Patent GB-680364-A (GB)
Title: Vat dyestuffs of the anthraquinone series
IPC: C09B1/00
Filed: 1950-02-16
Abstract: 2.5-Disubstituted 1.2.4-oxdiazoles containing the oxdiazole grouping once or several times, wherein at least one substituent is derived from a cyclic vattable compound and wherein at most one anthraquinone group is linked to one and the same oxdiazole grouping are made by treating with dehydrating condensing agents the corresponding N.N1-diacylhydrazides, or a mixture of a monoacylhydrazide and a carboxylic acid or a functional derivative thereof with fuming sulphuric acid or chlorsulphonic acid.  Nitro groups in the products may be reduced and acylated, and halogen atoms may be replaced by amino groups by reaction with toluene sulphonamide and hydrolysis. Vattable carboxylic acids from which the acyl groups may be derived are those of anthraquinone, benzanthrone, thiazol-anthrone, anthraquinone-acridone, and non-vattable carboxylic acids are acetic acid, benzoic acid, oxalic acid, adipic acid, terephthalic acid, trimesic acid.  Dehydrating condensing agents specified are fuming sulphuric acid, chlorsulphonic acid, thionyl chloride, toluene sulphochloride, and toluene sulphonic acid.  In examples: (1) a dihydrazide is formed from anthraquinone-2-carboxylic chloride and p-nitrobenzoyl hydrazide, and is ring-closed with fuming sulphuric acid or thionyl chloride in nitrobenzine, followed by reduction by vatting to give 2-(p-aminophenyl)-5-(21-anthraquinonyl)-oxdiazole, an intermediate which is acylated with thiazolanthrone carboxylic chloride to give a greenish-yellow dye; the intermediate may also be obtained from anthraquinone-2-carboxylic acid and p-nitrobenzoyl hydrazide in fuming sulphuric acid or chlorsulphonic acid.  Also, (2) the dihydrazide from 1-aminoanthraquinone-2-carboxylic chloride and p-nitrobenzoyl hydrazide is ring-closed with chlorsulphonic acid, the nitro group is reduced, and acylated with benzoyl chloride (scarlet shades on cotton), or thiazolanthrone carboxylic chloride (yellow shades), or 1-aminoanthraquinone - 2 - carboxylic chloride (red shades); the intermediate may also be converted to the urea derivative or reacted with cyanuric chloride (yellow-scarlet shades). Also, (3) a tetrahydrazide formed from adipic acid dihydrazide and 1-chloranthraquinone-2-carboxylic chloride is ring-closed with fuming sulphuric acid, and the product is melted with p-toluenesulphonamide, followed by hydrolysis (scralet shades). Also, (4) terephthalic and oxalic acid dihydrazides are reacted with 1 - aminoanthraquinone - 2 - carboxylic chloride and the products ring-closed with fuming sulphuric acid; (5) 1.5-dichloroanthraquinone-2.6-dicarboxylic chloride and p-chlorobenzoyl hydrazide (2 mols.) are reacted and ring-closed with fuming sulphuric acid, followed by application of the toluene sulphonamide melt (bluish-violet shades); (6) 1-amino-anthraquinone-2-carboxylic acid hydrazide is reacted with an anthraquinone-benzacridone carboxylic chloride or azobenzene-p.p1-dicarboxylic acid dichloride followed by ring-closure with fuming sulphuric acid (red and scarlet shades).ALSO:The invention comprises 2,5-disubstituted 1,3,4-oxidiazoles containing the oxidiazole grouping once or several times wherein at least one substituent is derived from a cyclic vattable compound and wherein at most one anthraquinone group is linked to one and the same oxidiazole grouping.  They are made by treating with dehydrating condensing agents the corresponding N,N1-diacylhydrazides, or a mixture of a monoacylhydrazide and a carboxylic acid or a functional derivative thereof with fuming sulphuric acid or chlorsulphonic acid.  Nitro groups in the products may be reduced and acylated and halogen atoms may be replaced by amino groups by reaction with toluene sulphonamide and hydrolysis.  Vat-table carboxylic acids from which the acyl groups may be derived are those of anthraquinone, benzanthrone, thiazolanthrone, anthraquinone-acridone, and non-vattable carboxylic acids are acetic acid, benzoic acid, oxalic acid, adipic acid, terephthalic acid, trimesic acid.  Dehydrating condensing agents specified are fuming sulphuric acid, chlorsulphonic acid, thionyl chloride, toluene sulphochloride, and toluene sulphonic acid.  In examples: (1) a dihydrazide is formed from anthraquinone-2-carboxylic chloride and p - nitrobenzoyl hydrazide, and is ringclosed with fuming sulphuric acid or thionyl chloride in nitrobenzene, followed by reduction by vatting to give 2-(p - aminophenyl) - 5 - (21 - anthraquinoxyl)-oxidiazole, an intermediate which is acylated with thiazolanthrone carboxylic chloride to give a greenish-yellow dye; the intermediate may also be obtained from anthraquinone-2-carboxylic acid and p-nitrobenzoyl hydrazide in fuming sulphuric acid or chlorsulphonic acid.  Also, (2) the dihydrazide from 1-aminoanthraquinone-2-carboxylic chloride and p-nitrobenzoyl hydrazide is ringclosed with chlorsulphonic acid, the nitro group is reduced, and acylated with benzoyl chloride (scarlet shades on cotton), or thiazolanthrone carboxylic chloride (yellow shades), or 1-aminoanthraquinone - 2 - carboxylic choride (red shades); the intermediate may also be converted to the urea derivative or reacted with cyanuric chloride (yellow-scarlet shades).  Also, (3) a tetrahydrazide formed from adipic acid dihydrazide and 1-chloranthraquinone-2-carboxylic chloride is ringclosed with fuming sulphuric acid, and the product is melted with p-toluenesulphonamide, followed by hydrolysis (scarlet shades). Also, (4) terephthalic and oxalic acid dihydrazide are reacted with 1-aminoanthraquinone-2-carboxylic chloride and the products ringclosed with fuming sulphuric acid; (5) 1,5-dichloroanthraquinone-2,6-dicarboxylic chloride and p - chlorobenzoyl hydrazide (2 mols) are reacted and ringclosed with fuming sulphuric acid, followed by application of the toluene sulphonamide melt (bluish - violet shades); (6) 1 - aminoanthraquinone - 2 - carboxylic acid hydrazide is reacted with an anthraquinone-benzacridone carboxylic chloride or azobenzene-p,p1 - dicarboxylic acid dichloride followed by ring-closure with fuming sulphuric acid (red and scarlet shades).