Patent GB-796211-A (GB)
Title: Fluorescent stilbene derivatives
Filed: 1956-06-18
Abstract: The invention comprises compounds of the formula: <FORM:0796211/IV (b)/1> wherein X is the acyl radical of a carbocyclic aromatic carboxylic acid, M is a cation, and n is an integer 0, 1 or 2, and also two methods of preparing them starting from an aminonitrostilbene disulphonic acid of the formula: <FORM:0796211/IV (b)/2> by (a) diazotization, coupling with a naphthylamine capable of coupling in o-position to the amino group or with a mono- or di-sulphonic acid thereof, oxidizing the o-amino-azo compound obtained to the 1,2,3-triazole, and then reducing the nitro group to amino, and acylating with an agent introducing radical X, and by (b) acylating the amino group to introduce X, reducing nitro to amino, and diazotizing, coupling, and oxidizing as under (a).  The products are useful as brightening agents, and as green toners for brightening agents having a reddish fluorescence and may be mixed with detergents in cleansing compositions or used to treat fabrics such as cotton, linen, viscose, nylon, or wool.  In examples: (1) sodium-4-[41-, 51-, or 61-sulphonaphtho-11,21,41,5 - triazolyl - (2)] 41 - aminostilbene - 2,21-disulphonate is acylated with phenoxyacetyl chloride, phenylacetyl chloride, anisoyl chloride, o-ethoxybenzoyl chloride, and benzoyl chloride, and the corresponding body unsulphonated with o-chlorobenzoyl chloride; (2) 4 - nitro - 41 - aminostilbene - 2,21 - disulphonic acid is acylated with benzoyl chloride (or toluyl chloride), the benzoylated product is reduced to give sodium 4-amino-41-benzoylamino - stilbene - 2,21 - disulphonate, which is diazotized and coupled with 2-naphthylamine-3,6- or 5,7-disulphonic acid, and the resultant o-aminoazo dye is oxidized with hypochlorite solution to give sodium-4-[31,61-disulphonaphtho - 11,21,4,5 - triazolyl - (2)] - 41 - benzoylaminostilbene - 2,21 - disulphonate. Further examples describe cleansing compositions consisting of (3) sodium-4-[61-sulphonaphtho-11,21,4,5 - triazolyl - (2)] - 41 - benzoylaminostilbene - 2,21 - disulphonate, sodium - 4,41-bis - (phenylcarbamylamino) - stilbene - 2,21-disulphonate, glauber's salt, sodium dodecylbenzene sulphonate, sodium tripolyphosphate and sodium carbonate; (4) common soap, sodium carbonate and tripolyphosphate, sodium 4,41 - dibenzoylaminostilbene - 2,21 - disulphonate and sodium - 4 - [51 - sulphonaphtho-11,21,4,5 - triazolyl - (2)] - 41 - phenoxyacetylaminostilbene - 2,21 - disulphonate, and also the whitening of (5) linen, with a mixture of sodium - 4,41 - bis - (anilino - 4 - hydroxy - 1,3,5-triazinyl - (6) - amino) stilbene - 2,21 - disulphonate and sodium - 4 - [61 - sulphonaphtho-11,21,4,5 - triazolyl - (2)] - 41 - benzoylaminostilbene - 2,21 - disulphonate; (6) cotton, with sodium 4 - [51 - sulphonaphtho - 11,21,4,5 - tri azolyl - (2)] - 41 - anisoyl - aminostilbene - 2,21-disulphonate or with sodium - 4 - [41 - sulphonaphtho - 11,21,4,5 - triazolyl - (2)] - 41 - o - ethoxybenzoylaminostilbene - 2,21 - disulphonate; (7) nylon (previously treated with 4-methyl-7-diethylaminocoumarin) with sodium-4 - [61 - sulphonaphtho - 11,21,4,5 - triazolyl-(2) - 41 - anisoylaminostilbene - 2,21 - disulphonate, or with sodium-4-(naphtho-11,21,4,5-triazolyl - (2)] - 41 - chlorobenzoylaminostilbene-2,21-disulphonate; (8) wool, with a mixture of 4,5 - di - (sulphophenyl) - 2 - imidazolone and sodium - 4 - [51 - sulphonaphtho - 11,21,4,5 - triazolyl - (2)] - 41 - benzoylamino - stilbene - 2,21-disulphonate.  A further example describes the incorporation of sodium-4,41-bis-(phenylcarbamylamino) - stilbene - 2,21 - disulphonate and sodium - 4 - [31,61 - disulphonaphtho - 11,21,4,5-triazolyl - (2)] - 41 - benzoylaminostilbene - 2,21-disulphonate in a sulphite-cellulose paper mass and the working up of the mass into paper.ALSO:The invention comprises compounds of the formula: <FORM:0796211/IV (b)/1> wherein X is the acyl radical of a carbocyclic aromatic carboxylic acid, M is a cation, and n is an integer 0, 1 or 2, and also two methods of preparing them starting from an amino-nitrostilbene disulphonic acid of the formula: <FORM:0796211/IV (b)/2> by (a) diazotization, coupling with a naphthylamine capable of coupling in o-position to the amino group or with a mono- or di-sulphonic acid thereof, oxidizing the o-amino-azo compound obtained to the 1.2.3-triazole, and then reducing the nitro group to amino, and acylating with an agent introducing radical X; and by (b) acylating the amino group to introduce X, reducing nitro to amino, and diazotizing, coupling, and oxidizing as under (a). The products are useful as brightening agents, and as green toners for brightening agents having a reddish fluorescence and may be mixed with detergents in cleansing compositions or used to treat fabrics such as cotton, linen, viscose, nylon or wool.  