Patent GB-601369-A (GB)
Title: Process for the production of metallizable azo dyestuffs and complex metal compounds thereof
IPC: C09B45/14
Filed: 1946-01-21
Abstract: Aminobenzoylsalicylic acids of the general formula A-CO-B-NH2 (wherein A represents an o-hydroxycarboxyarl residue and B an aryl residue and wherein A or B or both may be further substituted, e.g. by halogen or an alkyl, carboxyl, nitro, sulphonic acid, hydroxy, alkoxy or aryloxy group) are obtainable by condensing an aromatic carboxylic acid halide which contains a nitrogen-containing group other than but convertible to an amino group (e.g. an acylamino or nitro group), with a methyl ester of an aromatic o-hydroxycarboxylic acid in the presence of a Friedel-Crafts condensing agent, saponifying the ester, and previously, subsequently or (in the case of an acylamino group) simultaneously converting to an amino group the group so convertible, any desired substituents not present in the starting materials being introduced at an intermediate stage. Examples describe the preparation of: (1) 1-(31- or 41-aminobenzoyl)-4-hydroxybenzene-5-carboxylic acid by alkaline saponification and reduction from 1-(31-nitrobenzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid methyl ester and from the condensation product of 4-nitrobenzoyl chloride with methyl salicylate; (2) 1 - (31 p  - aminobenzoyl) - 3 or -2-methyl - 4 - hydroxylbenzene - 5 - carboxylic acid, 1 - (31 - aminobenzoyl) - 5 - methyl - 2 - hydroxybenzene - 3 - carboxylic acid and 1-(31-amino-41-methylbenzoyl) -4-hydroxy-benzene-5-carboxylic acid similarly from 3-nitrobenzoyl chloride and o-, m- and p-cresotinic acid methyl esters and from 3-nitro-4-methylbenzoyl chloride and methyl salicylate; (3) 1-(31-aminobenzoyl)-3-sulpho-4-hydroxybenzene - 5 - carboxylic acid by sulphonation of 1-(31-nitrobenzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid with oleum, and reduction of the nitro group; (4) 1-(31-aminobenzoyl)-4-hydroxynaphthalene - 3 - carboxylic acid from 1-hydroxy-2-naphthoic acid methyl ester as in (2); (8) 1-(31-amino-41-sulphobenzoyl) -4-hydroxybenzene-5-carboxylic acid by condensation of 4-chloro-3-nitrobenzoyl chloride and methyl salicylate, followed by saponification in an alkaline soda medium, replacement of the chlorine atom by a sulphonic acid group by boiling with sodium sulphite solution and reduction of the nitro group with iron; (9) 1-(41-hydroxy - 31 - aminobenzoyl) - 4 - hydroxybenzene-5-carboxylic acid from the same condensation product by saponification, replacement of the chlorine atom by a hydroxy group by refluxing in a solution alkaline to mimosa indicator and reduction of the nitro group with sodium sulphide; (11)1-(41-methoxy-31-aminobenzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid similarly, using methyl alcoholic potassium hydroxide to replace the chlorine atom by a methoxy group and iron for the reduction step; (13) 1-(41-chloro-31-aminobenzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid by condensation of 4-chloro-3-nitrobenzoyl chloride with methyl salicylate, followed by saponification in an alkaline soda medium and reduction of the nitro group with iron and hydrochloric acid.  Specification 519,454 is referred to.ALSO:Metallizable azo dyestuffs and complex metal compounds thereof are manufactured by diazotizing a compound of the general formula A-CO-B-NH2 (wherein A represents an o-hydroxycarboxyaryl residue and B an aryl residue and wherein A or B or both may be further substituted, e.g. by halogen or an alkyl, carboxyl, nitro, sulphonic acid, hydroxy, alkoxy or aryloxy group) and coupling with any coupling component, especially a 5-pyrazolone, and, if desired, treating the products with metallizing agents.  The components may be so chosen that the products have sufficient solubility in water for the purpose desired, which may be dyeing by the single bath chroming process, dyeing wool by the after-chroming process, dyeing cellulose with after-treatment of the dyeings with copper salts, or chromium printing.  If the diazo component contains a lake-forming group (e.g. a hydroxy, alkoxy or carboxyl group) in o-position to the amino group, there is preferably chosen a coupling component which also contains a lake-forming group in o-position to the coupling position, in which case the product may be treated in substance with a metallizing agent in an amount insufficient to combine with all the metallizable groups in the dyestuff.  