Patent GB-315664-A (GB)
Title: Manufacture of azo-dyestuffs containing copper
IPC: C09B45/28
Filed: 1929-07-15
Abstract: 315,664. Soc. of Chemical Industry in Basle. July 14, 1928, [Convention date]. Azo dyes, soluble metal compounds of.-Azo dyestuffs containing copper are produced by treating with agents yielding copper the primary disazo dyes obtainable by coupling in an alkaline medium a diazotized anthranilic acid or an alkyl ester thereof (2 mols.) or a diazotized anthranilic acid or an alkyl ester thereof (1 mol.) and a diazotized o-aminophenol (1 mol.) with a compound of the formula (1 mol.) in which X is a divalent residue such as CO or CS or a triazine, quinazoline, pyridazine, or pyrimidine or like heterocyclic residue. The dyestuff may be treated with the agent yielding copper during its formation by coupling, in substance, in the dyebath, or on the fibre. The same parent dyestuffs are also obtainable by uniting 1 mol. of a monoazo dyestuff, an anthranilic acid or an alkyl ester thereof # (alkaline) 2 : 5 : 7-aminonaphtholsulphonic acid, with 1 mol. of one of the same dyestuffs, or with 1 mol. of a monoazo dyestuff obtained by coupling (alkaline) a diazotized o-aminophenol or o-aminonaphthol with 2 : 5 : 7-aminonaphtholsulphonic acid, by means of phosgene, carbon disulphide or other suitable compound corresponding with the residue X as defined above. The introduction of the copper may be effected simultaneously with the coupling or before or after the uniting of the 2 mols. of monoazo dyestuffs. The products dye cotton, viscose silk, cuprammonium silk, and like fibres orange to brown and bordeaux tints fast to light. The following examples are specified. (1) The dyestuff anthranilic acid (2 mols.) # (alkaline) the urea of 2 : 5 : 7-acid gives on cotton brown-orange dyeings which change toward yellow-bordeaux on after-treatment with copper salts; it is convertible without isolation into the copper compound by acidifying the solution from the coupling operation and heating for 2 hrs. at 80-90‹ C. with a solution of copper sulphate; this copper compound gives on cotton red-brown dyeings very fast to light. (2) The dyestuff anthranilic acid methyl ester (2 mols.) # (alkaline) the urea of 2 : 5 : 7-acid is heated at 70‹ C. with an ammoniacal solution of copper sulphate; the product gives on cotton red-brown dyeings very fast to light; a similar product is obtainable by treating the dyestuff anthranilic acid methyl ester # (alkaline) 2 : 5 : 7-acid with a copper salt and with phosgene in either order. (3) The dyestuff anthranilic acid (1 mol.) # (alkaline) the urea of 2 : 5: 7-acid (alkaline) #2-aminophenol-4-sulphonic acid (1 mol.) is heated for 2 hrs. at 80-85‹ C. with a solution of copper sulphate; the product gives on cotton bordeaux red dyeings very fast to light. (4) The dyestuff anthranilic acid (2 mols.) # the condensation product from cyanuric chloride (1 mol.), 2 : 5 : 7-acid (2 mols.) and aniline (1 mol.) is treated with an ammoniacal copper sulphate solution; the product gives on cotton red-brown dyeings fast to light. A table is also given showing various combinations of components which mav be used in making the parent dyestuffs, additional diazo components specified being 5-chloraniline-2-carboxylic acid, 5-nitraniline-2-carboxylic acid, 5-methoxyaniline-2-carboxylic acid, z-aminophenol-4-sulphamide, 4- nitro-2-aminophenol, 4 : 6-dinitro-2-aminophenol, 4 - methyl - 6 - nitro-2-aminophenol, 6-carboxy-2- aminophenol - 4 - sulphonic acid, 1 : 2 - aminonaphthol-4-sulphonic acid and its nitrated diazo compound, 4-chlor-2-aminophenol, and 2-carboxyaniline-4-sulphonic acid. Specifications 116,530, 209,723, 298,494, 299,331, and 306,859 are referred to. The Specification as open to inspection under Sect. 91 (3) (a) comprises also the similar production of complex metal compounds in general of the parent dyestuffs, and refers to aftertreatments of the dyeings with the parent dyestuff of example (1) with chromium or manganese salts to change the shade toward red, and with iron, nickel, or cobalt salts to change the shade toward brown. The use of agents yielding molybdenum and the use as diazo components of aniline-2-sulphonic acid and 2-methoxyaniline-5- sulphonic acid are also referred to. This subjectmatter does not appear in the Specification as accepted.