Patent GB-790921-A (GB)
Title: New nitro-dyestuffs and process for making them
IPC: C09B51/00
Filed: 1954-11-23
Abstract: 1 - Halogen - 2 - nitrobenzene - 4 - sulphonic acid esters are obtained by reacting 1-halogen-2-nitrobenzene-4-sulphonic acid chlorides with hydroxybenzenes or hydroxy naphthalenes which are condensed with suitable arylamines to form nitro dyes (see Group IV (c)).  Specific esters referred to include the phenyl-, 4-chlorophenyl-, 2-methyl phenyl, 4-b  : b -dimethylpropyl phenyl-, a -naphthyl-, b -naphthyl-, 4-methoxyphenyl -, 2 - phenylphenyl -, 3 - N : N-dimethylaminophenyl -, 21 : 41 - dichlorophenyl -, 4 - ethoxyphenyl -, esters of 1 - chloro-2 - nitrobenzene - 4 - sulphonic acid, 1 : 6 - dichloro - 2 - nitrobenzene - 4 - sulphonic acid phenyl ester, 1 - chloro - 2 : 6 - dinitrobenzene-4-sulphonic acid phenyl ester, the 21 : 4-dichlorophenyl -, ethoxyphenyl -, 2 - or 4 - carboxamido - phenyl -, 2 - or 4 - carbamylphenyl esters of 1 - chloro - 2 - nitrobenzene-4 - sulphonic acid.  The 1 - halogen - 2 - nitrobenzene - 4 - sulphonic acid halides are prepared by treating appropriate halogen-nitrobenzene sulphonic acids with phosphorus pentabromide or phosphorus pentachoride or by reacting a 1-halogen-2-nitrobenzene with chlorsulphonic acid.ALSO:The invention comprises nitro-dyestuffs which are phenylarylamines free from groups known to impart to azo- and nitro-dyestuffs solubility in water and which contain in the same benzene nucleus a nitro group in ortho-position as the nitrogen bridge and in para-position to the nitrogen bridge a sulphonic acid aryl ester group which is linked by the sulphur atom to the benzene nucleus to which the nitro group is attached, and in which the phenyl and the aryl group may contain substituents in addition to the essential substituents.  In a process for making the above dyestuffs, a benzene compound which contains in ortho-position to a nitro group a substituent exchangeable by known methods for an amino group, advantageously a halogen atom, and in para-position to the said substituent a substituent convertible by known methods into a sulphonic acid ester group, is treated on the one hand to convert by known methods into a sulphonic acid aryl ester group the substituent so convertible and on the other to exchange by known methods for an arylamino group the substituent exchangeable for an amino group, and the starting materials are chosen that the resulting nitro-dyestuff is free from groups known to impart to azo- and nitro-dyestuffs solubility in water, but may contain substituents in addition to the essential substituents.  Groups mentioned as imparting to azo- and nitro-dyestuffs solubility in water are sulphonic acid, carboxylic acid, sulphone and sulphonamide groups. The substituent exchangeable for an amino group may be e.g. a low molecular weight alkoxy group, e.g. having at most two carbon atoms or a halogen atom e.g. a bromine or chlorine atom.  Sulphonic acid halide groups are mentioned as groups convertible into a sulphonic acid ester group.  Suitable starting materials include 1-halogen-2-nitrobenzene-4-sulphonic acid halides prepared, for example, by reacting 1-halogen-2-nitrobenzene with chlorosulphonic acid.  The introduction of the arylamino group and of the sulphonic acid aryl ester group may take place in either order.  