Patent GB-692347-A (GB)
Title: Process for the manufacture of new optical brightening agents, and new compounds produced
Filed: 1949-06-23
Abstract: The invention comprises blue-fluorescent compounds of the general formula <FORM:0692347/IV (b)/1> in which X is halogen, hydroxy or an amino group, Y is hydrogen or methyl, and R is a substituted or unsubstituted lower alkyl radical, and also their preparation by reacting a 4,41-diaminostilbene - 2,21 - disulphonic acid monosubstituted by either a 1,2,5-triazinyl radical or a 2-alkoxy- or 2-acyloxy-benzoyl radical which may be methyl-substituted, with a reactive compound of the other of the two radicals and, if desired or necessary, substituting reactive groups in the triazinyl radical by amino or hydroxy groups, saponifying the acyloxy group, if any, to the hydroxy group and alkylating the latter.  In example (1), 4-nitro-41-aminostilbene-2,21-disulphonic acid (I) is acylated with 2-acetoxy-4-methylbenzoyl chloride and hydrolysed to give 4-nitro-41-(211-hydroxy-411-methylbenzoylamino) - stilbene - 2,21 - disulphonic acid (II).  This is alkylated with diethyl sulphate, reduced to 4-amino-41-(211-ethoxy-411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid, treated with cyanuric chloride and then with ammonia to yield 4-[2111,4111-diamino - triazinylamino - (6111)] - 41 - (211 - ethoxy - 411 - methyl - benzoylamino) - stilbene - 2,21-disulphonic acid.  Instead of diethyl sulphate, dimethyl sulphate may be used, and instead of ammonia there may be used methylamine, ethylamine, monoethanolamine, diethanolamine or amino-propane-diol.  In (2) the compound (I) is acylated with 2-methoxy-4-methylbenzoyl chloride, reduced to 4-amino-41-(211 - methoxy - 411 - methylbenzoylamino) - stilbene-2,21-disulphonic acid which is reacted with cyanuric chloride and then sufficient aniline to replace one of the chlorine atoms in the product whilst the other chlorine atom is subsequently hydrolysed to a hydroxy group; the final product is 4-[2111-anilino-4111-hydroxytriazinylamino - (6111)] - 41 - (211 - methoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid. N-Methylaniline or toluidine may replace the aniline.  In (3) compound (II) is acylated with ethylene chlorohydrin, reduced, and condensed with cyanuric chloride and ammonia to yield 4-[2111,4111-diaminotriazinylamino - (6111)] - 41 - (211 - b  - hydroxyethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid. In example (4), the compound (I) is condensed with cyanuric chloride, reacted with metanilic acid and then aniline, reduced, and the amino compound obtained then acylated with acetyl-o-, m- or p-cresotic acid chloride, hydrolysed and ethylated with diethyl sulphate.  Instead of the acetyl-cresotic acid chloride, acetyl-salicylic acid chloride may be used.  (5) 4-Amino-41-(211-ethoxybenzoylamino) - stilbene - 2,21 - disulphonic acid is reacted with cyanuric chloride and the product reacted with ammonia to yield 4-[2111,4111-diaminotriazinylamino - (6111)] - 41 - (211 - ethoxybenzoylamino) - stilbene - 2,21 - disulphonic acid.  In (6), 4-[2111-anilino-4111-hydroxytriazinylamino - (6111)] - 41 - (211 - isobutoxy - 411 - methylbenzoylamino) - stilbene - 2,211 - disulphonic acid is obtained as in (2) but using 2 - isobutoxy - 4 - methylbenzoyl chloride as the acylating agent.  Specifications 595,065 and 692,346 are referred to.ALSO:Textile materials are brightened by treatment with a blue-fluorescent compound of the general formula <FORM:0692347/IV (c)/1> in which X is halogen, hydroxy or an amino group, Y is hydrogen or methyl, and R is a substituted or unsubstituted lower alkyl group (see Group IV (b)). In examples: (7) white cotton poplin is treated in a bath with 4 - [2111,4111 - diaminotriazinylamino - (6111)] - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid in the presence of Glauber's salt, and (8) white textile goods are washed in a liquor containing soap, sodium carbonate and 4 - [2111 - anilino - 4111 - hydroxytriazinylamino - (6111)] - 41 - (211 - methoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid.  Other compounds specified are those in which X in the general formula is the residue of methylamine, ethylamine, ethanolamine, diethanolamine or aminopropane-diol, Y is 411-methyl and R is ethyl; X is amino, Y is 411-methyl and R is b -hydroxyethyl; one X is anilino and the other the residue of metanilic acid, Y is methyl or hydrogen and R is ethyl; X is amino, Y is hydrogen and R is ethyl; and one X is anilino and the other hydroxy, Y is 411-methyl and R is isobutyl.