Patent GB-450244-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
IPC: C09B5/00
Filed: 1934-12-10
Abstract: Vat dyes or intermediates are prepared by the treatment with alkaline condensing agents of Bz2-, 3-, 4-, 6- or 7-azabenzanthrones or homologues or derivatives thereof which are not substituted in either of the peri positions or are only substituted therein by substituents which are readily split off or which may be connected in a peri position with an aromatic radicle containing at least two condensed rings by means of a nitrogen bridge.  Those starting materials having two reactive peri positions (including those wherein one peri position p  contains a substituent which is easily displaced) yield by the above treatment carried out below 100 DEG  C. diazabenzanthronyls but by treatment at higher temperatures, when a peri-position is occupied by a pyrazolanthrone or anthraquinone or other vattable radicle condensation products containing an acridine ring are derived.  Bz2-azabenzanthrones are obtained by condensing anthraquinone-1-carboxylic acid chloride with aminoacetic acid esters, treating the resulting compound with aminoacetic acid esters and splitting off carbon dioxide.  3-Azabenzanthrones are prepared by treating 4-benzoylisoquinolines having a reactive 5-position with a condensing agent of the type of aluminium chloride. 4-Azabenzanthrones are similarly derived from 1-benzoylisoquinolines having a reactive 8-position.  6- And 7-azabenzanthrones are obtained from b -azanthraquinones or the corresponding reduction products by treating them with glycerine in the presence of sulphuric acid.  In examples: (1) the azabenzanthrone obtained by treating 2-azanthraquinone with glycerine and sulphuric acid is condensed with alcoholic potash at 140--145 DEG  C.; the product dyes vegetable fibres violet shades; the 3- or 4-azabenzanthrones may similarly be used as starting material; (2) Bzl-hydroxy-Bz2-azabenzanthrone (prepared by condensing anthraquinone-1-carboxylic acid chloride with aminoacetic acid ethyl ester, splitting off water, saponifying and decarboxylating) is treated with caustic potash at 215--222 DEG  C.; the product dyes blue-green shades; using Bzl-chloro-Bz2-azabenzanthrone (derived by the action of phosphorus pentachloride on the Bzl-hydroxy derivative) as starting material a violet-blue dye is obtained; a similar condensation of the product derived by condensing a dibromo derivative of Bzl-hydroxy-Bz2-azabenzanthrone with two molar proportions of 1-aminoanthraquinone gives a brownish-grey dye; (3) the product derived by condensing the bromination product of the azabenzanthrone of (1) with 1-aminoanthraquinone is condensed with alcoholic potash at 145 DEG  C. (olive-grey shades); (4) the mixture of 6- and 7-azabenzanthrones obtained from 2-azanthraquinone is separated by running slowly through a column of aluminium oxide to effect differential adsorption and extracting the appropriate parts of the column with quinoline, and each component condensed with potash to give dyes of violet shades; (5) dimethyl-6-azabenzanthrone (which is prepared by condensing 1.3-dimethyl-2-azanthraquinone with glycerine and sulphuric acid) or the Bzl-bromo derivative thereof derived by bromination in nitrobenzene, or a methylphenyl-6-azabenzanthrone (derived from 3-phenyl-1-methyl-2-azanthraquinone, which is prepared by condensing 2 - methyl - 6 - phenylpyridine - 3 . 4 - dicarboxylic acid anhydride with benzene in presence of aluminium chloride and ring-closing by means of strong sulphuric acid, by treatment with glycerin in strong sulphuric acid) is treated with alcoholic potash at 130--150 DEG  C. to give violet to blue shades; (6) the condensation products of Bzl-bromo-dimethyl - 6 - azabenzanthrone (cf. 5) and 1-aminoanthraquinone or pyrazolanthrone or the condensation product of a dibrominated derivative of dimethylazabenzanthrone (cf. 5) and 1-aminoanthraquinone are condensed with alcoholic potash at about 140 DEG  C. (olive-green, blue and grey shades respectively).