Patent GB-657515-A (GB)
Title: Manufacture of acylacetic acid arylides and azo-dyestuffs derived therefrom
IPC: C09B33/153
Filed: 1948-11-03
Abstract: Arylides of the formula <FORM:0657515/IV (b)/1> are obtained by reacting 2 mols. of a reactive derivative of an acylacetic acid with 1 mol. of a 2 : 5-dialkoxy-1 : 4-diamino-benzene.  The acyl group may be derived from an aliphatic, araliphatic or aromatic carboxylic acid, e.g. acetic, benzoic, o- or p-chlorbenzoic, 2 : 4-dichlorbenzoic or p-nitrobenzoic acid.  The ethyl ester is the preferred reactive derivative of the acylacetic acid.  The alkoxy groups in the nucleus have preferably not more than 6 carbon atoms and may be the same or different, e.g. methoxy, ethoxy, propoxy, isopropoxy or n-butoxy.  The reaction may take place in an inert solvent in the presence of a catalytic or enolising substance such as dimethylamine, pyridine, an ethanolamine, caustic soda or alcohol. The products in which the acyl group is an acetyl group may be further treated with an acylating agent containing more than 3 carbon atoms (e.g. the acid chloride of benzoic acid or of one of the substituted benzoic acids mentioned above) by the process of Specification 632,341 or 20391/47 (as open to inspection under Sect. 91).  The acetoacetic arylide is converted into its alkali metal compound and treated with half an equivalent of the acylating agent. The unconverted acetoacetic arylide in the reaction mixture is then again treated with alkali hydroxide and a further half equivalent of acylating agent.  The resulting diacylacetic arylide, probably <FORM:0657515/IV (b)/2> is then hydrolysed with an acid or an alkali to split off the acetyl groups and leave the high-molecular acyl residues, which can also be introduced by direct acylation.  In the example, ethyl acetoacetate is condensed with 2 : 5-dimethoxy-1 : 4-diamino-benzene and the resulting arylide further condensed with benzoyl chloride; the product is hydrolysed to give 1 : 4 - di - benzoylacetylamino - 2 : 5 - dimethoxybenzene.  The corresponding diethoxy compound is made similarly, and aroylacetic arylides may be made directly if ethyl acetoacetate is replaced by ethyl benzoylacetate or a substitution derivative thereof, e.g. the chloro- or nitro-derivative.  Specifications 210,217 and 211,772, [both in Class 2 (iii)], are referred to.ALSO:Arylides of the formula <FORM:0657515/IV (c)/1> are used as coupling components for azo dyestuffs prepared in substance or on a substratum such as a textile fibre, e.g. cotton, linen, artificial silk or staple fibres of regenerated cellulose.  The diazo components may be of the benzene or naphthalene series and are preferably those which are suitable for ice colours, i.e. free from solubilizing groups.  Typical diazo compounds are those from p-toluidine, o- or m-chloraniline, o- or m-nitraniline, 2 : 5-dichloraniline, 1-methoxy-or 1-methyl-2-amino-4- or 5-chlorbenzene, 1-methoxy-2-amino-5-nitro-benzene and 4-chlor-2-amino-diphenyl ether.  For printing, the arylide may be applied in conjunction with a stabilized diazo compound, e.g. a diazoamino derivative from an amino-carboxylic or an amino-sulphonic acid.  In examples: (1) 2 : 5-dimethoxy-1 : 4-diacetoacetylamino-benzene is coupled with diazotized 2-methyl-4-chloraniline; (2) a mixture of 1 : 4-diacetoacetylamino-2 : 5-diethoxybenzene and the anti-diazotate of 2-methyl-4-chloraniline is made into a paste p  with caustic soda, Turkey red oil and starch-tragacanth thickening and printed on cotton.  The colour (orange) is fixed by steaming and developed with formic and acetic acids; (3) cotton is printed with a paste of 1 : 4-diacetoacetylamino-2 : 5-dimethoxy-benzene, the diazoamino compound from p-toluidine and sodium methylamino-acetate, Turkey red oil, alcohol, caustic soda and starch-tragacanth thickener; after-treatment as in (2); (4) as in (3) using the diazoamino compound from m-chloraniline and 2-amino-5-sulpho-benzoic acid (di-sodium salt) or from 2-methyl-5-chloraniline and the same acid; (5) as in (3) using the diazoamino compound from 2-methoxy-5-chlor-aniline and sodium methylaminoacetate; (6) as in (3) using the diazoamino compound from 2-methoxy-4-nitraniline and the disodium salt of 2-methylamino-5-sulpho-benzoic acid; (7) cotton is grounded in a solution of 1 : 4-diacetoacetylamino-2 : 5-dimethoxy-benzene in caustic soda containing Turkey red oil and sodium chloride; the colour is then developed in a solution containing diazotized 2-methoxy-5-chloraniline, sodium acetate and acetic acid; (8) as in (7) using diazotized 2-methyl-4-chloraniline. Specifications 210,217 and 211,772, [both in Class 15 (ii)], are referred to.