Patent GB-512483-A (GB)
Title: Improvements in the manufacture and production of organic dyestuffs
IPC: C09B1/28
Filed: 1938-03-03
Abstract: 512,483. Dyes. I. G. FARBENINDUSTRIE AKT.-GES., and JOHNSON, G. W. March 3, 1938, No. 6708. Addition to 421,117. [Classes 2 (iii) and 15 (ii)] Dyestuffs are manufactured by reacting a compound of the general formula A-(X)n with a compound of the general formula Y-(C2H4-O-)m-C2H4OH (in which formulae A is an anthraquinone radicle, Y is an amino group containing at least one hydrogen atom attached to nitrogen, X is a substituent capable of condensing with Y with the formation of a nitrogen-containing bridge, e.g.; a halogen atom, a hydroxy, alkoxy, amino, nitro, sulphonic acid or carboxylic group including a .substituted carboxylic group such as a carboxylic halide group, and m and n are whole numbers from 1 to 4), the components being so selected that the final product contains at least one auxochromic amino group or a nitro group which may be reduced thereto. The introduction of the polyglycol ether radical may be combined with a simultaneous introduction of a substituted amino group by starting from a compound capable of being substituted in several positions and acting on it with a mixture of a compound of the above general formula Y-(C2H4-O-)m-C2H4OH and a primary aliphatic amine. Suitable anthraquinone compounds are quinizarine, 1-amino-4- hydroxyanthraquinone, 1 : 4-diaminoanthraquinone, 1 : 4-diaminoanthraquinone-6-carboxylic acid; 1-amino-4-nitroanthraquinone-2- carboxylic acid chloride, 1: 4-dibromanthraquinone and 1-methoxy-4-nitroanthraquinone. When starting from amino- or hydroxyanthraquinones, the reaction is advantageously effected in the presence of leuco-compounds of.anthraquinone derivatives, e.g., leuco-quinizarine or leuco-1 : 4-diaminoanthraquinone. The reaction may also be effected in the presence of diluents and/or catalysts, e.g., copper, and, when halogen is to be split off, advantageously in the presence of acid-binding agents. The products are suitable for dyeing acetate artificial silk and mixed fabrics from acetate and viscose artificial silk. In examples : (1) quinizarine is heated with ethylene glycol mono-#-aminoethyl ether in the presence of leuco-quinizarine and isobutanol ; alternatively the leuco-quinizarine is replaced by quinizarine and the reaction is effected in the presence of zinc dust or sodium hydrosulphite ; the product dyes acetate artificial silk from an aqueous bath violet shades ; (2) the proportion of ethylene glycol mono-#-aminoethyl ether in (1) is increased (blue or somewhat reddish blue shades according to the proportions of the, reactants) ; the ethylene glycol mono-#-aminoethyl ether may be replaced by polyethylene glycol #-aminoethyl ethers or mixtures thereof with other amines, e.g., methylamine; the quinizarine may be replaced by 1: 4 : 5 : 8- tetrahydroxyanthraquinone (bluish-green shades) ; (3) 1-amino-4-nitroanthraquinone-2- carboxylic acid chloride is heated with mono-, di-, tri- or tetra-ethylene glycol mono-#- aminoethyl ether in the presence of water, and the nitro group 'is reduced, e.g., with sodium sulphite (blue shades); (4) 1-nitroanthraquinone-2-carboxylic acid chloride is heated with excess of ethylene glycol mono-#-aminoethyl ether in the presence of water (red shades) ; (5) leuco-1 : 4: 5: 6-tetrahydroxyanthraquinone is heated with ethylene glycol mono-#-aminoethyl ether in the presence of isobutyl alcohol, and the product' is heated with nitrobenzene in the presence of piperidine (bluish-green shades) ; (6) quinizarine and leuco-quinizarine are heated with ethylene glycol mono-#-aminoethyl ether and methylamine in the presence of butanol (blue shades) ; (7) leuco-1 : 4- diaminoanthraquinone is heated with ethylene glycol mono-#-aminoethyl ether and nitrobenzene with subsequent addition of piperidine (blue-violet shades). 1 : 4-Diaminoanthraquinone-6-carboxylic acid is obtainable by condensing 1 : 4-dichloroanthraquione-6-carboxylic acid with p-toluenesulphonamide and saponifying the product.' 1 - Amino - 4 4-nitroanthraquinone-2 - carboxylic acid chloride is obtainable by nitrating 1-aminoanthraquinone-2-carboxylic, acid and treating the product with thionyl chloride. Ethylene glycol mono-#-aminoethyl ether is obtainable by treating ethylene glycol mono-#- chloroethyl ether with alcoholic ammonia.