Patent IE-41696-B1 (IE)
Title: 4-stilbenyl-1,2,3-triazoles process for preparing them andtheir use as optical brighteners
IPC: C08L23/00
Filed: 1975-09-12
Abstract: 1510545 Triazole derivatives and intermediates therefor HOESCHT AG 11 Sept 1975 [13 Sept 1974] 37381/75 Headings C2C and C2P Novel triazole derivatives of the Formula I wherein R is a hydrogen atom, a triphenylmethyl group or an alkyl group optionally substituted by phenyl, hydroxy, alkoxy, carbonyl, cyano, carbamyl, mono- or di-alkyl carbamyl, carboxy or benzoyl; Z is a cyano group or a group of the formula -COOR1, -CONR11R111 or wherein R1, R11 and R111 are hydrogen atoms or alkyl groups, optionally substituted by hydroxy, alkoxy, dialkylamino or trialkyl ammonium groups, or phenyl groups optionally substituted by halogen or by alkyl or alkoxy groups, or -NR11R111 is a pyrrolidine, piperidine, hexamethyleneimine, morpholine or piperazine ring, Y is -O-, -S- or -N(R4)-, R4 being a hydrogen atom or a C 1-4 alkyl group, and the benzene ring B may be substituted by C 1-4 alkyl, C 1-4 alkoxy or halogen; A is one of certain aromatic or heteroaromatic radicals; X is a hydrogen, fluorine, chlorine or bromine atom atom or an alkyl, alkoxy, amino, alkylamino, dialkylamino, trialkylammonium, or acylamino group or an optionally functionally modified carboxy or sulpho group, or two adjacent Xs together form an alkylene or 1,3-dioxapropylene group; and n= 1 to 3; are obtained (1) by reacting compounds of the formula R1(-CH=C(Z)-SO 2 -Ar)a with sodium azide, a being 1 or 2, R1 being or or and Ar being a phenyl group optionally substituted by one or more fluorine, chlorine or bromine atoms or alkyl, alkoxy, nitro, or alkanoylamino groups, or (2) by reacting compounds of the formula with 1 to 1À2 mol of sodium azide at 0 to 200‹ C. or (3) (when R is other than hydrogen) or reacting compounds of the Formula I in which R is a hydrogen atom with appropriate organic sulphates or halides. The above compounds are useful as optical brightening agents. The aryl sulphonyl derivatives used in processes (1) and (2) and having the formulae shown above, may be synthesized from aryl sulphonyl derivatives of the formula ZCH 2 SO 2 Ar. Alternatively some of the compounds of the formula R1(-CH=C(Z)SO 2 Ar)a, may be obtained by reacting phosphorous compounds of the formula with aldehydes or 1 - (4 - Bromomethylphenyl) - 2 - cyano - 2- phenylsulphonyl ethylene may be obtained by brominating 1 - p - tolyl - 2 - cyano - 2 - phenylsulphonyl ethylene, which may be obtained by reacting p-methylbenzaldehyde with phenylsulphonylacetonitrile. 4 - (41 - Benzovazole - 2 - yl) - stilbene - carboxylic acid chloride may be obtained by reacting thionyl chloride with the corresponding free carboxylic acid, which may be obtained by condensing 2 - p - tolyl - benzoxazole (obtained from p-toluic acid and p-aminophenol) with 4 - (p - chlorophenylamino - methyl)benzoic acid methyl ester (obtained from carbomethoxybenzaldehyde and 4-chloroaniline). 2 - (p - Bromomethylphenyl - benzoxazole may be obtained by brominating 2-p-tolyl-benzoxazole. 4 - (41 - Benzoxazole - 2 - yl) - stilbene - aldehyde may be obtained by reacting 2-(4-triphenylphosphonium-methylene-phenyl) benzoxazole bromide with terephthal-aldehyde. 2 - (Phenylsulphonyl)methylbenzoxazole may be obtained by reacting sodium benzene sulphonate with 2 - chloromethylbenzoxazole. Other phenyl sulphonyl compounds of the formula Z-CH 2 -SO 2 -C 6 H 5 , Z being methoxycarbonyl, ethoxycarbonyl, carbamoyl, p - (2 - benzoxazolyl)phenyl, p - methoxycarbonyl phenyl or 2 - benzimidazolyl, are also prepared. 1 - (4 - Triphenylphosphonium - methylphenyl)- 2 - cyano - 2 - phenyl - sulphonyl - ethylene bromide may be obtained by reacting 1-(4- bromomethylphenyl) - 2 - cyano - 2 - phenylsulphonylethylene with triphenyl phosphine. 2 - (4 - Triphenylphosphonium methylenephenyl)benzoxazole bromide may be obtained by reacting 2 - p - bromomethylphenyl benzoxazole with triphenyl phosphine.