In examples: (1) sodium-4-[41-, 51- or 61-sulphonaphtho - 11.21.4.5 - triazolyl - (2)]41 aminostilbene-2.21-disulphonate is acylated with phenoxyacetyl chloride, phenylacetyl chloride, anisoyl chloride, o-ethoxybenzoyl chloridc, and benzoyl chloride, and the corresponding body unsulphonated in the naphthalene nucleus is acylated with o-chlorobenzoyl chloride; (2) 4-nitro - 41 - aminostilbene - 2.21 - disulphonic acid is acylated with benzoyl chloride (or toluyl chloride), the benzoylated product is reduced to give sodium 4 - amino - 41 - benzoylaminostilbene-2.21-disulphonate, which is diazotized and coupled with 2-naphthylamine-3.6- or 5.7-disulphonic acid, and the resultant o-aminoazo dye is oxidized with hypochlorite solution to give sodium 4 - [3161 - disulphonaphtho11.21.4.5 - triazolyl - (2)] - 41 - benzoylamino stilbene - 2.21 - disulphonate. Further examples describe cleansing compositions consisting of (6) sodium - 4 - [61 - sulphonaphtho11.21.4.5 - triazolyl - (2)] - 41 - benzoylamino stilbene - 2.21 - disulphonate, sodium - 4.41 - bis(phenylcarbamylamino) - stilbene - 2.21 - disulphonate, Glauber's salt, sodium dodecylbenzene sulphonate, sodium tri-polyphosphate and sodium carbonate; (7) common soap, sodium carbonate and tripolyphosphate, sodium 4.41-dibenzoylaminostilbene - 2.21 - disulphonate and sodium - 4 - [51 - sulphonaphtho - 11.21.4.5 - triazolyl - (2)] - 41 - phenoxyacetylaminostilbene2.21-disulphonate and also the whitening of (8) linen, with a mixture of sodium-4.41-bis(anilino - 4 - hydroxy - 1.3.5 - triazinyl - (6)-amino) stilbene - 2.21 - disulphonate and sodium - 4 - [61 - sulphonaphtho - 11.21.4.5 - triazolyl - (2)] - 41 - benzoylaminostilbene - 2.21 - disulphonate; (9) cotton, with sodium 4 - [51-sulphonaphtho - 11.21.4.5 - triazolyl - (2)] - 41-anisoyl - aminostilbene - 2.21 - disulphonate or with sodium - 4 - [41 - sulphonaphtho - 11.21.4.5-triazolyl - (2)] - 41 - o - ethoxybenzoylaminostilbene - 2.21 - disulphonate; (11) nylon (previously treated with 4 - methyl - 7 - diethylaminocoumarin) with sodium-4-[61-sulphonaphtho - 11.21.4.5 - triazolyl - (2)] - 41 - ansioylaminostilbene - 2.21 - disulphonate, or with sodium-4 - (naphtho - 11.21.4.5 - triazolyl - (2)] - 41-chlorobenzoylaminostilbene - 2.21 - disulphonate; (12) wool, with a mixture of 4.5-di-(sulphophenyl) - 2 - imidazolone and sodium-4 - [51 - sulphonaphtho - 11.21.4.5 - triazolyl - (2)]-41 - benzoylaminostilbene - 2.21 - disulphonate.  A further example describes the incorporation of sodium - 4.41 - bis - (phenylcarbamylamino)-stilbene - 2.21 - disulphonate and sodium - 4-[31.61 - disulphonaphtho - 11.21.4.5 - triazolyl-(2)] - 41 - benzoylaminostilbene - 2.21 - disulphonate in a sulphite-cellulose paper mass and the working-up of the mass into paper.ALSO:The invention relates to cleansing compositions comprising brightening agents of the formula: <FORM:0796211/III/1> wherein X is the acyl radical of a carbocyclic aromatic carboxylic acid, M is a cation, and n is an integer 0, 1 or 2 (see Group IV (b)).  These compounds may be used as green toners for brightening agents having a reddish fluorescence and may be mixed with detergents in cleansing compositions or used to treat fabrics such as cotton, linen, viscose, nylon or wool.  Examples describe cleansing compositions consisting of (6) sodium - 4 - [61 - sulphonaphtho - 11.21.4.5 - triazolyl - (2)] - 41 - benzoylaminostilbene - 2.21-disulphonate, sodium - 4.41 - bis - (phenylcarbamylamino) - stilbene - 2.21 - disulphonate, Glauber's salt, sodium dodecylbenzene sulphonate, sodium tri-polyphosphate and sodium carbonate; (7) common soap, sodium carbonate and tripolyphosphate, sodium 4.41 - dibenzoyl aminostilbene - 2.21 - disulphonate and sodium- 4 - [51 - sulphonaphtho - 11.21.4.5 - triazolyl-(2)] - 41 - phenoxyacetylaminostilbene - 2.21 - disulphonate.