GB349714A - Process for the manufacture of vat dyestuffs of the anthraquinone series - Google Patents

Abstract

a -(b -Anthraquinonoylamino)-anthrimidocarbazoles are prepared by introducing by the customary methods at least one anthraquinone-b -carboxylic acid residue into the amino groups of a -amino-anthrimidocarbazoles. Or at least one anthraquinone-b -carboxylic acid residue is introduced by the customary methods into an amino-1.11-anthrimide and the product converted into the carbazole by the customary methods. Or a halogen-a -aminoanthraquinone is reacted with an anthraquinone-b -carboxylic acid halide, the product treated with an aminoanthraquinone in a high-boiling solvent in the presence of copper and sodium acetate, and carbazole ring-formation effected by the customary methods; the anthraquinone-b -carboxy residue may contain a hydroxy substituent which may be subsequently etherified, and the aminoanthraquinone may be further substituted by an aroylamino group. Or an a -aroylaminohalogenanthraquinone is condensed with an a .a 1-diaminoanthraquinone, one amino group of which is substituted by an anthraquinone-b -carboxylic acid residue, and carbazole ring-formation effected by the customary methods. Or an a .a 1-aroylamino-aminoanthraquinone is reacted on a (b -anthraquinonoylamino)-halogenanthraquinone, and carbazole ring-formation effected by the customary methods. These products dye orange to olive-green shades which are lighter than the corresponding a -benzoylamino derivatives (see Specification 29352/10, [Class 2 (iii), Dyes &c.],), and in some cases more fast to water. Those products containing two anthraquinone-b -carboxylic acids residues or one such residue and one benzoic acid residue are particularly valuable. In examples: (1) 4.41-diamino-1.11-anthrimide is acylated with anthraquinone-b -carboxylic acid chloride and the product treated with strong sulphuric acid and oxidized with chromic acid: (2) 5.5-diamino-1.11-anthrimidocarbazole (prepared by saponification of the corresponding dibenzoylamino derivative) is acylated with anthraquinone-b -carboxylic acid chloride; the 5.51-diamino-1.21-anthrimidocarbazole (prepared by condensing 1-benzoylamino-6-chloranthraquinone with 1-benzoylamino-5-aminoanthraquinone, causing carbazole ring-closure in the customary manner, and saponifying the dibenzoylamino derivative with 96 per cent sulphuric acid at about 100 DEG C.) may also be treated in this way: (3) 1-benzoylamino-4-aminoanthraquinone is reacted with 11-hydroxy-21-carboxylic acid-(5-chloranthraquinone-1-)-amide and the product treated with sulphuric acid and oxidized with sodium nitrite; the properties are improved by etherification: (4) 1-chloro-5-(b -anthraquinonoyl) - aminoanthraquinone (obtained by reacting upon 1-amino-5-chloranthraquinone with anthraquinone-b -carboxylic acid chloride) is condensed with 1-benzoylamino-4-aminoanthraquinone and the product treated with sulphuric acid and oxidized with sodium nitrite to yield 5-(b -anthraquinonoylamino) -41-benzoylamino-1.11-anthrimidocarbazole which dyes brown shades: (5) 1-amino-4-(b -anthraquinonoylamino)-anthraquinone (obtained by reacting upon 1-amino-4-nitroanthraquinone with anthraquinone-b -carboxylic acid chloride and reduction of the nitro group) is condensed with 1-benzoylamino-4-chloranthraquinone and the product treated with sulphuric acid and oxidized with chromic acid to yield 4-(b -anthraquinonoylamino) -41-benzoylamino-1.11-anthrimidocarbazole which dyes olive shades. The Specification as open to inspection under Sect. 91 (3) (a) claims the introduction of anthraquinone-b -carboxylic acid residues into a -amino-anthrimidocarbazoles by the known methods, and states that all the known methods used for preparing other acylaminoanthrimidocarbazoles are applicable; this subject-matter does not appear in the Specification as accepted.