Patent GB-589536-A (GB)
Title: Manufacture of tetrakisazo-dyestuffs capable of being metallised
IPC: C09B33/26
Filed: 1945-04-03
Abstract: Tetrakisazo dyestuffs capable of being metallized are prepared by coupling a diazo compound of an amino disazo dyestuff of the general formula A-N = N-B-N = N-C-NH2 (in which A represents a benzene residue containing a hydroxy group and a carboxyl group in ortho-position with respect to each other, and B and C represent residues of the benzene or naphthalene series) with a monoazo dyestuff obtainable by coupling an ortho-carboxydiazonium compound of the benzene series, which may contain further substituents, in an acid medium with a 2-amino-5-oxynaphthalene-7-sulphonic acid.  The dyestuffs may be converted into the complex copper compounds, or the dyeings may be metallized by treatment in the dyebath or in a fresh bath with an agent yielding a metal, e.g. copper, chromium, cobalt, manganese or nickel.  Alternatively, the dyestuffs may be metallized with one mol. of an agent yielding copper and the dyeing aftertreated with an agent yielding copper or other metal. The following examples are given: (1) diazotized 1 - amino - 4 - oxybenzene - 3 - carboxylic acid is coupled with a mixture of 1-aminonaphthalene-6 and 7-sulphonic acids, then diazotized and coupled with 1-amino-2-methoxy-5-methylbenzene, after which the amino disazo dyestuff obtained is diazotized and coupled with the monoazo dyestuff obtainable by coupling diazotized 5-chloro-2-aminobenzoic acid in acid medium with 2-amino-5-oxynaphthalene-7-sulphonic acid, or with the monoazo dyestuff obtainable by coupling 2 - amino - 5 - oxynaphthalene - 7 - sulphonic acid with diazotized 2-aminobenzoic acid, 5-nitro-2-amino-benzoic acid, 3-chloro-2-aminobenzoic acid, 3,6-dichloro-2-aminobenzoic acid, 5-acetyl-amino-2-aminobenzoic acid or 5-cyano-2-aminobenzoic acid.  (2) Diazotized 4-amino-41-oxyazobenzene-31-carboxylic acid is coupled with 1 - amino - 2 - methoxy - 5 - methylbenzene, p  diazotized and coupled with the monoazo dyestuff, 5-nitro-2-aminobenzoic acid --> 2-amino-5-oxynaphthalene-7-sulphonic acid, or one of the other monoazo dyestuffs referred to in example (1).  Instead of 4-amino-41-oxyazobenzene-31-carboxylic acid, 3-amino-41-oxyazobenzene-31-carboxylic acid, 4-amino-41-oxyazobenzene-3-sulpho-31-carboxylic acid or 4-amino-41-oxyazobenzene-51-sulpho-31 -carboxylic acid may be used. (3) Diazotized 1-amino-4-oxybenzene-3-carboxylic acid is coupled with 1-aminonaphthalene-7-sulphonic acid, diazotized and coupled with 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid or with 1-aminonaphthalene-6- or 7-sulphonic acid.  The product is diazotized and coupled with the monoazo dyestuff anthranilic acid --> 2-amino - 5 - oxynaphthalene - 7 - sulphonic acid.  (4) The monoazo dyestuff 1 - amino - 4 - oxybenzene-3-carboxylic acid --> 1-aminonaphthalene-7-sulphonic acid is diazotized and coupled with 1-amino-2,5-dimethoxybenzene, and the amino disazo dyestuff so obtained is diazotized and coupled with the monoazo dyestuff 5-nitro-2-aminobenzoic acid --> 2-amino - 5 - oxy - naphthalene - 7 - sulphonic acid.  (5) Diazotized 4-amino-41-oxyazobenzene-31-carboxylic acid is coupled with 1 - amino - 2 - methoxynaphthalene - 6 - sulphonic acid and the product is diazotized and coupled with the monoazo dyestuff 5-nitro-2-aminobenzoic acid --> 2-amino-5-oxynaphthalene-7-sulphonic acid.  The dyestuff is converted into the copper complex by adding aqueous copper sulphate.  Instead of 4 - amino - 41 - oxyazo - benzene-31-carboxylic acid, the monoazo dyestuff 1-amino-4-oxybenzene-3-carboxylic acid --> 1 - amino - 2 - methoxy - 5 - methylbenzene may be used.  (6) The dyestuff 1-amino-2-oxy-5-sulpho-3-benzoic acid --> 1-amino-naphthalene is diazotized and coupled with 1-amino-2,5-dimethoxybenzene and the amino disazo dyestuff so formed is diazotized and coupled with the monoazo dyestuff 1-aminobenzene-2,4-dicarboxylic acid --> 2-amino-5-oxynaphthalene-7-sulphonic acid, or with the dyestuff 1 - aminobenzene - 2,5 - dicarboxylic acid --> 2 - amino - 5 - oxynaphthalene - 7 - sulphonic acid, or one of the other monoazo dyestuffs mentioned in example (1).  The dyestuffs dye cellulose fibres such as cotton or regenerated cellulose fibres grey-blue to green tints.  Specification 495,552 is referred to.