Patent GB-469449-A (GB)
Title: New anthraquinone dyestuffs
IPC: C09B1/52
Filed: 1936-01-22
Abstract: 1-Hydroxy-, amino- and methylamino-4-carboalkoxy- and carboalkenoxyanilinoanthraquinonesulphonic acids in which the alkyl or alkenyl radicle has 8--18 carbon atoms and in which there may be up to 2 additional halogen or methyl substituents are manufactured by suitably esterifying the corresponding free carboxylic acids, e.g. by heating with the alcohol and an esterification catalyst consisting of concentrated sulphuric acid or chlorosulphonic acid, or by sulphonating the corresponding unsulphonated carboxylic esters by treating them with a sulphonating acid or, when there is a bromo or chloro substituent in m-position to the phenylamino group, by treating with a soluble sulphite, or by both methods of sulphonation. The free carboxylic acids used as starting materials are obtained by reacting a 1-bromo- or chloro-4-hydroxy-, amino- or methylaminoanthraquinone with an o-, m-, or p-aminophenylcarboxylic acid and then sulphonating, or by reacting a 1 : 3-dibromo- or dichloro-4-hydroxy-, amino- or methylaminoanthraquinone with an o-, m-, or p-aminophenylcarboxylic acid and then sulphonating with a sulphonating acid or by the action of a soluble sulphite or by both methods, or by reacting a 1-bromo- or chloro-4-hydroxy-, amino- or methylaminoanthraquinone - 3 - sulphonic acid with an o-, m-, or p-aminophenyl carboxylic acid.  The carboxylic esters used as starting materials are obtainable by esterifying the corresponding carboxylic acids.  In examples: (1) 1-amino-4-m-carboxyanilinoanthraquinone-2-sulphonic acid is heated with dodecyl alcohol and sulphuric acid; the product dyes wool blue shades; (2) 2-bromo-1-amino-4-o-carbododecoxyanilinoanthraquinone (obtainable by heating the free acid with dodecyl alcohol and sulphuric acid) is heated with sodium sulphite, phenol and water; the product dyes wool blue shades; (3) 1-methylamino-4-o-carbododecoxyanilinoanthraquinone (obtainable by condensing 1-bromo-4-methylaminoanthraquinone with anthranilic acid and heating the product with dodecyl alcohol and sulphuric acid) is dissolved in chloroform and treated with chlorosulphonic acid; the product dyes wool greenish-blue shades; 1-amino-2-methyl-4-o-carbododecoxyanilinoanthraquinone (obtainable by reacting 1-amino-2-methyl-4-bromoanthraquinone with anthranilic acid and esterifying with dodecyl alcohol) may be similarly sulphonated; (4) 1-amino-4-m-carboxyanilinoanthraquinone-2-sulphonic acid is heated with decyl, cetyl or octadecyl alcohol and chlorosulphonic acid; the products dye wool blue shades; (5) oleyl alcohol is used in the process of (4); (6) 1-hydroxy-4-m-carboxyanilinoanthraquinone-2-sulphonic acid (obtainable by reacting 1 : 3 - dibromo - 4 - hydroxy anthraquinone with m-aminobenzoic acid and treating the product with sodium sulphite in phenol) is heated with dodecyl alcohol and chlorosulphonic acid; the product dyes wool violet shades; (7) 1-methylamino-4-m-carboxyanilinoanthraquinone-2-sulphonic acid (obtainable by reacting 1-bromo-4-methylaminoanthraquinone-3-sulphonic acid with m-aminobenzoic acid) is similarly esterified; (8) sodium 2-bromo-1-amino-4-m-carboxyanilinoanthraquinone-6-sulphonate is similarly esterified; the product dyes wool reddish-blue shades; p by heating it with sodium sulphite, water and phenol, the corresponding 2 : 6-disulphonic acid is obtained; (9) 2-bromo-1-amino-4-m-carbododecoxyanilinoanthraquinone is heated with sodium sulphite, phenol and water.  Other alcohols specified for the esterification are octyl and tetradecyl alcohols, other alcohols obtainable by reduction of the fatty acids of natural fats and oils, and mixed alcohols, e.g. technical lorol. Specification 355,810 is referred to.