Patent GB-517629-A (GB)
Title: Manufacture of soluble nitro dyestuffs and their application
IPC: C09B51/00
Filed: 1938-08-02
Abstract: 517,629. Dyes ; dyeing cellulose esters. KNIGHT, A. H., PEARMAN, F. H., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. Aug. 2, 1938, No. 22848. [Classes 2 (iii) and 15 (ii)] New water-soluble nitro dyestuffs, useful for dyeing acetate artificial silk have the general formula MOOC-Y-CO.O.A.X-C6H4-NH-C6H4- NO2 in which A stands for -C2H4, -C3H6- or -C4H8-; X stands for -O- or -NR- where R is hydrogen or alkyl (methyl to butyl); M stands for sodium, potassium, ammonium and Y (COOH) 2 stands for the following dicarboxylic acids : phthalic, halogen-substituted phthalic or an acid of the general formula CnH2n (COOH)2 where CnH2n stands for a divalent hydrocarbon radical containing not more than four carbon atoms. The compounds may have non-solubilizing acetate artificial silk dyestuff substituents, for instance chloro, methanesulphonyl, nitro (in addition to the one in the general formula) and methoxy substituents, i.e. excluding the solubilizing carboxy and sulpho substituents. The dyestuffs are made by (a) esterifying a substituted nitrodiphenylamine of the general formula HO.A.X.C6H4-NH.C6H4 NO 2 by treatment with the anhydride of a dicarboxylic acid of general formula Y (COOH) 2 and then converting to a soluble salt, the esterification being conveniently carried out in a solvent, e.g., toluene or pyridene or (b) reacting a substituted amine of the benzene series of the general formula MOOC-Y-CO.O.A.X.C6H4-NH2 with an appropriate nitrohalogenobenzene, carrying a replaceable halogen or nitro substituent and also carrying if desired, a further substituent as already indicated, and then converting into a soluble salt if necessary. In the examples (1) 2:4-dinitro-4<1>-#-hydroxyethoxydiphenylamine is dissolved in toluene and treated with succinic anhydride and the 2:4- dinitro-4<1>-#-hydroxyethoxy-diphenylamineformed is treated with sodium bicarbonate to give the sodium salt ; (2) 4-amino-1-(N-N ethyl-#-hydroxy-ethylamino)benzene acid succinic ester (obtained by coupling a diazotized unsulphonated amine of the benzene series with the sodium salt of NN-ethyl-#-hydroxyethylaniline acid succinic ester and reducing the monoazo compound formed) is treated with 1- chloro-2:4-dinitrobenzene in the presence of sodium bicarbonate ; (3) 2:4-dinitro-4<1>-NN- ethyl-#-hydroxyethylaminodiphenylamine is dissolved in toluene and is then treated with phthalic anhydride ; (4) 2:4 dinitro-4<1>-#- hydroxyethoxydiphenylamine is treated with 3-chlorophthalic anhydride and the resulting compound is converted into its sodium salt ; (5) 2:4 dinitro-3<1>-chloro-4<1>-#-hydroxyethoxydiphenylamine (obtained by condensing 1- chloro-2:4-dinitrobenzene with 2-chloro-4- aminophenyl-#-hydroxyethyl ether) is dissolved in toluene, treated with succinic anhydride and the resulting compound is converted into its sodium salt ; (6) 2:4-dinitro-4<1>-gamma-hydroxypropyloxydiphenylamine (obtained by reacting 1-chloro-2:4-dinitrobenzene with p-aminophenyl-gamma-hydroxy propyl ether) is treated with succinic anhydride and the product is converted into its sodium salt; (7) 4<1>-#-hydroxyethoxy-2- nitrodiphenylamine - 4 - methyl - sulphone (obtained by reacting 1-chloro-2-nitrobenzene- 4 - methyl - sulphone with p - aminophenyl - #-hydroxyethyl ether) is reacted with succinic anhydride and the resulting compound is converted into its sodium salt; (8) -5-chloro-2- nitro - 4<1> - # - hydroxyethoxydiphenylamine (obtained by reacting 1 - chloro - 3:4 - dinitrobenzene with p - aminophenyl - # - hydroxy ethyl ether) is dissolved in toluene and treated with succinic anhydride and the product is converted into its sodium salt; (9) 2:4-dinitro- 4<1> - (NN - ethyl ; # - hydroxy - ethylamino) - diphenylamine is heated with adipic anhydride and the resulting compound is converted into its sodium salt; (10) the sodium salt of pamino-phenyl-#-hydroxyethyl ether acid succinic ester (obtained by reacting p-nitrophenyl- #-hydroxyethyl ether and, succinic anhydride, by reducing the product to an amine and then making the sodium salt) is reacted with 1- chloro - 2:4 - dinitrobenzene; (11) 2:4 - dinitro - 4<1>-#-hydroxy ethoxy diphenylamine is treated with glutaric anhydride (12) 2:4-dinitro-4<1>-#- hydroxyethoxy-diphenylamine is reacted with 3:4-dichlorophthalic anhydride ; (13) 4-chloro- 2 - nitro - 4<1> - # - hydroxyethoxydiphenylamine (obtained by reacting 2:5 dichloro-1-nitrobenzene with p-amino-phenyl-hydroxyethyl ether is treated with succinic anhydride and (14) 2:4 dinitro - 21 - methyl - 4<1> - (NN ethyl - # - hydroxyethylamino) diphenylamine is treated with succinic anhydride. The dyestuffs obtained dye acetate artificial silk reddish-yellow to yellowish-brown shades. An example is given of the dyeing of acetate artificial silk yarn with the product of example 1.