Patent GB-718524-A (GB)
Title: Manufacture of vat dyestuffs of the anthraquinone series
Filed: 1951-11-21
Abstract: 1 - Fluoro - 2 - methyl - 4 - or 5 - chlorobenzene may be made by treating the corresponding 1-amino compound with hydrofluoric acid and sodium nitrite or with hydrofluoboric acid.  2 - Fluoro - 4 - or 5 - chlorobenzoic acid may be made by oxidizing the corresponding 1-methyl derivative, e.g. with potassium permanganate, or hydrolysing the corresponding 1-trichloromethyl derivative.  2 - Fluoro - 4 - or 5 - chlorobenzoyl chloride is obtained from the corresponding acid on treatment with thionyl chloride. Specification 555,055 is referred to.ALSO:The invention comprises dyestuffs of formula:- <FORM:0718524/IV(c)/1> where n is 1 or 2.  X is the residue of a carboxylic acid of n carboxyl groups and R is a benzene residue containing in ortho position to the -CO-group a fluorine atom and in para position with respect to one of these substituents a chlorine atom.  They may be made by treating 1, 5-diaminoanthraquinone or a 1-amino-5-acylaminoanthraquinone with an acylating agent chosen so that the final product contains the requisite groupings and orientations.  Thus 1, 5-diaminoanthraquinone may be treated with two mols of 2-fluoro-4- or -5-chlorobenzoic acid or its acid chloride to yield a product similar to that obtained by acylating 1-amino-5-(21-fluoro-41- or -51-chlorobenzoylamino)-anthraquinone with the same chlorobenzoic acid.  Alternatively the latter anthraquinone may be acylated with a monohalogen benzene carboxylic acid and is advantageously acylated with agents derived from dicarboxylic acids such as oxalic, iso and tere-phthalic, naphthalene-2, 6-dicarboxylic, fluoranthene-4, 11-dicarboxylic or thianthrene dicarboxylic acids.  When the 1-amino-5-acylaminoanthraquinone does not contain the desired fluoro, chloro acyl residue it is acylated with a 2-fluoro-4-or -5-chloro-benzoic acid. Advantageously the dyestuffs do not contain more than three halogen atoms per anthraquinone residue.  Acylation is preferably effected by means of reactive functional derivatives of the acids concerned.  Solvents or dispersing media may be present especially those of high boiling point e.g. mono-, di- or tri-chlorobenzene, nitrobenzene or naphthalene, reaction being effected at about 100 DEG C. to the boiling point of the acylation mixture.  The products dye and print animal and especially vegetable fibres, artificial silk or regenerated cellulose and superpolyamide fibres.  In examples (1) 1-amino-5-(41- or 51-chloro - 21 - fluorobenzoylamino) anthraquinone is treated with 4-chlorobenzoyl chloride, the anthraquinone being made by the partial acylation of 1, 5 - diaminoanthraquinone with 2 - fluoro - 4 - or 5 - chlorobenzoyl chloride or from 1-chloro-5-(41- or 51-chloro-21-fluorobenzoylamino)-anthraquinone by replacing the Cl. atom by a toluene sulphonamide residue and splitting off a sulphonic acid residue, and 1-amino-5-(41-chloro - 21 - fluorobenzoylamino)-anthraquinone is treated with (2) oxalyl chloride, (3) tere phthalic acid dichloride and (4) thianthrene dicarboxylic acid dichloride.  Representative of other acids listed for reaction with the anthraquinone of (2) (preferably as their dichlorides) are diphenyl-4, 41-dicarboxylic and azobenzene-4, 41-dicarboxylic acids and for reaction with the 51-chloroisomer of the above anthraquinone representative are isophthalic, thianthrene dicarboxylic, diphenyl - 4, 41 - dicarboxylic and azodiphenyldicarboxylic acids.  1 - amino - 5 - (41 - chloro - 21 - fluoro - benzoylamino)-anthraquinone may be made by the partial acylation of 1, 5-diaminoanthraquinone with 2-fluoro-4-chlorobenzoyl chloride or from 1-chloro-5 - (41 - chloro - 21 - fluorobenzoylamino) - anthraquinone by replacing the chlorine atom by a toluene sulphonamide group followed by the removal of the sulphonic acid residue. 1-amino-5-(51 - chloro - 21 - fluorobenzoylamino) - anthraquinone may be made in a similar way.  Specification 555,055 is referred to.