Patent GB-518725-A (GB)
Title: Manufacture of anthraquinone dyestuffs and process of colouring therewith
IPC: C09B1/20
Filed: 1938-08-29
Abstract: 518,725. Dyes ; dyeing cellulose esters and ethers. ELLIS, G. H., and BROWN, F. Aug. 29, 1938, No. 25289. [Classes 2 (iii) and 15 (ii)] New dyestuffs are obtained by the action of a primary or secondary alkylamine, containing a simple hydroxyl group, on an anthraquinone- 2-carboxylic chloride having in the 1- and 4- positions either two amino groups or an amino group and a hydroxyl group, the anthraquinone-2-carboxylic chloride being free from other substituents carrying hydroxy groups or basic amino-groups. The hydroxylalkylamine must contain one hydroxyl group only and must have at least one hydrogen atom attached to the amine nitrogen, e.g., monoethanolamine, mono (#-hydroxypropyl)-amine, mono (#-hydroxy-propyl)-amine and methyl- #-hydroxyethyl-amine. Either or both nuclear amino groups of the anthraquinone-2-carboxylic acid may carry a substituent e.g.,, a simple alkyl group, a cycloalkyl group, an aryl group or an alkyl group. As examples of 1:4-diaminoanthraquinone-2-carboxylic chlorides the following are mentioned : 1:4 diamino-, 1-amino-4- phenylamino-, 1 - amino - 4 - p - tolylamino -, 1 - amino - 4 - m - tolylamino -, 1 - amino - 4 - o - anisidino - , 1 - amino - 4 - p - acetylamino - phenylamino -, 1 - methylamino - 4 - phenylamino -, 1 - methylamino - 4 - p - tolylamino -, 1 - amino - 4 - cyclohexylamino - anthraquinone- 2-carboxylic chlorides. As examples of hydroxy - amino - anthraquinone - 2 carboxylic chlorides, 1 - amino - 4 - hydroxy - anthraquinone - 2 - or 3 - carboxylic chloride and its N-alkyl or N-aryl derivatives are mentioned. The products are dyes for cellulose acetate and other cellulose esters and ethers, e.g. cellulose formate, propionate and butyrate and ethyl, methyl and benzyl cellulose. The 1-amino or 1 - alkylamino - 4 - arylamino - anthraquinone - 2 - carboxylic - mono - (hydroxyalkyl) - amides (the aryls of which are of the benzene series) are especially useful and dye cellulose acetate in blue shades. The 1:4-diamino-anthraquinone-2- carboxylic - (monohydroxyalkyl) - amides are obtained from anthraquinone - 2 - carboxylic - (monohydroxy - alkyl) - amides having an amino group or a substituted amino group in one of the 1- and 4-positions and an acidylamino group, a nitro group of a halogen atom in the other, by hydrolysis in the case of an acidylamino group, by reduction in the case'of a nitro group or by the action of an appropriate amine in the case of a halogen atom, e.g. 1:4- diamino - anthraquinone - 2 - carboxylic - mono - (hydroxyethyl)-amide can be obtained by hydrolysing 1 - amino - 4 - p - toluene - sulph - amino - anthraquinone - 2 - carboxylic - mono- (hydroxyethyl)-amide or by reducing 1-amino- 4 - nitro - anthraquinone - 2 - carboxylic - mono - (hydroxyethyl) - amide. The dyes can be converted into acid sulphuric esters by the action of sulphuric acid or chlor-sulphonic acid in the presence of a tertiary base. The sulphuric esters are useful for dyeing cellulose esters and ethers and also as dyes for animal fibres. In the examples (1) 1-amino-4-phenylaminoanthraquinone-2-carboxylic acid is treated with phosphorus pentachloride and the acid chloride is treated with monoethanolamine to give 1 - amino - 4 - phenylamino - anthraquinone - 2 - carboxylic - mono - (hydroxyethyl) - amide which dyes cellulose acetate blue shades; (2) 1 - amino - 4 - brom - anthraquinone - 2 - carboxylic acid chloride (prepared by the action of thionyl chloride on the corresponding acid) is treated with mono-ethanolamine and the 1 - amino - 4 - brom - anthraquinone - 2 - carboxylic - oxyethyl - amide formed is treated with aniline ; (3) 1 - amino - 4 - hydroxy - anthraquinone - 2 - carboxylic chloride is treated with monoethanolamine to give 1-amino 4 - hydroxy - anthraquinone - 2 - carboxylic - mono - (hydroxyethyl) - amide which dyes cellulose acetate violet shades. 1:4 Diaminoanthraquinone - 2 - carboxylic-mono-(hydroxy - alkyl) - amides can also be prepared in the following ways : (a) by the action of an anthraquinone - 2 - carboxylic - (mono - hydroxyalkyl)- amide having a halogen atom in each of the 1- and 4-positions on an amine, e.g. 1:4 - di - (methylamino) - anthraquinone - 2 - carboxylic - mono - (hydroxyethyl) - amide can be obtained by the action of methylamine on 1:4 - dichlor - anthraquinone - 2 - carboxylic-mono-(hydroxy - ethyl)-amide ; (b) by the action of an alkylene chlorhydrin on the corresponding compounds in which the carboxylic amide group is unsubstituted or is mono-substituted by a group which is not a hydroxyalkyl group ; (c) the action of an amino-alcohol on a 1:4-diaminoanthraquinone - 2 - carboxylic ester or halide other than the chloride ; (d) action of ammonia or an amine or an anthraquinone - 2 - carboxylic- (monohydroxylakyl) - amide having in one of the 1- and 4-positions an unsubstituted or substituted amino group and in the other a substituent (other than a halogen atom or nitro group) capable of being replaced by an unsubstituted or substituted amino group by the action of the ammonia or amine, e.g., an alkyloxy or aryloxy group. -