Patent GB-568933-A (GB)
Title: New anthraquinone dyestuffs
IPC: C09B1/42
Filed: 1943-08-03
Abstract: Anthraquinone vat dyes of the general formula <FORM:0568933/IV/1> wherein A and B represent each an alkyl or phenylalkyl group and are not identical, the alkyl groups each containing not more than 4 carbon atoms, the phenyl residue being substituted, if desired, by alkoxy, alkyl or halogen, and the anthraquinone nucleus being, if desired, further substituted, are obtained by introducing the required groups into the 1 and 4 positions by (a) reaction of an appropriate alkane- or phenylalkane - sulphonylbenzoyl halide or (in presence of hydrogen chloride) the corresponding alkane- or phenylalkane - sul - phonyl benzamide with a 1-amino-4-alkane- or phenylalkane-sulphonylbenzoylamino - anthra - quinone obtained (as described in Specification 571,154) by oxidizing the product of acylation of stable leuco-1 : 4-diaminoanthraquinone with an appropriate alkane- or phenylalkane-sulphonylbenzoyl halide; (b) reaction of an appropriate alkane- or phenylalkane-sulphonylbenzamide with the product of reaction of 1 - amino - 4 - chloro - anthraquinone with an appropriate alkane- or phenylalkane-sulphonylbenzoyl halide; or (c) reaction of 1 : 4-diaminoanthraquinone with a mixture of two appropriate alkane- or phenylalkane - sulphonyl - benzoyl halides or (in presence of hydrogen chloride) a mixture of the corresponding benzamides. Specified alkane- or phenylalkanesulphonylbenzoic acids corresponding to the benzoyl halides or benzamides used are m- and p - methane - sulphonylbenzoic, p - isopropane - sulphonylbenzoic, p-n-butane-sulphonylbenzoic, m - ethane - sulphonylbenzoic, m- and p - phenyl - methane - sulphonylbenzoic, 4 - (o - chlorophenyl - methane-sulphonyl) benzoic, 4-(p-tolylmethanesulphonyl)benzoic, 4 - (p - methoxyphenyl - methane-sulphonyl)benzoic, 4-(a -and b -phenyl-ethanesulphonyl)benzoic and 4 - (g  - phenylpropanesulphonyl)benzoic acids.  In examples: (1) 1 - amino - 4 - p - methane - sulphonylbenzoyl - amino-anthraquinone, obtained as described in Specification 571,154, is heated with p-n-butane-sulphonylbenzoyl chloride for 2 1/2 hours in nitrobenzene at 120 DEG  C.; (2) 1-amino-4-p-n-butane-sulphonylbenzoylamino-anthraquinone, obtained by the process of Specification 571,154, is similarly heated with p-methane-sulphonylbenzoyl chloride; (3) 1-amino-4-p-phenylmethane - sulphonylbenzoylamino - an - thraquinone is similarly heated with m-methane-sulphonylbenzoyl chloride; (4) 1-amino-4-p-methane - sulphonylbenzoylamino - anthra - quinone is similarly heated with p-phenylmethane-sulphonylbenzoyl chloride; (5) 1 : 4-diaminoanthraquinone is similarly heated with a mixture of p - methane - sulphonylbenzoyl chloride and p - n - butane - sulphonylbenzoyl chloride; (6) 1-amino-4-p-methane-sulphonyl-benzoylamino-anthraquinone is heated with p-phenylmethane - sulphonylbenzamide for 10 hours in nitrobenzene at 200-210 DEG  C. while passing dry hydrogen chloride through the mixture; (7) 1-chloro-4-p-methane-sulphonyl-benzoylamino-anthraquinone is heated with p-phenylmethane-sulphonylbenzamide at 130 DEG  C. in o - dichlorobenzene containing cuprous bromide with addition of potassium carbonate during 1/2 hour followed by heating for 10 hours at 165-170 DEG  C.  Specifications 513,866, 549,640 and 555,132 also are referred to.  Alkane- and phenylalkane-sulphonylbenzoyl chlorides are obtained by the action of phosphorous pentachloride or thionyl chloride on the corresponding derivatives of benzoic acid.  Alkane- and phenylalkane-sulphonylbenzamides are obtained by the action of ammonia on the corresponding benzoyl chloride or benzoic acid ester derivatives.  p-Methane-sulphonylbenzoic acid is obtained by oxidation of p-methylmercaptobenzoic acid with hydrogen peroxide in glacial acetic acid.  p-Isopropane-sulphonylbenzoic acid is obtained by oxidizing with potassium permanganate, in a neutral aqueous solution of magnesium sulphate, the product of reaction of sodium p-toluenesulphinate with isopropyl bromide. p-n-Butane-sulphonylbenzoic acid is obtained by oxidation of p-tolyl-n-butylsulphone with potassium permanganate.  m- and p - Phenylmethane - sulphonylbenzoic acids are obtained by reaction of m- and p-sulphinobenzoic acids respectively with benzyl chloride.  4 - (o - Chlorophenylmethanesulphonyl) benzoic acid, 4 - (p - tolylmethanesulphonyl) benzoic acid, 4 - (p - methoxyphenylmethanesulphonyl) benzoic acid, 4 - (b  - phenylethanesulphonyl) benzoic acid and 4 - (g  - phenylpropanesulphonyl) benzoic acid are obtained by reaction of p-sulphinobenzoic acid with o-chlorobenzyl chloride, p-methylbenzyl chloride, p-methoxybenzyl chloride, b -phenylethyl bromide and g  - phenylpropyl bromide respectively.  4 - (a  - Phenylethanesulphonyl) benzoic acid is obtained by oxidation with potassium permanganate in neutral aqueous solution of the product of reaction of sodium p-toluenesulphinate with a -phenylethyl bromide.