Patent GB-421264-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
IPC: C09B5/00
Filed: 1933-03-13
Abstract: Relates to the condensation of certain "azabenzanthrones" by which term is meant benzanthrones containing a nitrogen atom instead of any --CH= group of the benzanthrone nucleus (cf. Specification 412,586). b z3-, 5- or 8-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, are treated with alkaline condensing agents; or b z3-, 5- or 8-azabenzanthrones or homologues or derivatives thereof which are connected with an aromatic radicle containing at least two condensed rings by means of a nitrogen atom or with an aromatic radicle by means of a carbon atom, are treated with acid condensing agents. These products may be halogenated or nitrated and those containing hydroxy or free amino groups may be alkylated or acylated; those products containing halogen may be condensed with primary or secondary amines or hydroxy compounds.  By alkaline condensation of the specified azabenzanthrones unsubstituted in the peri positions or substituted therein by substituents which are readily split off such as halogen, amino, hydroxy, mercapto or nitro groups or groups corresponding to the formula --OR (R denoting alkyl or aryl) or the phenylamino group, the resulting compounds appear to be formed by linkage in one or both peri positions of two molecules of starting materials; when an azabenzanthrone linked in peri position through a nitrogen atom with an aromatic radicle containing at least two condensed rings is so treated an acridine ring formation results, while treatment of the latter with acid condensing agents yields carbazolized derivatives.  Alkaline condensing agents referred to are caustic potash or soda, sodamide, sodium anilide or mixtures thereof. Where subsequent halogenation is desired this is effected in the presence or absence of diluents and/or catalysts.  The products are vat dyes or intermediates.  In examples: (1) the condensation product of b z1-bromo-8-azabenzanthrone and a -aminoanthraquinone is condensed in alcoholic potash (dyes olive-green) and the product treated with sulphurylchloride in nitrobenzene in presence of iodine (dyes dark green) or brominated in chlorsulphonic acid in presence of iodine and iron (olive-green); condensation of this bromo derivative with a -aminoanthraquinone yields a product dyeing grey shades; condensation of the initial starting material in concentrated sulphuric acid gives an orange-yellow carbazol; (2) the condensation product of b z1-bromo-8-azabenzanthrone with pyrazolanthrone or a bromo derivative of this product (cf. example 13 of Specification 412,586) is condensed in alcoholic potash (blue shades); the non-halogenated product is brominated in nitrobenzene in presence of iodine or in chlorsulphonic acid in presence of iodine, sulphur or antimony, a chlorobromo derivative being obtainable in the latter case; oleum, concentrated sulphuric acid, aqueous suspension may also be used or a diluent may be absent; chlorination may be effected in nitrobenzene by means of chlorine or sulphurylchloride; the above chlorbromo derivative is condensed with phenol (blue); nitration is effected in nitrobenzene using concentrated sulphuric acid (green shades changed to green or black by chlorine); (3) the condensation products of b z1-bromo-8-azabenzanthrone with 1,5-diaminoanthraquinone (\ba1/2\be and 1 mol.) (grey), 1-amino-5-methylaminoanthraquinone, 1 - amino - 5 - dimethylaminoanthra - quinone (grey), 1-amino-5-benzoylaminoanthraquinone (grey) are condensed in alcoholic potash or in the case of the last-named product sodium alcoholate, sodium anilide or sodamide may be used; (4) the condensation products of b z1,6-dibromo-8-azabenzanthrone (cf. example 6 of Specification 412,586) and a -aminoanthraquinone (2 mols.) or pyrazolanthrone (1 mol.) and a -aminoanthraquinone (1 mol.) are condensed in alcoholic potash (grey shades); (5) 8-azabenzanthrone (cf. example 1 of Specification 412,586) is condensed in alcoholic potash at about 90 DEG  to give a diazabenzanthronyl; halogen and alkyl derivatives of the starting material may be similarly converted; conducting the reaction at 150--155 DEG  C. gives a reddish-violet dye and this on nitration yields green to blue dyes; (6) by fusion with potash of 8 - azabenzanthrone sulphonic acid (cf. example 8 of Specification 412,586), b z1-mercapto-8-azabenzanthrone and monamino-8-azabenzanthrone (prepared by nitration and reduction) blue to green dyes are obtained; (7) 2-benzoyl-8-azabenzanthrone (prepared by condensing benzylcyanide with 8 - azabenzanthrone in an alkaline medium and oxidation of the reaction product by means of chromic acid in acetic acid) is condensed with sodium aluminium chloride while leading in oxygen (orange shades); (8) the condensation product of b z1-bromo-b z3-azabenzanthrone (prepared by brominating b z3-azabenzanthrone in nitrobenzene in presence of iodine; b z3-azabenzanthrone is prepared by condensing phenylethylamine with o-toluylcarboxylic acid chloride, condensing this with phosphorus pentoxide in presence of tetrahydronaphthalene, dehydrogenating the resulting dihydroisoquinoline derivative in an iron tube at about 700 DEG  C. and oxidizing with chromic acid) and a -aminoanthraquinone is condensed in alcoholic potash (bluish-green) and in concentrated sulphuric acid (yellow); condensation in alcoholic potash of the reaction product of this bromo derivative with 1-amino-5-dimethylaminoanthraquinone, 5-amino-1,9-anthrapyrimidine, pyrazolanthrone and 1 - amino - 5 - benzoylaminoanthraquinone yields grey to violet dyes; in the last-named case subsequent benzoylation or condensation by means of sodium alcoholate or sodium anilide yields olive-dyeing products; (9) alkali condensation of the reaction product of dibromo-b z3-azabenzanthrone with 2 mols. a -aminoanthraquinone yields a grey dye.  In the second Provisional Specification, a further example describes the condensation of b z1-benzoyl-8-azabenzanthrone with sodium aluminium chloride while leading in air or oxygen to give a monopyridinomonobenzpyrenequinone (yellow) and the preparation of b z1-aroylazabenzanthrones generally by reaction of the b z1-carboxylic acid chlorides with aromatic hydrocarbons according to the Friedel-Crafts' synthesis is mentioned. Reference is made to the manufacture of condensation products containing amino, substituted amino, hydroxy, alkoxy, phenoxy, alkyl, aryl, nitro, sulphonic, cyano and thiocyano substituents and in this connection azabenzanthrones containing amino or thiocyano groups are prepared by reaction b z - bromoazabenzanthrones with primary amines (methylamine) or with alkali metal thiocyanates respectively. Samples have been furnished under Sect. 2 (5) of dyes prepared by (a) alkali condensation of b z1-methoxy-5-azabenzanthrone (prepared by quinolizing 2-aminonaphthalene-3-hydroxy-6-sulphonic acid with glycerine in presence of an oxidizing agent and concentrated sulphuric acid followed by fusion with potash and methylation by means of p-toluenesulphonic acid methyl ester) (red-violet shades); (b) alkali condensation of b z1-(5<1>-anthrapyrimidylamino)-5-azabenzanthrone (prepared by treating b z1-hydroxy-5-azabenzanthrone with phosphorus pentachloride and condensing the b z1-chloro derivative with 5-amino-1,9-anthrapyrimidine) (grey-olive shades); and (c) alkali fusion of the condensation product of b z1-hydroxy-5-azabenzanthrone with 1,5-diaminoanthraquinone (grey shades).