Patent GB-544817-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B29/00
Filed: 1940-10-25
Abstract: 544,817. Dyes. SOC. OF CHEMICAL. INDUSTRY IN BASLE. Oct. 25, 1940, Nos. 15684 and 15685. Convention dates, Oct. 26, 1939 and Sept. 10, 1940. [Classes 2 (iii) and 15 (ii)] Monoa o dyes of the general formula wherein R-OH represents a " yellow component # which is a phenol or an enolisable ketone capable of coupling, x represents a bivalent grouping containing at least 2 carbon atoms, y represents a group consisting of, or containing, a hydroxyl (esterified or not to an ester residue capable of salt formation), a carboxylic, sulphonic or thiosulphuric acid group, and the benzene mucleus may be further substituted, are obtained (a) by diazotization and coupling as indicated by the arrow, (b) by the successive action on a. compound of the general formula of an agent which reduces the nitro group, nitrous acid, the coupling component R-OH and, if desired, an esterifying polybasic acid, (c) by the successive action on a compound of the general formula of an agent which reduces the nitro group, nitrous acid, the coupling components R-OH and a salt of sulphurous or thiosulphuric acid. Specified esterifying polybasic acids are sulphuric, phosphoric, oxalic, malonic, succinic, maleic, glutaric, adipic, pimelic, phthalic and sulphophthalic acids. The products give fast yellow dyeings on cellulose ester or ether materials. Specified' diazo components are aniline-4-carboxylic acid-#-hydroxyethyl or #- hydroxybutyl ester, 4-chloroaniline-5-carboxylic acid-#-hydroxyethyl ester, 3-chloroaniline-4- carboxylic acid-#-hydroxyethyl ester, and 2- nitroaniline-4-carboxylic acid-#-hydroxyethyl ester and specified coupling components are phenol, p-cresol, 3:4-dimethylphenol, resorcinol and its monoalkyl ethers, dihydroxyquinolines, esters and . amides of acetoacetic acid, and pyrazolones and their carboxylic and sulphonic acids, e.g. 3-methyl-5-pyrazolone, 1-phenyl-3- methyl-5-pyrazolone and its 21-methyl, 2<SP>1</SP>- chloro and dichloro derivatives. Examples relate to the production of the dyestuffs, (1) aniline-4-carboxylic acid-#-hydroxyethyl ester # 1-(2<SP>1</SP>-chloro) phenyl-3-methyl-5-pyrazolone; (2) the product of (1) esterified with maleic anhydride and'the products of esterification with maleic or succinic acid or phthalic anhydride of the dyestuffs, aniline-4-carboxylic acid - #- hydroxyethyl ester or 3 - cbloroaniline - 4 - carboxylic acid - # - hydroxyethyl ester # 1 - phenyl - 3 - methyl - 5 - pyrazolone or its 2<SP>1</SP>-methyl derivative, 2:4-dihydroxyquinoline, p-cresol or 3:4-dimethylphenol, or 2-nitroaniline - 4 - carboxylic acid - # - hydroxyethyl ester # 3-methyl-5-pyrazolone ; alternatively, the esterification may be applied to the diazo component before coupling ; (3) the product of (1) esterified with conc. - sulphuric acid ; (4) aniline-4-carboxylic acid ethyl ester- #-sulphonic acid # 1-(21-chloro) phenyl-3- methyl - 5 - pyrazolone ; (5) aniline - 4 - carboxylic acid ethyl ester-#-thiosulphuric acid - 1 - (21 - chloro) phenyl - 3 - methyl - 5 - pyrazolone. An example is also given of the dyeing process for cellulose acetate artificial silk, using the dyestuff cf (1). Specification 516,929 is referred to. Hydroxyalkyl esters of anilinecarboxylic acids are obtained by reducing the nitro groups in the products of re-action of a salt of a nitrobenzenecarboxylic acid with an alkylene halohydrin such as ethylenechlorhydrin or epichlorhydrin.  Aniline-4-carboxylic acid ethyl ester-#-sulphonic acid is obtained, as sodium salt, by the action of sodium sulphite on the product obtained by reducing the nitro group in the re-action product from nitrobenzene-4-carboxylic acid chloride and ethylenechlorhydrin. Aniline - 4 - - carboxylic acid ethyl ester-#- - thiosulphuric acid is obtained by the action of sodium thiosulphate on aniline-4-carboxylic acid-#-chlorethyl ester. The Specification as open to inspection under Sect. 91 comprises also the use, as diazo components, of the corresponding anilinecarboxylic acid amides, N-substituted by the group-x-y, specified components being aniline-4-carboxylic acid - # hydroxyethyl - and #- hydroxybutyl - amides, aniline-3-carboxylic acid-#-hydroxyethylamide, 2-nitroaniline-4- or 5-carboxylic acid-#-hydroxyethylamide and 4-chloro aniline- 5-carboxylic acid-#-hydroxyethylamide. Additional examples relate to the production of the dyestuffs, (1) aniline-3- or 4-carboxylic acid-#-hydroxyethylamide# 1-phenyl-3-methyl. - 5-parazolone, and 2-nitroaniline-4- or 5-carboxylic acid-#-hydroxyethylamide of 4-chloroaniline-5-carboxylic acid-#-hydroxyethylamide - 3 - methyl - 5 - pyrazolone ; (2) the product of (1) esterified with the anhydride, of maleic, succinic, phthalic or sulphophthalic acid ; (3) the product of (1) esterified with cone. sulphuric or chlorosulphonic acid. An example is also given of the dyeing process for cellulose acetate artificial silk, using the dyestuff of (3). N-hydroxyalkylamides of aniline-carboxylic acids are obtained by reducing the nitro groups in the products of reaction of a nitrobenzenecarboxylic acid halide with a hydroxyalkylamine, e.g. mono- or di-ethanolamine or an N- hydroxyalkylaniline. Carboxyalkyl esters and N-carboxyalkyl amides of anilinecarboxylic acids are obtainable from the corresponding halogenalkyl esters or amides of nitrobenzenecarboxylic acids by reducing the nitro group and, at any suitable stage, replacing the halogen by the cyano group and hydrolysing the latter to the carboxylic group.  This subject-matter does not appear in the Specification as accepted.