Patent GB-686805-A (GB)
Title: Manufacture and use of new derivatives of 4:4-diaminostilbene-2:2-disulphonic acid
Filed: 1950-10-06
Abstract: The invention comprises compounds of the formula <FORM:0686805/IV (b)/1> and their salts; X is an aromatic or heterocyclic residue, Y is amino or substituted amino and Z is chlorine, aryloxy, alkylthio, arylthio, heterocyclythio, amino or substituted amino; those are excepted in which X is aromatic, Y is arylamino and Z is chlorine. They are made by (1) reacting 1 mol. of cyanuric chloride in either order with 1 mol. of 4-nitro-41-aminostilbene - 2 : 21 - disulphonic acid and 1-2 mols. of ammonia or a primary or secondary amine or 1 mol. of a phenol and 1 mol. of ammonia or an amine or 1 mol. of a mercaptan and 1 mol. of ammonia or an amine; the nitro group is then reduced to amino and the latter acylated with an aromatic or heterocyclic acid or reactive derivative thereof; or (2) acylating 4 - nitro - 41 - aminostilbene - 2 : 21 - disulphonic acid, reducing the nitro group to amino and condensing 1 mol. of cyanuric chloride in either order with 1 mol. of the product and 1-2 mols. of other reactants as above.  The products may be converted into water-soluble alkali metal, ammonium or amine salts.  If X is aromatic, it is preferably a benzene residue which may contain 1 or 2 substituents such as chlorine, bromine, alkyl or alkoxy (up to 4 carbon atoms) or acylamino.  In the examples the following are obtained as sodium salts: 4 - p - anisoylamino - 41 - (2 - methylamino - 4-ethanolamino - 6 - triazylamino) -, 4 - p - anisoylamino - 41 - (2 - chloro - 4 - diethanolamino6 - triazylamino) -, 4 - p - anisoylamino - 41-(2 - phenoxy - 4 - ethanolamino - 6 - triazylamino) -, 4 - p - anisoylamino - 41 - (2 - phenylthio - 4 - methylamino - 6 - triazylamino)-, 4 - o - anisoylamino - 41 - (2 - o - anisidino - 4-ethylamino - 6 - triazylamino) -, 4 - (thenoyl-2 - amino) - 41 - (2 - morpholino - 4 - o - anisidino-6 - triazylamino) - and 4 - p - nitrobenzoylamino - 41 - (2 - methylamino - 4 - ethanolamino - 6 - triazinylamino) - stilbene - 2 : 21-disulphonic acids.  The nitro group in the last named may be reduced to amino and the product condensed with o-anisoyl chloride, p-anisoyl chloride or acetyl chloride.  Other products are mentioned.  Other specified groups are: X : benzoyl, p - chlorobenzoyl, 2 : 4-dichlorobenzoyl, o - bromobenzoyl, p - toluyl, p - isopropylbenzoyl, p - tert - butylbenzoyl, naphthoyl, furan - 2 - carboxyl and 5 - chloro-2 - thenoyl; Y : amino, propylamino, butylamino, dimethylamino, dipropylamino, dibutylamino, isopropylamino, isobutylamino, di-isobutylamino, allylamino, propanolamino, diethylaminoethylamino, anilino, toluidino, p-anisidino, o- and p-chloroanilino, pipecolino, pyrrolidino, tetrahydroquinolino, thiazolyl-2-amino and tetrazolyl - 5 - amino; Z : allylthio, amylthio, carboxymethylthio, hydroxyethylthio, thiazolyl - 2 - thio, benzthiazolyl-2 - thio, chlorophenoxy, 2 : 4 - dichlorophenoxy, tolyloxy, 4 - bromophenoxy, naphthoxy, 4 - tert - butylphenoxy, 2 - and 4 - carboxyphenoxy, sulphophenoxy, thymoxy, 2-methoxyphenoxy, acylaminoaryloxy or -arylthio, dialkylaminoaryloxy or -arylthio, and the groups specified for Y.  4 - Amino - 41 - (6 - triazinylamino) - stilbene-2 : 21 - disulphonic acids are prepared by reacting cyanuric chloride with 1 mol. of 4-nitro - 41 - aminostilbene - 2 : 21 - disulphonic acid and then 1 mol. each of two further amino compounds, followed by reduction of the nitro group.  There are thus prepared compounds with the following substituents in the triazine ring: 2-methylamino-4-ethanolamino, 2 - o - anisidino - 4 - ethylamino and 2-morpholino-4-o-anisidino.  4 - (p - anisoylamino) - 41 - aminostilbene-2 : 21 - disulphonic acid is prepared by reacting p-anisoyl chloride with p  4-amino-41-nitrostilbene-2 : 21-disulphonic acid and reducing the product.  The o-anisoylamino compound is made similarly.ALSO:Stilbene derivatives of the formula <FORM:0686805/IV (c)/1> and salts thereof are used as fluorescent brightening agents; X is an aromatic or heterocyclic residue, Y is amino or substituted amino and Z is chlorine, amino, substituted amino, aryloxy or -SR, where R is an aliphatic, aromatic or heterocyclic residue; those are excluded in which X is aromatic, Y is arylamino and Z is chlorine.  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 washed at the boil in a bath containing soap, sodium carbonate, sodium pyrophosphate, sodium perborate, magnesium silicate and the disodium salt of 4-p-anisoylamino - 41 - (2 - methylamino - 4 - ethanolamino - 6 - triazinylamino) - stilbene - 2 : 21 - disulphonic acid; (2) wool is treated with an aqueous solution of formic acid and the disodium salt of 4-p-anisoylamino-41-(2-chloro-4-diethanolamino - 6 - triazinylamino) - 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-o-anisoylamino-41-(2-o-anisidino - 4 - ethylamino - 6 - triazinylamino) - stilbene-2 : 21-disulphonic acid. p  Other suitable compounds are mentioned.ALSO:Stilbene derivatives of the formula <FORM:0686805/III/1> and salts thereof are used as fluorescent brightening agents; X is an aromatic or heterocyclic residue, Y is amino or substituted amino group and Z is chlorine, amino, substituted amino, aryloxy or -SR, where R is an aliphatic, aromatic or heterocyclic residue; those compounds are excluded in which X is aromatic, Y is arylamino and Z is chlorine.  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-p-anisoylamino-41-(2-methylamino-4-ethanolamino-6-triazinyl 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.