GB440263A - Improvements in the manufacture and production of ketones of the anthracene series - Google Patents

Abstract

Ketones of the anthracene, anthraquinone, thiazolanthrone and benzanthrone series, are obtained by treating with acid or alkaline saponifying agents, compounds of the formula <FORM:0440263/IV/1> where A is a radicle of the above-mentioned series, attached in a b - or Bz-position, X is hydrogen or a metal of the alkali or alkaline earth group or magnesium, R1 is a free or esterified carboxylic group, and R2 is hydrogen an acyl radicle, or a free or esterified carboxylic group, the said compounds being obtainable by condensing an acid chloride of the above-mentioned series with alkali alkaline earth or magnesium malonic or acyl-acetic esters. The metal compounds may be suspended in a dispersing agent. The saponification may take place in one or 2 stages. Specification 289,585, [Class 2 (iii)], is referred to in the first Provisional Specification. According to examples: (1) the compound obtained by condensing anthraquinone-2-carboxylic chloride with acetoaceticester and sodium ethylate, is saponified with concentrated sulphuric acid to give b -anthraquinonylmethylketone; (2) the compound obtained from 2-chloranthraquinone-3-carboxylic chloride, malonic ester and sodium ethylate is saponified with phosphoric acid, to give 2-chloro-3-anthraquinonylmethyl ketone; (3) hydrochloric acid, and aluminium chloride, may also be employed as saponifying agents; a product still containing one carboxylic ester group from the malonic ester, linked to the 2-CO group, may be obtained as an intermediate stage with sodium hydroxide; and with methylsulphuric acid, a similar intermediate product with the ester group hydrolyzed to carboxylic acid is obtained; the same products are obtained with the use of the corresponding calcium, strontium or barium, malonic ester condensation products; (4) the compounds obtained by condensing magnesium malonic ester with anthracene 2-carboxylic chloride, 1 : 4 dichloranthraquinone-6-carboxylic chloride, bz 1-benzanthronyl carboxylic chloride, thiazolanthrone-2-carboxylic chloride, 2 - chloranthracene - 3 - carboxylic chloride, 1-nitroanthraquinone-2-carboxylic chloride, are hydrolyzed with sulphuric, hydrochloric phosphoric acids or aluminium chloride to give the corresponding b - or Bz-methyl ketones; (5) the compounds obtained by condensing malonic ester with 1 : 4 dichloranthraquinone-2-carboxylic chloride, 1-nitroanthraquinone-2-carboxylic chloride, bz1-benzanthrone-carboxylic chloride, thiazolanthrone-2-carboxylic chloride, anthracene- and 3-chloranthracene-2-carboxylic chloride, are hydrolyzed with sulphuric acid to give the corresponding b - or Bz-methyl ketones, which may be further treated in the case of bz-1-benzanthronyl methyl ketone, by oxidation to give the corresponding carboxylic acid and in the case of the nitro compound by reduction to give the corresponding amino derivative.