Examples describe the preparation of the following dyestuffs: (1) 1-(31- or 41-aminobenzoyl)-4-hydroxybenzene-5-carboxylic acid --> 1-(21-chloro-51-sulpho- or 21 : 51-dichloro-41-sulphophenyl) - 3 - methyl - 5 - pyrazolone, which dye wool from acid baths in greenish yellow shades which may be after-chromed; (2) 1-(31-aminobenzoyl)-3- or -2-methyl-4-hydroxybenzene-5-carboxylic acid, 1-(31-aminobenzoyl)-5-methyl-2-hydroxybenzene-3-carboxylic acid or 1-(31-amino-41-methylbenzoyl) -4-hydroxybenzene-5-carboxylic acid --> the coupling components of (1), which dye wool similarly in yellow shades; (3) 1-(31-aminobenzoyl)-3-sulpho-4-hydroxybenzene-5-carboxylic acid --> 1-(21-chlorophenyl) - 3 - methyl - 5 - pyrazolone, which has similar properties to the products of (1); (4) 1-(31-aminobenzoyl)-4-hydroxynaphthalene-3-carboxylic acid --> 1-(21-chloro-51-sulphophenyl) - 3 - methyl - 5 - pyrazolone, which has similar properties to the products of (2); (5) 1 - (31-aminobenzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid --> 2-acetylamino-8-naphthol-6-sulphonic acid, which dyes wool from acid baths in yellowish-red shades which may be after-chromed; (6) 1-(31- or 41-aminobenzoyl)-4 - hydroxybenzene - 5 - carboxylic acid --> 2 : 3 : 6-, 1 : 3 : 6- or 2 : 6 : 8-hydroxynaphthalenedisulphonic acid, which yield orange shades by chromium printing on cotton; (7) the same diazo components --> 1-acetylamino-8 - naphthol - 3 : 6 - disulphonic acid, which similarly yield bluish-red prints; (8) 1-(31-amino-41-sulphobenzoyl) -4-hydroxybenzene-5-carboxylic acid --> (alkaline) 2 : 8 : 6-amino-naphtholsulphonic acid, which has similar properties to the product of (5); (9) 1-(41-hydroxy31-aminobenzoyl) -4-hydroxybenzene-5-carboxylic acid --> 1-acetylamino-7-hydroxynaphthalene, which is refluxed with a solution of chromsalicylate of ammonia to form its chromium compound, which dyes wool from acid baths in grey shades which may be further treated with compounds of hexavalent chromium; (10) the same diazo component (2 mols.) \sQ J-acid urea or 5 : 51-dihydroxy-2 : 21-dinaphthylamine-7 : 71-disulphonic acid, which dye cellulose from a bath containing Glauber's salt in reddish- and blueish-violet shades which become ruby red and violet respectively on after-treatment with cupric salts, and of which the copper compounds prepared in substance dye cellulose in ruby red and violet shades which may be further treated with salts of heavy metals, e.g. of tervalent chromium; (11) 1-(41-methoxy- or -hydroxy - 31 - aminobenzoyl) - 4 - hydroxybenzene-5-carboxylic acid --> J-acid urea -->- anthranilic acid, which similarly dye cellulose in yellowish-red shades becoming bluish-red on after-coppering, and which may be heated with copper sulphate solution to yield copper compounds which similarly dye cellulose in bluish-red shades; (12) 1-(41-hydroxyl-31-aminobenzoyl) -4-hydroxybenzene-5-carboxylic acid --> 2-benzoylamino-, 2-phenylamino- or 2 - (41 - hydroxy - 31 - carboxyphenylamino) - 5 - naphthol-7-sulphonic acid, the copper compounds of which dye regenerated cellulose fibres from a bath containing Glauber's salt in blueish-red, ruby red and reddish-violet shades; (13) 1-(31-aminobenzoyl)-4-hydroxybenzene-5-carboxylic acid or its 41-chloro-derivative --> 1 - (31 - sulphonamidophenyl) - 3 - methyl - 5 - pyrazolone, which dye wool by the single bath chroming process in greenish- and reddish-yellow shades; the diazo components in any of the foregoing examples may be replaced by 1-(21-amino-51-nitrobenzoyl)-, 1-(31-amino-61-acylamino-, -chloro-, -alkoxy-, -aryloxy- or -aralkyloxy - benzoyl)- or 1 - (31 - amino - 41 - aryloxy-, -aralkyloxy-, -carboxymethoxy- or -carboxy - benzoyl) - 4 - hydroxybenzene - 5 - carboxylic acid; (14) 1 - (31 - aminobenzoyl) - 3 - sulpho-4-hydroxybenzene-5-carboxylic acid or 1 - (31 - amino - 41 - sulphobenzoyl) - 4 - hydroxybenzene-5-carboxylic acid --> 3-methyl-5-pyrazolone, which dye wool from an acid bath in greenish-yellow shades which may be after-chromed; (15) 1-(31-aminobenzoyl)-3-sulpho-4-hydroxybenzene-5-carboxylic acid or 1-(31-amino-41-sulphobenzoyl) -4-hydroxybenzene-5-carboxylic acid --> 1-phenyl-3-carbethoxy-5-pyrazolone or 1-(31-chlorophenyl)-5-pyrazolone-3-carboxylic acid or its esters or amides, and 1 - (31 - amino - 41 - sulphobenzoyl) - 4 - hydroxybenzene-5-carboxylic acid --> 1-phenyl-5-pyrazolone-3-carboxylic acid or its amide, which dye wool similarly in yellow to greenish-yellow shades.  Specification 591,454 is referred to.