Patent GB-774010-A (GB)
Title: Improvements relating to fluorescent stilbyl triazole compounds and to their use
Filed: 1954-10-15
Abstract: Polymers and copolymers of vinyl chloride, vinylidene chloride, acrylonitrile, acrylic esters, styrene and ethylene are brightened or whitened by preferably incorporating in the plasticisers therefor 2-(stilbyl-411)-(4 : 5-benzo- or naphtho-) 1 : 2 : 3-triazoles of formula <FORM:0774010/IV(a)/1> wherein A represents a benzene or naphthalene radical in which two vicinal carbon atoms are bound to nitrogen atoms of the triazole ring, at least one X represents a non-acid dissociating sulphonyl substituent -SO2R, R being an aryl, alkyl, aryloxy, amino or organically substituted amino group, and the other X's represent hydrogen or, with the exception of chromophores, hydroxyl and amino groups, any non-ionogenic substituent, and the aromatic radicals may be further substituted as required except by chromophores, auxochromes and other ionogenic substituents. Specified further substituents are halogens and alkyl, alkoxy, alkylenedioxy, aryloxy, phenyl, acylamino, cyano, carboxylic amide, -SO2R and 4 : 5-benzo- or naphtho-1 : 2 : 3-triazolyl-(2)-groups.  Dioctyl phthalate is specified as a plasticiser.  Exemplified stilbene-triazoles are phenyl, tolyl, xenyl, para-tert.-butylphenyl, para-tert.-amylphenyl-, para-n-octylphenyl, a -naphthyl and b -naphthyl esters and amides, dimethylamides, ethylamides, n-butylamides, di-n-butylamides, n-octylamides, n-decylamides, n-dodecylamides, n-hexadecylamides, n-octadecylamides, diethanolamides, aminoethylamides, diethylaminoethylamides, cyclohexylamides, dicyclohexylamides, anilides, benzylamides, N-methyl-anilides, (5-phenylsulphone-2-methyl)-anilides, 3-sulphamylamides, 4-sulphamylamides, a -naphthylamides, b -naphthylamides, a -N-ethylnaphthylamides, (41-amyl-diphenylether-2)-amides, morpholides, piperidides and 2-pyridylamides of 211-sulpho-, 2111-sulpho-, 4111-sulpho-, 211 : 51-disulpho-, 211 : 61-disulpho-, 211 : 51 : 7-trisulpho-, 31 - phenoxycarbonyl - 211 - sulpho -, 31 - cyclohexylcarbamoyl - 211 - sulpho -, 31 - ethylcarbamoyl - 211 - sulpho -, 211 - sulpho - 3111 : 4111-dimethoxy -, 211 - sulpho - 2111 : 3111 - dimeth oxy-, 211-sulpho-4111-phenoxy-, 211-sulpho-2111-methoxy-, 211-sulpho-3111-methoxy-, 211 : 2111-disulpho - 4111 - (naphtho - 11 : 21 : 4 : 5 - triazolyl - 2) - and 211 - sulpho - 3111 : 4111 - methylenedioxy - 2 - (stilbyl - 411) - (naphtho - 11 : 21 : 4 : 5) - 1 : 2 : 3 - triazoles and 5 - methoxy - 6 - methyl - 21 - sulpho -, 5 - acetamido - 21 - sulpho -, 5 - benzamido - 21 - sulpho -, 5 - methoxy - 6 - chloro-21-sulpho-and 5:6-dimethoxy-21-sulpho-2 - (stilbyl - 41) - 1:2:3 - benztriazoles; and 211 - methylsulphonyl-, 2111-methylsulphonyl-, 4111-methylsulphonyl-, 2111 - n - butylsulphonyl -, 4111 - n - butylsulphonyl -, 211-(2:4 - dimethylphenyl) - sulphonyl - and 211 - (4 - methylphenyl) - sulphonyl - 2 - (stilbyl - 411) - naphtho11:21:4:5)-1:2:3-triazoles. In examples: (1) sheets are made from a gelatinised mixture of polyvinyl chloride, dioctyl phthalate, di-n-butyldilauryldioxystannate, sodium penta-octyltripolyphosphate and stilbyl-triazole brightening-agent with or without titanium dioxide; (2) a mixture of polystyrene and stilbyl-triazole brightening agent is homogenized to give an injection