphonic acid and 4 : 41 - bis - (2 - o - chlorophenoxy - 4 - methylamino - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21-disulphonic acid; (4) cotton is washed at the boil in a bath containing soap, sodium carbonate, sodium pyrophosphate, sodium perborate, magnesium silicate and the disodium salt of 4 - (2 - phenoxy - 4 - ethanolamino - 1 : 3 : 5 - triazyl - 6 - amino) - 41 - (2 - ethylamino - 4 - o - anisidino - 1 : 3 : 5 - triazyl - 6 - amino) - stilbene - 2 : 21 - disulphonic acid.  Other suitable compounds are mentioned.ALSO:Stilbene derivatives of the formula <FORM:0681642/III/1> and salts thereof are used as fluorescent brightening agents; W is aryloxy or -SR, R being an aliphatic, aromatic or heterocyclic residue which may be substituted; X and Y are -NH2 or substituted amino; Z is chlorine, amino, substituted amino, aryloxy or -SR.  They may be incorporated in washing compositions for textile materials.  In an example, cotton is washed at the boil in a bath containing soap, sodium carbonate, sodium pyrophosphate, sodium perborate, magnesium silicate, and the disodium salt of 4-(2-phenoxy-4-ethanolamino-1 : 3 : 5-triazyl-6-amino)-41-(2-ethylamino-4-o-anisidino-1 : 3 : 5-triazyl-6-amino)-stilbene-2 : 21-disulphonic acid.  The stilbene derivatives may also be mixed with other synthetic washing agents such as salts of sulphonated 2-higher-alkylbenzimidazoles, salts of monocarboxylic esters of 4-sulphophthalic acid with higher fatty alcohols, fatty alcohol sulphonates, or condensation products of higher fatty acids with aliphatic hydroxy- or amino-sulphonic acids.