Patent GB-366055-A (GB)
Title: Improvements in the manufacture and production of chloro derivatives of the anthraquinonebenzacridone series
Filed: 1930-07-23
Abstract: Chloranthraquinone-2.1-benzacridones are prepared by condensing 1-halogen (or nitro)-anthraquinone-2-carboxylic acids with 2.5-dichloraniline or a trichloraniline having a free o-position to the amino group, the product being further condensed to the acridone derivative.  Or a 1-halogen (or nitro)-anthraquinone is condensed with an o-aminobenzoic acid substituted by chlorine in positions 3- and 6-, or containing three chlorine atoms, the product being further condensed to the acridone derivative.  The above Bz-trichloro derivatives are also obtained by treating an anthraquinone-2.1-benzacridone substituted by chlorine in the Bz2-, Bz4, Bz2.3-, Bz3.4-, Bz4.5- or Bz2.5- positions, with chlorine or agents supplying chlorine in organic solvents in the absence of halogenating catalysts.  In such halogenation process the initial materials must be freed from agents employed in their preparation and which may act as halogenating catalysts.  The products dye orange to yellow-red shades and are particularly valuable in view of the fastness of the dyeings to alkali; details of the alkali heat treatment tests to which the dyeings conform are given.  In examples (1) 1-chloranthraquinone-2-carboxylic acid is condensed with 3.4.5-trichloraniline in the presence of trichlorbenzene and boric acid, and the reaction product completely converted to Bz2.3.4-trichloranthraquinone-2.1-benzacridone by warming in chlorsulphonic acid or in nitrobenzene with phosphorus pentachloride; esters or amides of 1-chloranthraquinone-2-carboxylic acid or the corresponding 1-bromo derivative may be employed instead; (2) 1-chloranthraquinone-2-carboxylic acid is condensed with 2.5-dichloraniline and the product ring-closed by means of phosphorus pentachloride in nitrobenzene or by means of chlorsulphonic acid to give Bz2.5-dichloranthraquinone-2.1-benzacridone; (3) 1-chloranthraquinone-2-carboxylic acid-benzyl ester is condensed with 2.4.5-trichloraniline and the product ring-closed as in (2) to give Bz2.3.5-trichloranthraquinone-2.1-benzacridone; (4) 1-chloranthraquinone-2-carboxylic acid-benzyl ester is condensed with 2.3.5-trichloraniline and the product ring-closed to Bz2.4.5-trichloranthraquinone-2.1-benzacridone; (5) Bz3.4-dichloranthraquinone-2.1-benzacridone (prepared by condensing 1-chloranthraquinone with 4.5-dichloranthranilic acid and ring-closure to the acridone) is treated with chlorine in trichlorbenzene to give Bz3.4.5-trichloroanthraquinone-2.1-benzacridone; the same product is obtained by treatment with chlorine or sulphuryl chloride of Bz4-monochloro- or Bz4.5-dichloranthraquinone-2.1-benzacridone (these acridones being prepared by condensing 1-chloranthraquinone with 4-chloranthranilic acid and 3.4-dichloranthranilic acids respectively, followed by ring-closure to the acridones); (6) Bz2-chloranthraquinone-2.1-benzacridone (prepared by condensing 1-chloranthraquinone with 6-chloranthranilic acid followed by ring-closure to the acridone) is treated with chlorine in trichlorbenzene to give Bz2.3.5-trichloranthraquinone-2.1-benzacridone; the similar treatment of Bz2.3-dichloranthraquinone-2.1-benzacridone (prepared by condensing 1-chloranthraquinone with 5.6-dichloranthranilic acid followed by ring-closure to the acridone) yields the same product. Specifications 13907/09, 894/11, 260,588, 324,084, 338,182, [all in Class 2 (iii), Dyes &c.], 346,676, and 347,722 are referred to.