Patent GB-726119-A (GB)
Title: Improvements relating to fluorescent benzotriazole compounds and their use
Filed: 1953-04-30
Abstract: Azo-stilbene dyestuffs are obtained by coupling diazotized 4 - aminostilbene - 2 - sulphonic acids, which may contain further substituents as desired, with azo components of the benzene series coupling in the ortho-position to a primary amino or acylamino group. Azo components coupling in the ortho-position to a primary amino group are, for example, 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulphonic acid, 4-methyl-, 4-chloro-, 4-methoxy-, 4-phenoxy- and 4-methylsulphone-1,3-diaminobenzene, 4 - chloro - 3 - methoxy - and 4 - methyl - 3 - methoxy - 1 - aminobenzene; those coupling in the ortho-position to a primary axylated amino group are, for example, 3-acetaminophenol, 3-acetamino-, 6-methyl-3-acetamino-, 6-chloro-3-acetamino-, and 6-methoxy - 3 - acetamino - 1 - aminobenzene.  Diazo components are, for example, 4-amino-, 4 - amino - 41 - chloro -, 4 - amino - 41 - methyl-, 4 - amino - 41 - methoxy -, 4 - amino - 21 - chloro-, and 4 - amino - 21 - methoxystilbene - 2 - sulphonic acid; 4-amino-, 4-amino-41-nitro-, and 4 - amino - 41 - acylaminostilbene - 2,21 - disulphonic acid.  In the examples 4-aminostilbene - 2 - sulphonic acid is diazotized and coupled with 4-methoxy-1,3-diaminobenzene, 1,3 - diaminobenzene, 4 - chloro - 1,3 - diaminobenzene, 4 - methyl - 1,3 - diaminobenzene and 3 - methoxy - 4 - methyl - 1 - aminobenzene; 4 - amino - 41 - chloro - and 4 - amino - 41 - methylstilbene - 2 - sulphonic acid, 4 - amino - 41 - chloro -, 4 - amino - 41 - acetamino - and 4 - amino - 41 - nitrostilbene - 2,21 - disulphonic acid are diazotized and coupled with 3-methoxy-4 - methyl - 1 - aminobenzene; 4 - amino - 41 - acetaminostilbene - 2,21 - disulphonic acid is diazotized and coupled with 1,3-diaminobenzene, 4 - methyl - 1,3 - diaminobenzene and 4 - methoxy - 1,3 - diaminobenzene; and 4 - amino - 41 - nitrostilbene - 2,21 - disulphonic acid is diazotized and coupled with 1,3-diaminobenzene.  2 - (Stilbyl - 41) - 1,2,3 - benzotriazole compounds of formula <FORM:0726119/IV (c)/1> wherein A represents an ortho-phenylene radical and B a benzene radical, one or both of which are further substituted with chromophore or salt-forming auxochrome groups are prepared by oxidizing the appropriate azo-stilbene dyestuffs described above using, for example, ammoniacal copper sulphate in aqueous solution or suspension at raised temperature, or alkali or alkaline earth hypochlorites. The examples describe the preparation of the following: 5 - amino - 6 - methoxy -, 5 - amino -, 6 - chloro - 5 - amino -, and 6 - methyl - 5 - amino-2 - (stilbyl - 41) - 1,2,3 - benzotriazole - 21 - sulsuphonic acid; 5 - amino - 2 - (411 - acetamino - stilbyl - 41) -, 6 - methyl - 5 - methoxy - 2 - (411 - nitrostilbyl - 41) -, and 5 - amino - 2 - (411 - nitrostilbyl - 41) - 1,2,3 - benzotriazole - 2,21 - disulphonic acid.  2 - (Stilbyl - 41) - 1,2,3 - benzotriazole compounds of the formula given above (see also Group IV (b)), wherein A represents an orthophenylene radical and B a benzene radical, both of which may be further substituted as desired (e.g. by halogens, alkyl, alkoxy, aryloxy, acylamino, acyloxy, carboxyl, sulphonic acid, carboxylic acid amide, sulphonic acid amide, alkyl sulphone and aryl sulphone groups) except by chromophore or salt-forming auxochrome groups are used as such (or as their alkali salts) in neutral to weakly acid baths in which active chlorine may also be present for whitening and brightening cellulose, wool and synthetic fibres, e.g. super-polyamide and -polyurethane fibres. The brightened cellulose fibres may receive after-treatment with diluted hypochlorite solution.  The compounds may also be added to textile treatment liquors and to textile auxiliary products such as soaps, soap powders and synthetic washing agents.  The examples describe the treatment of cotton poplin, woollen yarn and nylon with brightening agents and of household wash (i.e. linen) using (1) curd soap pre-treated with brightening agent, (2) a liquor containing curd soap, sodium carbonate and brightening agent.  