Patent GB-797427-A (GB)
Title: New 4:4-diaminostilbenedisulphonic acid derivatives and their manufacture and use
IPC: G01N31/22
Filed: 1954-10-25
Abstract: The invention comprises N : N1-disubstituted-4 : 41-diaminostilbene-2 : 21-disulphonic acids of the general formula: <FORM:0797427/IV (b)/1> where L is -SO3H or a salt thereof, R is an aryl residue which may be substituted, and R1 is an acyl, triazinyl or carbamic acid residue which may be substituted, which disulphonic acids contain no group imparting colour thereto.  The compounds are prepared by reacting in molecular proportions a compound of the formula: <FORM:0797427/IV (b)/2> where A is an amino or nitro group with a sulphonyl halide of the formula R-SO2-halogen or a compound capable of introducing the residue R1, and when A is nitro reducing the latter to amino, the product being reacted with the sulphonyl halide R-SO2-halogen or the compound capable of introducing the residue R1, provided that each of the residues R-SO2-and R1 is introduced only once.  Specified sulphonyl halides of the formula R-SO2-halogen are benzene-, o- and p-toluene-, p-chlorobenzene-and naphthalene-sulphochlorides.  When the residue R1 is acyl, the compounds may have the formula: <FORM:0797427/IV (b)/3> where R2 is a substituted or unsubstituted aryl, aralkyl, aryloxyalkyl or heterocyclic residue.  Compounds capable of introducing the residue -CO-R2 are acid anhydrides or acid halides.  Acids specified are benzoic, o- or p-chlorobenzoic, 2 : 4-dichlorobenzoic, o- or p-methoxybenzoic, o- or p-ethoxybenzoic, 2 : 4-dimethoxybenzoic, 2 - methoxy - 4 - or 5 - methyl - benzoic, 2 : 4 : 5-trimethoxybenzoic, 2-methoxy- or 2 - ethoxy - naphthalene - 3 - carboxylic, furane-2 - carboxylic, thiophene - 2 - carboxylic, phenylacetic and phenoxyacetic acids. Specified compounds of this type are 4-(benzenesulphonamido) - 41 - (o - methoxybenzoylamino) - stilbene - 2:21 - disulphonic acid, 4 - (p - methylbenzenesulphonamido) - 41 - (p - methoxybenzoylamino) - stilbene - 2:21 - disulphonic acid, and 4 - (benzenesulphonamido) - 41 - (phenylacetylamino) - stilbene - 2:21 - disulphonic acid. When R1 is a carbamic acid residue, the compounds may have the formula: <FORM:0797427/IV (b)/4> where R3 is a substituted or unsubstituted alkyl or aryl residue.  Compounds capable of introducing the residue -CO-NH-R3 are isocyanates; those mentioned are phenyl-, p-chlorophenyl-, p-methylphenyl-, p-methoxyphenyl- and methyl-isocyanates.  Compounds of this type specified are 4-(benzenesulphamido)-41 - (methylcarbamido) - stilbene - 2:21 - disulphonic acid and 4 - (p - methylbenzenesulphonamido) - 41 - (phenyl carbamido) - stilbene-2:21-disulphonic acid.  When R1 is a triazinyl residue, the compounds may have the formula: <FORM:0797427/IV (b)/5> where y is -OH, -NH2 or the residue of a primary or secondary amine, or a residue bound to the carbon atom of the triazine ring through an -O- or -S- bridge, and Z is a chlorine atom or has the meaning given for y.  The compound capable of introducing the triazinyl residue is triazinyl chloride, one or both of the unreacted chlorine atoms being replaced by -OH or -NH2 or being reacted with primary or secondary amines or hydroxy- or mercaptocompounds to form groups y and z.  Amines specified are the alkylamines and dialkylamines having alkyl groups of 1-4 carbon atoms, N:N1 - dimethylethylenediamine, allylamine, mono - and diethanolamine, propanolamine, aniline, p-chloroaniline, p-methoxyaniline, the toluidines, a - or b -naphthylamine, pipecolines, pyrrolidine, tetrahydroquinoline, 2-aminothiazole, 5-aminotetrazole, imidazole, benzimidazole and morpholine.  