moulding composition.ALSO:The invention comprises compounds of formula <FORM:0774010/IV(b)/1> wherein A represents a benzene or naphthalene radical in which two vicinal carbon atoms are bound to nitrogen atoms of the triazole ring, at least one X represents a non-acid dissociating sulphonyl substituent -SO2R, R being an aryl, alkyl, aryloxy, amino or organically substituted amino group, and the other X's represent hydrogen or, with the exception of chromophores, hydroxyl and amino groups, any non-ionogenic substituent, and the aromatic radicals may be further substituted as required except by chromophores, auxochromes and other ionogenic substituents. Specified further substituents are halogens and alkyl, alkoxy, alkylenedioxy, aryloxy, phenyl, acylamino, cyano, carboxylic amide, -SO2R and 4 : 5-benzo- or naphtho-1 : 2 : 3-triazolyl-(2)-groups.  The compounds are prepared (1) by treating the corresponding sulphonic acids (in which R is OH in the above formula) with phosphorus halides to form the corresponding acid halides, which are then treated with ammonia or organic primary or secondary amines to form sulphonamides, with aromatic hydroxyl compounds or salts thereof to form aryl sulphonates, with aromatic hydrocarbons in presence of Friedel-Crafts catalysts to form aryl sulphones or are reduced to sulphinic acids and aralkylated or alkylated to form aralkyl or alkyl sulphones; (2) by coupling a diazotized 4-aminostilbene compound containing at least one -SO2R substituent in a position ortho or para to the ethylene bridge with a benzene or naphthalene azo component coupling in a position adjacent to an amino substituent, oxidizing the ortho-aminoazo dyestuff so formed with alkali hypochlorite or cupric tetrammine sulphate and eliminating or converting any inadmissible substituent introduced with the azo component.  The examples describe the preparation of phenyl, tolyl, xenyl, para - tert. - butylphenyl, para - tert. - amylphenyl, para - n - octylphenyl, a  - naphthyl and b -naphthyl esters and amides, ethylamides, dimethylamides, di - n - butylamides, n - butylamides, n-octylamides, n-decylamides, n-hexadecylamides, n - dodecylamides, n - octadecylamides, diethanolamides, aminoethylamides, diethylaminoethylamides, cyclohexylamides, dicyclohexylamides, anilides, benzylamides, N-methyl-anilides, (5-phenylsulphone-2-methyl)-anilides, 3-sulphamylanilides, 4-sulphamylanilides, a -naphthylamides, b -naphthylamides, a -N - ethylnaphthylamides, (41 - amyl - diphenylether - 2) - amides, morpholides, piperidides and 2-pyridylamides of 211-sulpho-, 2111-sulpho-, 4111-sulpho-, 211 : 51-disulpho-, 211 : 61-disulpho-, 211 : 51 : 71 - trisulpho-, 31 - phenoxycarbonyl - 211 - sulpho-, 31 - cyclohexylcarbamoyl - 211 sulpho -, 31 - ethylcarbamoyl - 211 - sulpho -, 211 - sulpho - 3111 : 4111 - dimethoxy-, 211-sulpho-2111 : 3111 - dimethoxy-, 211 - sulpho - 4111 - phenoxy-, 211 - sulpho - 2111 - methoxy -, 211 - sulpho-3111 - methoxy-, 211 : 2111 - disulpho - 4111 - (naphtho - 11 : 21 : 4 : 5 - triazolyl - 2) - and 211 - sulpho - 3111 : 4111 - methylenedioxy - 2 - (stilbyl - 411) - (naphtho - 11 : 21 : 4 : 5) - 1 : 2 : 3 - triazoles and 5 - methoxy - 6 - methyl - 21 - sulpho -, 5 - acetamido - 21 - sulpho -, 5-benzamido - 21 - sulpho -, 5 - methoxy - 6 - chloro - 21 - sulpho - and 5 : 6 - dimethoxy - 21 - sulpho - 2 - (stilbyl-41) - 1 : 2 : 3 - benztriazoles; and 211 - methylsulphonyl -, 2111 - methylsulphonyl -, 4111 - methylsulphonyl -, 2111 - n - butylsulphonyl -, 4111 - n - butylsulphonyl -, 211 - (2 : 4 - dimethylphenyl) - sulphonyl - and 211 - (4 - methylphenyl) - sulphonyl - 2 - (stilbyl - 411) - (naphtho - 11 : 21 : 4 : 5)-1 : 2 : 3-triazoles.  