In examples: a yellow dyestuff is obtained by reacting phenol and 1-chloro-2-nitrobenzene-4-sulphonic acid chloride to obtain 1 - chloro - 2 - nitrobenzene - 4 - sulphonic acid phenyl ester which is reacted with aminobenzene; other products are similarly obtained by reacting appropriate phenols with 1-chloro-2-nitrobenzene-4-sulphonic acid to obtain sulphonic acid esters which are reacted with amines. 1-Chloro-2-nitrobenzene-4-sulphonic acid phenyl ester is reacted with N-monomethylaniline, 2-, 3- and 4-methyl anilines, 3- and 4-methoxy anilines, 2-, 3- and 4-chloranilines, 1:3- and 1:4-diaminobenzenes, 3- and 4-acetylaminoanilines, 1 - amino - 4 - dimethylamino - benzene, 1- and 2-amino-naphthalenes, 2:5-dimethyl-, 2 - methoxy - 5 - methyl-, and 2:5-dimethoxy anilines; 1 - chloro - 2 - nitrobenzene-4 - sulphonic acid - (41 - chlorophenylester) and the corresponding 21-methyl-, 41-b :b -dimethyl propyl-phenyl esters and the a - and b -naphthyl esters are reacted with aniline, 4-methyl-, 4-methoxy- and 4-chloro-anilines; 1-chloro-2-nitrobenzene - 4 - sulphonic acid phenyl ester is reacted with 1-amino-4-ethoxy benzene and 2 - methyl - 5 - amino - benzimidazole, 1 - chloro-2 - nitrobenzene - 4 - sulphonic acid - (41-chlorophenyl ester) is reacted with 2-methyl-5-aminobenzimidazole; 1 - chloro - 2 - nitrobenzene - 4 - sulphonic acid - 41 - ethoxy phenyl ester is reacted with 1-amino-, 1-amino-4-chloro- and 1 - amino - 4 - methoxy benzenes and 2-methyl-5 - aminobenzimidazole; 1 - chloro - 2 - nitro - benzene-4-sulphonic acid phenyl ester - 21 - carboxylic acid amide is reacted with aniline, 4-methoxy- and 2-chloroanilines; 1-chloro-2-nitrobenzene-4-sulphonic acid phenyl ester 41-carboxylic acid amide is reacted with aniline, 4-methoxy and 4-chloroanilines; 1-chloro-2-nitrobenzene-4-sulphonic acid phenyl ester-41-carboxylic acid ethyl ester is reacted with aniline, 4-methoxy and 4-chloroanilines; 1-chloro - 2 - nitrobenzene - 4 - sulphonic acid-(2:41-dichlorophenyl ester) is reacted with aniline, 4 - methyl-, 4 - chloro-, 4 - acetylamino- and 4-methoxy anilines and 2-methyl-5-aminobenzimidazole (1); 1-chloro-2-nitrobenzene-4-sulphonic acid chloride and phenol are reacted and the product is reacted with aniline in a similar process (2); 1-chloro-2-nitrobenzene sulphonic acid and aniline are reacted to form 2-nitro - diphenylamine - 4 - sulphonic acid which is converted to the acid chloride by reaction with phosphorus oxy- and pentachlorides and the acid chloride is reacted with phenol. Additional 1 - halogen - 2 - nitrobenzene - 4 - sulphonic aryl esters mentioned include the 41-methoxyphenyl-, 21 - phenyl phenyl-, 31-N:N-dimethylaminophenyl-, 21:41 - dichlorophenyl-, 4-ethoxy - phenyl-, phenyl ester - 21- or -41-carboxylic acid amide and phenyl ester -21- or -41-carboxylic acid ethyl ester of 1-chloro-2-nitrobenzene - 4 - sulphonic acid, 1:6 - dichloro-2-nitrobenzene- and 1-chloro-2:6-dinitrobenzene sulphonic acid phenyl esters. Additional amines mentioned include 1-amino-2:4- and 1 - amino - 2:6 - dimethyl benzene, N - mono - methylaminobenzene, 1-amino-4- or -2-phenylaminobenzene and 1-amino-4- or -2-phenoxybenzene.  The dyes are used for dyeing polyvinyl chloride, cellulose esters such as acetyl-cellulose and polyesters of aromatic dicarboxylic acids, especially of terephthalic acid. Dispersing agents mentioned include sulphide cellulose waste liquor, an octa-decyl-ethylene oxide condensate, soap and sodium m -heptadecyl-N-benzyl-benzimidazole disulphonate.