GB1064128A - New phenyl diazonium salts and their use in diazotype materials - Google Patents

Abstract

The invention comprises diazonium compounds of the general Formula (I) <FORM:1064128/C2/1> in which X is an anion, R1 is alkyl, cycloalkyl, or aralkyl; R2 is hydrogen or an alkyl, cycloalkyl, aralkyl or aryl radical or an alkoxy cycloalkoxy, aralkoxyl or aryloxy linked to the CO group by an oxygen atom, or a substituted amino or amido carbonyl group; R3 represents a substituted or unsubstituted saturated or unsaturated hydrocarbon radical; and R4 represents an alkyl, cycloalkyl, aralkyl or aryl radical. Compounds of the above formula in which the p-substituent is an etherified mercapto group or an acylthio group are prepared from a 5-chloro-2-substituted oxy-1-nitrobenzene by reducing to the corresponding substituted aniline; acylating the amino group; nitrating and deacylating the product to give the 5-chloro-4-nitro-aniline derivative; replacing the chlorine radical by a mono-substituted amino group and replacing the free amino group by a chlorine atom (by diazotization and the Sandmeyer diazo reaction). To obtain an etherified mercapto group in the p-position the 5 - substituted - 4 - chloro - 2 - substituted amino-1-nitrobenzene so obtained is treated with a mercaptan which is acylated, e.g. by treatment with a carboxylic acid chloride, or carboxylated with an ester of chloroformic acid and reduced; the required diazonium compound is produced from the product by standard methods. To obtain the diazonium compounds having acyl or carboxy thio derivatives in the p-position a 5-substituted-4-chloro-2-substituted amino-1-nitrobenzene is reacted with Na2S2 and a carboxylic acid chloride or a chloroformic ester. The nitro group of the 4-acyl thio compound thus produced is reduced to an amino group and the resulting compound is diazotized. Compounds having a cyanothio group in the p-position are prepared similarly except that the cyanothio group is introduced by reacting the 2-N-substituted-5-substituted-oxy -1-nitrobenzene with Br2 and KCNS, the product so obtained being reduced and diazotized. Numerous examples are given of the products and their preparation in which for example R1 is methyl, ethyl, normal butyl, cyclohexyl or hydroxyethyl; R2 is butyryl, methyl, ethyl, benzyloxy, ethoxy, methoxy, butoxy, phenoxy, diethyl- and dimethylaminoethoxy and chlorethoxy; R3 is ethyl, benzyl, p-toluyl, carboxymethyl, KSO4CH2-hydroxyethyl 2,4,4 - trimethylpentyl-, allyl, phenyl, cyano, C2H5COO-, propenyl and naphthyl; and R4 is methyl, butyl, cyclopentyl, p-chlorophenyl- and benzyl. In addition examples are given in which two of the diazophenyl are nuclei and are connected at the 2 or 4 positions by an alkylene bridging group.