Sodium 2 - (stilbyl - 411) - (naphtho - 11 : 21 4 : 5) - 1 : 2 : 3 - triazole - 4111 - sulphonate is prepared by a method similar to (2) above.  The following intermediates are prepared by method (1) above : 211-chlorosulphonyl-, 4111 -chlorosulphonyl -, 51 : 211 - di - (chlorosulphonyl)-, 61 : 211 - di - (chlorosulphonyl)-, 3111 : 4111-dimethoxy -211 - chlorosulphonyl -, 2111 : 3111 - dimethoxy - 211 - chlorosulphonyl -, 4111 - phenoxy - 211 - chlorosulphonyl - and 31 - chlorocarbonyl - 211 - chlorosulphonyl - 2 - (stilbyl - 411) - naphtho - 11 : 211 : 4 : 5) - 1 : 2 : 3 - triazoles; and 5 - methoxy - 6 - methyl - 21 - chlorosulphonyl - 2 - (stilbyl - 41) - 1 : 2 : 3 - benztriazole.  4 - Nitro - 2 - chlorosulphonylstilbene and 4 - nitro - 211 - chlorosulphonylstilbene are prepared by treating the corresponding sulphonic acid sodium salts with phosphorus pentachloride.  2 - Phenylsulphamoyl-, 2 - (2 : 4 - dimethylphenyl) - sulphonyl -, 21 - dimethylsulphamoyl-, 21 - cyclohexylsulphamoyl -, 21 - morpholinosulphonyl-, 21 - di - n - butylsulphamoyl-, 21 - phenoxysulphonyl -, 21 - methylsulphonyl - and 41 - methylsulphonyl - 4 - aminostilbenes are prepared by reduction of the corresponding 4-nitrostilbenes.  4 - Nitrostilbene - 21 - sulphinic acid is formed as the sodium salt by treating 4-nitrostilbene-21-sulphonic acid chloride with a solution of sodium sulphite and sodium hydroxide.  2 - Phenylsulphamoyl -, 2 - di - n - butylsulphamoyl- and 21-dimethylsulphamoyl-4-nitrostilbenes are prepared by reacting the corresponding 4-nitrostilbene sulphonyl chlorides with an appropriate amine.  4 - Nitro - 2 - phenoxysulphonylstilbene is prepared by reacting 4-nitro-2-chlorosulphonylstilbene with a mixture of phenol and sodium hydroxide.  4 - Nitro - 21 - methylsulphonylstilbene is prepared by reacting sodium 4-nitrostilbene-21-sulphinate with a mixture of dimethyl sulphate and magnesium oxide.  4 - Nitro - 41 - methylsulphonylstilbene is prepared by condensing para-nitrophenyacetic acid with para - methylsulphonylbenzaldehyde. 3 - Nitro - 6 : 21 : 4 - trimethyl - 1 : 11 - diphenyl sulphone is prepared by condensing 4-nitrotoluene-2-sulphonic acid chloride with metaxylene in presence of ferric chloride.  4 - Nitro - 2 - (2 : 4 - dimethylphenyl) - sulphonyl-stilbene is prepared by condensing 3 - nitro - 6 : 21 : 41 - trimethyl - 1 : 11 - diphenylsulphone with benzaldehyde. Specifications 717,889 and 726,119 are referred to.ALSO:Ortho - aminoazo - stilbene dyestuffs are prepared by coupling diazotized 4 - aminostilbenes containing at least one sulphonic acid or non-acid dissociating sulphonyl substituent - SO2R, R being an aryl, alkyl, aryloxy, amino or organically substituted amino group, in an ortho - or para - position to the ethylene bridge, with azo components coupling adjacent to an amino substituent. Exemplified 4-aminostilbenes are 2 - sulpho -, 21 - sulpho, 41 - sulpho -, 2:21 - disulpho, 2 - phenoxysulphonyl-, 21-phenoxysulphonyl -, 41 - phenoxysulphonyl, 2:21 -