Hydroxy- and mercapto-compounds specified are the primary, secondary and tertiary aliphatic alcohols of 1-4 carbon atoms, allyl alcohol, hexyl alcohol, 2-ethylbutanol, ethylene chlorhydrin, oxyethane sulphonic acid, allyl and amyl mercaptans, thioglycollic acid, thioethylene glycol, phenol, o-, m- and p-chlorophenol, 2:4-dichlorophenol, o-, m- and p-cresol, halogenated cresols, p-bromophenol, naphthols, p-tert.-butyl phenol, salicylic acid, p-oxybenzoic acid, phenol sulphonic acids, thymol, guaiacol, thiophenol, benzyl alcohol, ar-tetrahydro-a - and ar-tetrahydro-b -naphthyl carbinol, 2-mercaptothiazoline, 2-oxybenzthiazole and 2 - mercaptobenzthiazole. Specified compounds of this type are 4(benzenesulphamido) - 41 - [2:4 - di - (b  - hydroxyethylamino) - 1:3:5 - triazinyl - (6) - amino] - stilbene - 2:21 - disulphonic acid, 4 - (p - methylzenesulphonamido) - 41 - [2 - phenylamino - 4-di(b  - hydroxyethyl)amino - 1:3:5 - triazinyl-(6) - amino] - stilbene - 2:21 - disulphonic acid, and 4 - (benzenesulphonamido) - 41 - [2 - chloro-4(b  - hydroxyethylamino) - 1:3:5 - triazinyl-(6) - amino] - stilbene - 2:21 - disulphonic acid. The salts of the disulphonic acids mentioned are the alkali-metal, ammonium and amino salts.  The compounds are fluorescent brightening agents (see Groups IV (c) and VIII).  In examples: (1) benzene sulphochloride is reacted with 4-amino-41-nitrostilbene-2:21-disulphonic acid, the nitro group is reduced, and the 4 - amino - 41 - benzenesulphonamido - stilbene-2:21-disulphonic acid so obtained is treated with anisoyl chloride to yield the sodium salt of 4 - [(p - methoxybenzoyl)amino] - 41 - [benzenesulphonamido] - stilbene - 2:21 - disulphonic acid, the corresponding 4-[benzoylamino]-compound is similarly prepared using benzoyl chloride; (2) 4 - amino - 41 - [2:4 - di - (b  - oxyethylamino) - 1:3:5 - triazinyl - (6) - amino]-stilbene - 2:21 - disulphonic acid, obtained by condensing 4 - amino - 41 - nitro - stilbene - 2:21-disulphonic acid with cyanuric chloride and ethanolamine and reducing the nitro group, is reacted with benzene sulphochloride to give the corresponding 4 - [benzenesulphonamido]-derivative; (3) disodium 4 - [(o - methoxybenzoyl)amino] - 41 - (p - toluenesulphonamido]-stilbene - 2:21 - disulphonate is prepared by reacting p - toluene sulphochloride with 4-amino - 41 - [(o - methoxybenzoyl) - amino] - stilbene-2:21-disulphonic acid and neutralization with sodium carbonate; (4) 4-amino-41-(benzenesulphonamido) - stilbene - 2:21 - disulphonic acid is treated with phenyl isocyanate and sodium carbonate to give disodium 4-(benzenesulphonamido) - 41 - (phenyl carbamido)-stilbene - 2:21 - disulphonate, similar compounds are obtained using p-chloro- or p-methyl-phenyl isocyanate.ALSO:Textile and fibrous materials of animal, vegetable or synthetic origin such as fibres, threads, yarns, woven or knitted goods, felt, wool, silk, cotton, hemp, flax, linen, ramie, regenerated cellulose, polyesters, polyamides, feathers, hair, pelts, leather, straw, wood, paper and pasteboard, are treated with fluorescent brightening agents of the general formula <FORM:0797427/IV (b)/1> where L is -SO3H, R is a substituted or unsubstituted aryl residue and R1 is a substituted or unsubstituted acyl, triazinyl or carbamic acid residue, and salts thereof, which compounds contain no group imparting colour thereto. Many compounds of the above formula are specified.  Treatment may be effected by impregnating the material with a solution of the brightening agent and drying the material after centrifuging or squeezing it, or by incorporating the agent in the material during manufacture.  The materials treated may be undyed, dyed or printed.