Patent GB-533060-A (GB)
Title: Manufacture of hexakisazo dyestuffs, more especially suitable for dyeing leather
IPC: C09B35/64
Filed: 1939-10-04
Abstract: 533,060. Dyes. GEIGY AKT.-GES., J. R. Oct. 4, 1939, No. 27180. Convention date, Oct. 5, 1938. [Classes 2 (iii) and 15 (ii)] Hexakisazo dyes, suitable for dyeing leather, strong shades of reddish to yellowish brown, of the general formula wherein A represents the residue of resorcinol, B represents a naphthalene residue C represents a diphenylamine residue and D represents a radicle comprising two benzene nuclei connected directly or through an atom or group such as - O- ,-S-, -NH-, -CH<SP>2</SP>-, -SO  2 -, -CH 2 -CH 2 -, - CH = CH- or -HN.CO-, and in which the whole dyestuff contains at least four sulphonic acid groups, are obtained by (a) diazotizing the monazo dyestuff C-N = N-B-NH 2  (2 mols.) and coupling in alkaline solution with the disazo dyestuff (1 mol.) or (b) tetrazotizing the diamine H  2  N-D-NH 2  (1 mol.) and coupling with the disazo Examples relate to the preparation of the following dyestuffs, (1)4<SP>1</SP>-nitro-4-aminodiphenylamine - 2<SP>1</SP> - sulphonic acid # 1:6 - aminonaphthalenesulphonic acid (with or without the 1:7 - isomer) - resorcinol # benzidine - 2 - sulphonic acid or N, 3<SP>1</SP> - aminobenzoyl - 1:4 - diaminobenzene - 3 - sulphonic acid # resorcinol # 1:6 - aminonaphthalenesulphonic acid as above # 4<SP>1</SP> - nitro - 4 - aminodiphenylamine - 2<SP>1</SP> - sulphonic acid, by either of methods (a) or (b) above ; the products dye leather deep reddish brown ; (2) 4<SP>1</SP> - nitro - 4 - aminodiphenylamine - 2<SP>1</SP> - sulphonic acid # 1:6 - and 1:7 - aminonaphthalenesulphonic acids in admixture # resorcinol # 4:4<SP>1</SP> - diaminostilbene - 2:2<SP>1</SP> - disulpbonic acid or 4:4<SP>1</SP> - diaminodiphenylsulphide - 2:2<SP>1</SP> - disulphonic acid or 4:4<SP>1</SP>-diaminodibenzyl-2:21- disulphonic acid or 4:4<SP>1</SP>-diamino-3:3<SP>1</SP>-dimethyldiphenylmethane disulphonic acid or 4:4<SP>1</SP>- diaminodiphenylether - 3:3<SP>1</SP> - disulphonic acid # resorcinol # the 1:6 - and 1:7 - acid mixture as above # 4<SP>1</SP> - nitio - 4 - aminodiphenylamine - 2<SP>1</SP> - sulphonic acid, by method (a) above ; the products dye leather deep reddish brown; (3) 4-aminodiphenylamine-2-sulphonic acid # the 1:6- and 1:7-acid mixture as above - resorcinol # benzidine - 2:2<SP>1</SP> - disulphonic acid - resorcinol # the 1:6 - and 1:7 - acid mixture as above - 4 - aminodiphenylamine - 2 - sulphonic acid, by method (a) above ; the product dyes leather deep brown ; (4) 4<SP>1</SP>-nitro - 4 - aminodiphenylamine - 2<SP>1</SP> - sulphonic acid or the 2<SP>1</SP>-nitro-4<SP>1</SP>-sulpho isomer # the 1:6- and 1:7 - acid mixture as above or 1 - aminonaphthalene # resorcinol # benzidine - or tolidine - 2:2<SP>1</SP> - disulphonic acid or 4:4<SP>1</SP> - diaminodiphenylamine - 2 - sulphonic or 2:3<SP>1</SP> - disulphonic acid # resorcinol # the 1:6 - and 1:7 - acid mixture as above or 1 - aminonaphthalene # 4<SP>1</SP> - nitro - 4 - aminodiphenyl - amine - 2<SP>1</SP> - sulphonic acid or its 2<SP>1</SP> - nitro- 4' - sulpho isomer, by method (a) above the product dyes leather deep brown ; (5) 2<SP>1</SP>-nitro- 4 - aminodiphenylamine - 4<SP>1</SP> - phenylsulphone - 3<SP>11</SP> - sulphonic acid # the 1:6- and 1:7-acid mixture as above # resorcinol # benzidine - 2:2<SP>1</SP> - disulphonic acid - resorcinol - the 1:6 - and 1:7-acid mixture as above # 2<SP>1</SP> - nitro - 4 - aminodiphenylamine - 4<SP>1</SP> - phenylsulphone - 3<SP>11</SP> - sulphonic acid, by method (a) above ; the product dyes leather deep yellow-brown. An example of the process of dyeing leather is given. N, 3<SP>1</SP> - - Aminobenzoyl - 1:4 - - diaminobenzene-3 - sulphonic acid is obtained by reducing the nitro group in the product of reaction of 3-nitrobenzoyl chloride with 1:4-phenylenediamine sulphonic acid. 4:4<SP>1</SP>-Diaminodiphenyl ether-3:3<SP>1</SP>-disulphonicacid is obtained by reducing the nitro groups in the product of reaction of 1-chloro-4-nitrobenzene-3-sulphonic acid with 4-nitrophenol-3- sulphonic acid. 2<SP>1</SP>- Nitro - 4 - amiazodiphenylamine 4<SP>1</SP> - phenylsulphone-3<SP>11</SP>-sulphonic acid is obtained by saponifying the product of reaction of 4-chloro- 3-nitro-diphenylsulphone-3<SP>1</SP>-sulphonic acid with 4 -acetylaminoaniline.