Specifications 668,199, [Group IV (b)], and 717,889 are referred to.ALSO:The invention comprises 2-(stilbyl-41)-1,2,3-benzotriazole compounds of formula <FORM:0726119/IV (b)/1> wherein A represents an ortho-phenylene radical and B a benzene radical both of which may be further substituted as desired except by chromophore and salt-forming auxochrome groups.  Substituents in A and B are, for example, halogens, alkyl, alkoxy, aryloxy, acylamino, acyloxy, carboxyl, sulphonic acid, carboxylic acid amide, sulphonic acid amide, alkyl sulphone and aryl sulphone groups.  The compounds are prepared by coupling diazotized 4-aminostilbene-2-sulphonic acids with azo components of the benzene series coupling in the ortho-position to a primary amino group which may be acylated if necessary, oxidizing the ortho-aminoazo dyestuff obtained (after saponification of the acylamino group if necessary) and either modifying or eliminating any chromophore or salt-forming auxochrome groups which may be present. Diazo components are, for example, 4-amino-, 4-amino-41-chloro-, 4-amino-41-methyl-, 4-amino-41-methoxy -, 4 - amino - 21 - chloro -, and 4 - amino - 21 - methoxystilbene - 2 - sulphonic acid; 4-amino-, 4-amino-41-nitro-, and 4-amino - 41 - acylaminostilbene - 2,21 - disulphonic acid.  Azo components coupling in the ortho-position to a primary amino group are, for example, 1,3 - diaminobenzene, 1,3 - diaminobenzene - 4 - sulphonic acid, 4 - methyl -, 4 - chloro-, 4-methoxy-, 4-phenoxy- and 4-methylsulphone - 1,3 - diaminobenzene, 4 - chloro - 3 - methoxy- and 4-methyl-3-methoxy-1-aminobenzene; those coupling in the ortho-position to a primary acylated amino group are, for example, 3 - acetaminophenol, 3 - acetamino-, 6 - methyl - 3 - acetamino -, 6 - chloro - 3 - acetamino-, and 6-methoxy-3-acetamino-1-aminobenzene.  The intermediate ortho-aminoazo dyestuff is oxidized to the 1,2,3-triazole by known methods, e.g. with ammoniacal copper sulphate in aqueous solution or suspension at a raised temperature, or with alkali or alkaline earth hypochlorites.  In modifying auxochromic or chromophoric substituents present in the resulting 1,2,3-triazole phenolic hydroxyl groups are alkylated or acylated (e.g. using dialkyl sulphate or alkyl halide in alkaline solution on the one hand or para-toluene sulphochloride on the other); primary amino groups are either acylated (e.g. with acetic anhydride or benzoyl halides) or are diazotized and the diazo group either replaced by hydrogen (e.g. by boiling with alcohol) or by halogen (e.g. using Sandmeyer's reaction); and nitro groups are reduced to amino groups (e.g. with iron filings and hydrochloric acid) which are then subsequently treated as before.  The examples describe the preparation of 6-methoxy-2-(stilbyl-41)-, 6-methyl - 5 - methoxy - 2 - (stilbyl - 41) -, 6 - methyl - 5 - methoxy - 2 - (411 - chlorostilbyl - 41)-, 411,6-dimethyl-5-methoxy-2-(stilbyl-41)-5 - acetamino - 2 - (stilbyl - 41) -, 6 - chloro - 5 - acetamino - 2 - (stilbyl - 41) -, 6 - methyl - 5 - acetamino-2-(stilbyl-41)-, 6-methoxy-5-acetamino - 2 - (stilbyl - 41) -, 5 - benzoylamino - 2 - (stilbyl - 41) -, 6 - methyl - 5 - benzoylamino - 2-(stilbyl-41)-, and 6-methoxy-5-benzoylamino-2 - (stilbyl - 41) - 1,2,3 - benzotriazole - 21 - sulphonic acid; 6-methyl-5-methoxy-2-(411-chlorostilbyl - 41) -, 6 - methyl - 5 - methoxy - 2 - (411-acetaminostilbyl - 41) -, 2 - (411 - acetaminostilbyl - 41) -, 6 - methyl - 2 - (411 - acetaminostilbyl - 41) -, 6 - methoxy - 2 - (411 - acetaminostilbyl - 41) -, and 6 - methyl - 5 - methoxy - 2 - (411 - acetaminostilbyl - 41) - 1,2,3 - benzotriazole-21,211-disulphonic acid, all of which are isolated as the sodium or disodium salt respectively.  Specifications 668,199 and 717,889 are referred to.ALSO:2-(Stilbyl-41)-1.2.3-benzotriazole compounds of formula <FORM:0726119/III/1> (see Group IV (b)) wherein A represents an orthophenylene radical and B a benzene radical both of which may be further substituted as desired (e.g. by halogens, alkyl, alkoxy, aryloxy, acylamino, acyloxy, carboxyl, sulphonic acid, carboxylic acid amide, sulphonic acid amide, alkyl sulphone and aryl sulphone groups) except by chromophore and salt-forming auxochrome groups are used as additives to soaps and soap powders to which they confer a whiter appearance.  In an example the sodium salt of 6-methyl-5-methoxy - 2 - (stilbyl - 41) - 1.2.3-benzotriazole-21-sulphonic acid is added to curd soap. Specifications 668,199, [Group IV(b)], and 717,889 are referred to.