Patent GB-692348-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 stilbene derivative of the general formula <FORM:0692348/IV (b)/1> in which X is hydrogen or methyl, R is a substituted or unsubstituted lower alkyl group and Y is the acyl radical of a lower alkyl carboxylic acid, a lower phenalkyl carboxylic acid, a lower phenoxyalkyl carboxylic acid, a phenyl carboxylic acid different from the benzoyl radical A, a lower alkoxy carboxylic acid or a phenylamino carboxylic acid.  The invention also comprises the preparation of such compounds from a 4,41-diaminostilbene-2,21-disulphonic substituted in one of the amino groups by the radical Y or by the benzoyl radical A, by a process which introduces the other of these two radicals. In example (1) 4 - nitro - 41 - aminostilbene - 2,21 - disulphonic acid is acylated with 2-acetoxy-4-methylbenzoyl chloride and saponified and ethylated to give 4-nitro-41-(211-ethoxy-411-methylbenzoylamino) - stilbene - 2,21 - disulphonic acid which is then reduced to 4-amino-41-(211-ethoxy - 411 - methylbenzoylamino) - stilbene-2,21-disulphonic acid (I). The latter compound is then acylated with acetic anhydride or propionic anhydride to yield 4-acetyl (or propionyl) amino-41-(211-ethoxy-411-methylbenzoylamino) -stilbene-2,21-disulphonic acid; (2) 4-carbethoxyamino - 41 - (211 - ethoxy - 411-methylbenzoylamino) - stilbene - 2,21 - disulphonic acid is made from (I) by treatment with ethyl chloroformate; (3) 4-benzoylamino-41 - (211 - ethoxy - 411 - methylbenzoylamino)-stilbene - 2,21 - disulphonic acid is prepared from (I) by treatment with benzoyl chloride, and analogous products are obtained when using o, m or p-chlorobenzoyl chloride or p-toluyl chloride; (4) example (3) is repeated but the benzoyl chloride is replaced by phenylacetyl chloride or phenoxyacetyl chloride to give 4-phenyl (or phenoxy) acetamino-41-(211-ethoxy - 411 - methylbenzoylamino) - stilbene-2,21-disulphonic acid; (5) 4-phenyl (or o- or p-methylphenyl) ureido - 41 - (211 - ethoxy - 411-methylbenzoylamino) - stilbene - 2,21 - disulphonic acid is made by reacting (I) with phenyl isocyanate or o- or p-methylphenyl isocyanate.; (6) the compound (I) is treated with acetyl-salicylyl chloride and saponified to give the hydroxybenzoylamino derivative which is then ethylated to yield 4-(2111-ethoxybenzoylamino) - 41 - (211 - ethoxy - 411 - methybenzoylamino) - stilbene - 2,21 - disulphonic acid; the acetyl-salicylyl chloride may be replaced by acetyl-o-(or p-) cresotic acid chloride to give analogous products; (7) the ethylating agent in (6) is replaced by ethylene chlorohydrin to yield 4 - (2111 - b  - hydroxyethoxybenzoylamino) - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid.  Further examples describe the preparation of the following compounds by similar methods; (8) 4 - (2111 - methoxy - 4111 - methylbenzoylamino) - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid; (9) 4 - (2111 - b  - hydroxyethoxy - 4111 - methylbenzoylamino) - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid; (10) 4 - (211 - methoxybenzoylamino) - 41-benzoylaminostilbene - 2,21 - disulphonic acid; (11) 4 - (211 - ethoxy - 511 - (or 411-) methylbenzoylamino) - 41 - benzoylaminostilbene-2,21 - disulphonic acid; (12) 4 - (2111 - methoxybenzoylamino) - 41 - (211 - ethoxybenzoylamino)-stilbene - 2,21 - disulphonic acid; (13) 4-(2111 - b  - hydroxyethylbenzoylamino) - 41-(211 - ethoxybenzoylamino) - stilbene - 2,21-disulphonic acid, and (14) 4-phenylureido-41-(211 - ethoxybenzoylamino) - stilbene - 2,21-disulphonic acid. Specification 692,346 is referred to.ALSO:Textile materials are brightened by treatment with a blue-fluorescent stilbene derivative of the general formula <FORM:0692348/IV (c)/1> in which X is hydrogen or methyl, R is a substituted or unsubstituted lower alkyl group, and Y is the acyl radical of a lower alkyl carboxylic acid, a lower phenalkyl carboxylic acid, a lower phenoxyalkyl carboxylic acid, a phenyl carboxylic acid different from the benzoyl radical A, a lower alkoxy carboxylic acid or a phenylamino carboxylic acid (see Group IV (b)).  In examples: (15) prebleached woollen yarn is treated in a bath with 4-acetylamino-41-(211-ethoxy-411 -methylbenzoylamino) - stilbene - 2,21 - disulphonic acid in the presence of Glauber's salt and acetic acid; (16) white p  cotton poplin is treated with 4 - phenylureido - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid in the presence of Glauber's salt; and (17) white textile goods are washed in a bath containing soap, sodium carbonate and 4 - (2111 - b  - hydroxyethoxy - 4111 - methylbenzoylamino) - 41 - (211 - ethoxy - 411 - methylbenzoylamino) - stilbene - 2,21 - disulphonic acid.  Other brightening agents specified are those of the above general formula in which X is 4-methyl, R is ethyl and Y is carbethoxy, carbomethoxy, benzoyl, chlorobenzoyl, tolyl, phenacetyl, phenoxyacetyl, methyl-phenylcarbamyl, 2 - ethoxybenzoyl, 2 - ethoxymethylbenzoyl, 2 - hydroxyethoxybenzoyl, 2,3 - dihydroxypropyloxybenzoyl, 2-methoxybenzoyl, 2 - methoxymethylbenzoyl, 2 - hydroxyethoxy-4-methylbenzoyl; in which X is hydrogen, R is ethyl and Y is 2-methoxybenzoyl or 2 - hydroxyethoxybenzoyl or phenylcarbamyl; X is 5-methyl, R is ethyl and Y is benzoyl; and X is hydrogen, R is methyl and Y is benzoyl.