Patent GB-673226-A (GB)
Title: Manufacture of azo dyestuffs
IPC: C09B56/12
Filed: 1950-02-24
Abstract: The invention comprises the manufacture of azo dyestuffs by coupling a b -ketocarboxylic acid arylide, which contains in the molecule one b -ketocarboxylic acid residue and also the residue of a leuco sulphuric acid ester of the anthraquinone series and in which a hord exists between the amide nitrogen atom and an anthraquinone carbon atom in b -position, with a diazo compound free from solubilizing groups, or by coupling an arylide of the said kind, but containing two b -ketocarboxylic acid residues, with, on the one hand, a diazo compound free from solubilizing groups and, on the other hand, a diazo compound containing a sulphonic acid group; the dyestuffs so obtainable; and the use thereof in dyeing and printing (e.g. of animal or vegetable fibres or regenerated cellulose).  The amide nitrogenatom may be attached to the anthraquinone carbon atom in b -position directly or through a bridge member, e.g. it may be attached to a residue (e.g. a benzene residue) itself attached directly or through a bridge member (e.g. N = N-, -CONH-, -NHCO-, -NHCONH-, -SO2-, -SO2-N(CH3)- or -N(CH3)-SO2-); in particular it may be in a grouping of the general formula <FORM:0673226/IV (c)/1> wherein X and Y represent hydrogen, alkyl, alkoxy or halogen. Examples describe the preparation of monoazo dyestuffs from the following components: diazo components: 4 - chloro - 2 : 5 - dimethoxyaniline, o - anisidine, p-toluidine, 2-nitro-4-methylaniline, 5-methyl-2-methoxyaniline, a - and b -naphthylamine, 2-nitro-4-methoxyaniline, 4-chloro-2-nitraniline, 5-chloro-2-methoxyaniline, 5-chloro-2 : 4-dimethoxyaniline; coupling components: the disodium salts of the leuco sulphuric acid esters of 2-acetoacetylaminoanthraquinone and its 3-chloro derivative, of 2-(41-acetoacetylaminobenzoylamino) - anthraquinone, of 2-(31 - acetoacetyl - amino - 41 - methoxybenzoylamino) - anthraquinone, of anthraquinone - 3-carboxylic acid 41 - acetoacetyl - amino - 31-methoxyanilide and of 2-(N-methyl-N-31-acetoacetyl - amino - 41 - methoxybenzenesulphonylamino)-anthraquinone, and the dipotassium salt of the leuco sulphuric acid ester of 3-chloro - 2 - benzoylacetylaminoanthraquinone; the preparation of the disazo dyestuffs o-anisidine-->the disodium salt of the leuco sulphuric acid ester of 2 : 6-di-(acetoacetylamino) - anthraquinone\sM2 - methoxyaniline-5-sulphonic acid, 5-chloro-2-methoxy-1-amino benzen-->the acetoacetyl derivative obtained by the action of diketene on the dyestuff: the disodium salt of the leuco sulphuric acid ester of 3 - chloro - 2 - aminoanthraquinone-->5-methyl - 2 - methoxyaniline, and 4 - amino-2 : 5 : 21 - trimethoxy - 1 : 11 - azobenzene--> the disodium salt of the leuco sulphuric acid ester of 3 - chloro - 2 - acetoacetylaminoanthraquinone; and the printing of cotton with a paste containing the dyestuff 4-chloro-2-nitraniline-->the disodium salt of the leuco sulphuric acid ester of 3-chloro-2-acetoacetylaminoanthraquinone, thiodiethylene glycol, sodium nitrite and sodium carbonate, with subsequent steaming and development of a greenish yellow print in a dilute sulphuric acid bath.  Additional diazo components specified are o-chloraniline, o - nitraniline, 5 - methyl - 4 - chloro - 2-methoxyaniline and 2 : 6-dimethylaniline.  Leuco sulphuric acid esters of the types defined above are obtainable by treating a leuco sulphuric acid ester of an anthraquinone compound containing one or two amino groups attached directly or through a bridge member to an anthraquinone carbon atom in b -position, with an acylating agent capable of introducing the residue of a b -ketocarboxylic acid, e.g. with diketene to produce an acetoacetyl derivative, which may be converted by the action of an aromatic acid halide into an aroylacetyl derivative.  The specific coupling components enumerated above are thus prepared by the action of diketene on the disodium salts of the leuco sulphuric esters of 2-aminoanthraquinone (obtained by treating 2-acetylaminoanthraquinone with chlorosulphonic acid in pyridine in the presence of iron, and heating the product with aqueous caustic soda) and its 3-chloro derivative, 2 - (41 - amino - and 31 - amino 41 - methoxy - benzoylamino) - anthraquinone (obtained by treating the leuco sulphuric ester of 2-aminoanthraquinone with p-nitro- or 3-nitro - 4 - methoxy - benzoyl chloride and reducing the nitro group), anthraquinone-3-carboxylic acid 41 - amino - 31 - methoxyanilide (obtained by condensing anthraquinone-3-carboxylic acid chloride with 1-formylamino-2 - methoxy - 4 - aminobenzene, treating the product with chlorosulphonic acid and saponifying the formylamino group), 2-N-methyl-N-31 - amino - 41 - methoxybenzenesulphonylamino) - anthraquinone (obtained by condensing b -aminoanthraquinone with 4-methoxy-3 - acetylaminobenzene - 1 - sulphochloride, methylating, treating the product with chlorosulphonic acid and saponifying the acetylamino group), and 2 : 6-diaminoanthraquinone; and by the action of benzoyl chloride in aqueous caustic soda on the dipotassium salt of the leuco sulphuric acid ester of 2-acetoacetylamino-3-chloroanthraquinone.