Patent GB-696357-A (GB)
Title: Manufacture of new derivatives of 4:4-diaminostilbene-disulphonic acid-(2:2)
Filed: 1950-10-06
Abstract: The invention comprises compounds of the formula <FORM:0696357/IV (b)/1> where w is an amino group in which at least one hydrogen atom is replaced by an alkyl, hydroxyalkyl, dialkylaminoalkyl or heterocyclic residue, #c is chlorine and y and z are NH2 or the residues of primary or secondary amines attached via the nitrogen atom.  These are made by (1) reacting 1 mol. of cyanuric chloride in any order with 1 mol. of 4-nitro-41-aminostilbene-2 : 21-disulphonic acid, 0-2 mols. of an alkylamine, dialkylamine, hydroxyalkylamine, bis-hydroxyalkylamine, N1 : N1-dialkyl-alkylene diamine or heterocyclic amine and 1-2 mols. of ammonia or a primary or secondary amine; the nitro group is then reduced to amino and a further mol. of cyanuric chloride reacted in any order with 1 mol. of the product and 1-2 mols. of amino compounds as above; instead of the nitro group there may be present another group convertible to amino, e.g. acylamino; or (2) reacting 2 mols. of cyanuric chloride in any order with 1 mol. of 4 : 41-diaminostilbene-2 : 21-disulphonic acid and 3 mols. of amino compounds as above; in this case a mixture is usually formed.  The products form salts with alkali metals, ammonia and amines.  In the examples, the following derivatives of stilbene-2 : 21-disulphonic acid are obtained as sodium salts: 4 - (2 - ethylamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 - methylamino - 4 - ethanolamino - 6 - triazinylamino), 4 - (2 - morpholino - 4 - chloro - 6 - triazinylamino) - 41 - (2 : 4 - bis - diethanolamino - 6 - triazinylamino), 4 - (2 - diethanolamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 : 4 - di - o - anisidino - 6 - triazinylamino), 4 - (2 - isopropylamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 - morpholino - 4 - o - anisidino - 6 - triazinylamino) and 4 - (2 - ethanolamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 - ethylamino - 4 - o - anisidino - 6 - triazinylamino). Other specified groups are: w: methylamino, propylamino, butylamino, dimethylamino, dipropylamino, dibutylamino, isobutylamino, diisobutylamino, propanolamino, dimethylaminoethylamino, diethylaminoethylamino, pipecolino, pyrrolidino, tetrahydroquinolino, thiazolyl2-amino and tetrazolyl-5-amino; y and z: amino, anilino, o- and p-chloranilino, p-anisidino, toluidino, p-acetylaminoanilino, naphthylamino and the groups specified for w.  The following substituted 4-aminostilbene2 : 21-disulphonic acids are made by condensing cyanuric chloride with 4-nitro-41-aminostilbene2 : 21-disulphonic acid and the appropriate amino compounds, and reducing the nitro group: 41-(2-methylamino-4-ethanolamino - 6 - triazinylamino), 41 - (2 : 4 - di - o - anisidino - 6 - triazinylamino), 41 - (2 - morpholino - 4 - o - anisidino - 6 - triazinylamino) and 41 - (2 - ethylamino - 4 - o - anisidino - 6 - triazinylamino).ALSO:Stilbene derivatives of the formula <FORM:0696357/IV (c)/1> and salts thereof are used as fluorescent brightening agents; W is an amino group in which at least one hydrogen atom is replaced by an alkyl, hydroxyalkyl, dialkylaminoalkyl or heterocyclic residue, X is chlorine and Y and Z are NH2 or the residues of primary or secondary amines attached via the nitrogen atom.  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 and films of synthetic condensation and polymerization products, e.g. polyamides and 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 aminosulphonic acids.  In examples: (1) cotton is treated with a solution of the disodium salt of 4 - (2 - ethylamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 - methylamino - 4 - ethanolamino - 6 - triazinylamino) - stilbene - 2 : 21 - disulphonic acid; (2) wool is treated with a solution of formic acid and the compound of (1); (3) textiles are washed with a soap-like mass obtained by mixing fused soap (60 per cent fatty acid) with the disodium salt of 4-(2-morpholino - 4 - chloro - 6 - triazinylamino) - 41 - (2 : 4 - bis - diethanolamino - 6 - triazinylamino) - stilbene-2 : 21-disulphonic acid; (4) cotton is treated with a solution of water-glass, hydrogen peroxide and the disodium salt of 4-(2-ethanolamino - 4 - chloro - 6 - triazinylamino) - 41 - (2 - ethylamino - 4 - o - anisidino - 6 - triazinylamino) - stilbene - 2 : 21 - disulphonic acid.  Other suitable compounds are mentioned.ALSO:Stilbene derivatives of the formula <FORM:0696357/III/1> and salts thereof are used as fluorescent brightening agents; w is an amino group in which at least one hydrogen atom is replaced by an alkyl, hydroxyalkyl, dialkylaminoalkyl, or heterocyclic residue, x is chlorine and y and z are NH2, or the residues of primary or secondary amines attached via the nitrogen atom. They may be incorporated in washing compositions for textile materials.  An example is given of a preparation obtained by adding to a fused soap mass (60 per cent fatty acid) a small amount of the disodium salt of 4-(2 - morpholino - 4 - chloro - 6 - triazinyl - amino) - 41 - (2:4 - bis-diethanolamino - 6 - triazinylamino) - stilbene - 2 : 21 - disulphonic acid and allowing the mixture to cool.  The stilbene derivatives may be mixed with other synthetic washing agents such as 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.