Patent GB-492291-A (GB)
Title: Manufacture of dyestuffs of the anthraquinone series
IPC: C09B1/28
Filed: 1937-03-17
Abstract: Unsulphonated dyes of the anthraquinone series are made by (a) reacting an anthraquinone-2-carboxylic acid halide containing in 1-position a substituent exchangeable for an amine radical with a primary aliphatic amine or amines or ammonia to form a derivative containing similar or different amine radicals, halogenating the said derivative and causing the 4-halogenanthraquinone derivative thus produced to react further with a primary aliphatic amine or ammonia, care being taken by the use of a hydroxyalkylamine or hydroxyalkylamines that the final substance contains at least two hydroxy-alkyl groups one of which is present in the carboxyamide group; (b) reacting an anthraquinone-2-carboxylic acid halide containing in 1-position an amino group or the radical of a primary aliphatic amine with a primary hydroxyalkylamine to form a derivative containing similar or different amine radicals, halogenating the product and causing the 4 halogenanthraquinone derivative thus obtained to react further with a primary aliphatic amine or ammonia, a primary hydroxyalkylamine being used for the last-named reaction at least when the 4-halogenanthraquinone derivative does not contain in 1-position the radical of a hydroxyalkylamine; (c) reacting an anthraquinone-2-carboxylic acid halide containing in 1- and 4-positions substituents exchangeable for an amine radical or in 1-position an amino group or the radical of a primary aliphatic amine and in 4-position a substituent exchangeable for an amine radical with a primary aliphatic amine or amines or ammonia to form a derivative containing similar or different amine radicals, care being taken, by the use of a hydroxyalkylamine or hydroxyalkylamines that the final substance contains at least two hydroxyalkyl groups one of which is present in the carboxyamide group; (d) using a sulphonamide instead of ammonia in (a), (b) and (c) above, the sulphonamide group in the product being saponified; (e) reacting an anthraquinone-2-carboxylic halide of the formula <FORM:0492291/IV/1> (where X1 is the radical of a primary hydroxyalkylamine, and X2 is nitro or acylamino) with a primary hydroxyalkylamine to form a derivative containing similar or different amine radicals and reducing the nitro group or saponifying the acylamino group.  Amines specified are methylamine, ethylamine, 2-aminoethanol(1), 3-aminopropanol-(1). The products dye acetate artificial silk blue shades.  In examples, (1) 1-chlor-(or nitro-) anthraquinone-2- carboxylic acid chloride is reacted with aminoethanol to give 1-hydroxyethylamino-anthraquinone-2-carboxylic hydroxyethylamide, which is brominated to give the 4-bromo body, and reacted with aminoethanol to give 1,4-bis-hydroxyethylaminoanthraquinone - 2 - carboxylic hydroxyethylamide, which may also be prepared from 1,4-dichloranthraquinone-2-carboxylic acid chloride; 3-aminopropanol-1 may be used instead of aminoethanol, and alternatively 1-chloranthraquinone-2-carboxylic acid chloride may be reacted first with aminoethanol to give 1-chloranthraquinone-2-carboxylic hydroxyethylamide, which may then be reacted with 3-aminopropanol-1, ammonia, or methylamine, the product brominated and reacted with aminoethanol; (2) 1-aminoanthraquinone-2-carboxylic acid is brominated, converted to the acid chloride, and reacted with aminoethanol, or converted to the acid chloride, reacted with aminoethanol, brominated, and again reacted with aminoethanol; 3-aminopropanol-1 or 3-aminopropanediol-(1,2) may be used; (3) 1-hydroxyethylamino - 4 - bromanthraquinone - 2 - carboxylic hydroxyethylamide is reacted with p-toluenesulphamide in nitrobenzene, followed by hydrolysis with sulphuric acid to give 1-hydroxyethylamino - 4 - aminoanthraquinone-2 - carboxylic - hydroxyethylamide; (4) 1-methylamino (or ethylamino) - 4 - bromanthraquinone-2-carboxylic acid chloride (obtained from 1-methylaminoanthraquinone - 2 - carboxylic acid (as in 2) is reacted with aminoethanol to give the hydroxyethylamide and again to replace the bromine atom; the bromine atom may alternatively be replaced by the radical of 3-aminopropanol-1; (5) 1 - chloranthraquinone - 2 - carboxylic acid chloride is treated first with amino-ethanol and then with ammonia to give 1-aminoanthraquinone-2-carboxylic acid hydroxyethylamide, which is brominated and the 4-brom derivative reacted with aminoethanol to give the product of 2 above.