Patent GB-329960-A (GB)
Title: Manufacture of azo-dyestuffs insoluble in water
IPC: C09B29/20
Filed: 1929-02-25
Abstract: 329,960. I. G. Farbenindustrie Akt.- Ges., Hoffa, E., and Thoma, E. Feb. 25, 1929. Addition to 286,274. Azo dyes.-The process of the parent Specification in which certain 4-aminodiphenylamines are diazotized and coupled with 2:3-oxynaphthoylarylamines to form insoluble azo-dyestuffs is extended to the use in general of bases of the general formula R2-NH-R1-NH2(p) where R1 = an aromatic residue which may be substituted or not and R2 = an isocylic residue which may be substituted or not. The dyestuffs may be produced in substance or on a substratum. In examples the following dyestuffs are formed: (1) 4-aminophenyl-#-naphtylamine --7 2 : 3-oxynaphthoic acid anilide, (2) 4-aminophenyl-2-carboxylic acid methylester-/3-naphthylamine # 2 : 3-oxynaphthoic acid-4<1>-chloro-1<1>-anilide, (3) 4-amino-3- chloro (or 3: 5-dichloro-) phenyl-#-naphthylamine # the 4-chloroanilide, (4) 4-amino-4<1>-phenoxydiphenylamine the o-toluidide, (5) 4<1>-methoxy-2-carboxylic acid methylester-4-aminodiphenylamine --7 the 5-chlor-2-toluidide, (6) 4- aminodiphenylamine - 2 - carboxylic-acid-met.hyl ester (or 4-aminophenyl-cyclohexylamine) # the o-anisidide. In a table the shades obtained using dyestuffs from the following components are given : 4-aminophenyl-1<1>-naphthylamine, 4-aminophenyl-1-carboxylic acid-methylester-a-naplithylamine, 4-aminophenyl-1<1>-amino-4<1>-ethoxynaphthalene, 4-amino-2<1>-chloro-4<1>-methyldiphenylamine-2-carboxylic acid-methylester, 4-aminodiphenylamine-21-carboxylic acid-ethylester, 4- amino-4'-cyanodiphenylamine, 4-amino-4'-nitrodiphenylamine, 4-amino-4<1>-hexahydrophenyldiphenylamine, 4-amino-41-acetyl (or benzyl)- aminodiphenylamine, 4-amino-2-carboxylic acidanilide-diphenylamine, 4-amino-4'-methyl-2-carboxylic acid-anilide-diphenylamine, 4-amino-2'- (p-toluenesulphonyl)-diphenylamine, 4'-ethylthio- 4-aminodiphenylamine, 4-ammo-1: l'-dinaphthylamine and 4-aminodiphenylamine : the m-nitranilide 4-chlor-2-toluidide and /3-naphthylide of 2 : 3- oxynaphthoic acid. Specification 301,410 is referred to. Diarylamines. - 4-Aminophenyl-2-carboxylic acid methylester a- or #-naphthylamine is made by condensing a- or #-naphthylamine with 5- nitro-2-chlorobenzoic acid, reducing and esterifying; 4-amino-3-chlorophenyl-#-naphthylamine is made from 2 :3-oxynaphthoic acid and 3-chlor-pphenylenediamine in presence of bisulphite; 4- amino - 3 : 5-dichlorophenyl-#-naphthylamine is similarly prepared from 3: 5-dichloro-p-phenylenediamine; 4-amino-4<1>1phenoxydiphenylamine is similarly prepared from 3:-5-dichloro-p-phenylenediamine; 4-amino-4<1>-phenoxydiphenylamine is made from 4-phenoxyaniline and 1-chlor-4- nitrobenzene-2-sulphonic acid, splitting off the sulpho group and reducing; 4<1>-methoxy-2-carboxylic acid methylester-4-aminodiphenylamine is made by condensing p-anisidine with 5-nitro-2- chloro-1-benzoic acid, reducing and esterifying; 4-aminodiphenylamine-2-carboxylic acid-methylester is prepared similarly starting from aniline; I 4-aminophenylcyclohexylamine is made by splitting off the sulpho group from 1-N-cyclohexylamino-4-nitrobenzene-2-sulphonic acid and reducing; 4-aminophenyl-1<1>-amino-4<1>-ethoxynaphthalene is made by melting p-phenylenediamine with 1-amino-4-naphthalene ethylether hydrochloride; 4 - amino - 2<1>-chlor-4<1>-methyldiphenylamine-2-carboxylic acid methylester is made from 3-chlor-4- toluidine and 5-nitro-2-chlorbenzoic acid, reducing and esterifying; 4-aminodiphenylamine-2'-carboxylic acid ethylester is made from o-chlorbenzoic acid and 4-aminoazobenzene, splitting the azo group by reduction and esterifying; 4-amino- 4<1>-cyanodiphenylamine is made from 4-amino-4<1>- nitrodiphenylamine by replacing the amino by cyano and reducing; 4-amino-4<1>-hexahydrodiphenylamine is made from 4-hexahydrophenyl-laniline and 4-nitro-1-chlorabenzene-2-sulphonate, eliminating the sulpho group and reducing; 4- amino-2-carboxylic acid anilide-diphenylamine is made by condensing 2-chlor-5-nitrobenzoic acid with aniline, treating the 4-nitrodiphenylamine- 2-carboxylic acid with aniline and phosphorus pentachloride in toluene and reducing the nitro group ; 4-amino-41-methyl-2-carboxylic acidanilide-diphenylamine is similarly made by starting with p-toluidine; 4<1>-ethylthio-4-aminodiphenylamine is made from 4-ethylthio-1-aniline and 4-nitro-1-chlorobenzene-2-sulphonic acid, eliminating the sulpho group and reducing.