Patent GB-678087-A (GB)
Title: New vat dyestuffs
IPC: C09B1/42
Filed: 1949-04-25
Abstract: Mono- and di-halogenomethanesulphonylbenzoyl chlorides are made by reacting the corresponding acids with thionyl chloride. The mono-halo-acids may be made by condensing the sodium dihalogenoacetate with the required sulphinobenzoic acid the carboxyl group derived from the acetate being eliminated during the condensation and the di-halo-acids may be made by halogenating the appropriate carboxy-phenylsulphonyl acetate in dilute caustic soda when the carboxylic ester group is also eliminated.  Examples are given of the preparation of (1) m- and (2) p-chloromethanesulphonylbenzoic acid from sodium dichloroacetate and disodium m- or p-sulphinobenzoic acids respectively; (4) m-chloromethanesulphonylbenzoyl chloride from the corresponding acid and (7) m-dibromomethanesulphoxylbenzoic acid is made from bromine and ethyl m-carboxyphenyl-sulphonyl acetate (or the free acid made by reacting sodium chloroacetate with disodium m-sulphinobenzoic acid) in dilute caustic soda.ALSO:The invention comprises dyestuffs of formula <FORM:0678087/IV (c)/1> wherein X is mono- or di-halogenomethyl and at least one of the carbon atoms 4, 5 and 8 is directly attached to a nitrogen atom which forms part of a substituted amino group or of a condensed ring.  They may be made by treating the corresponding a -amino- or a  : a -diamino-anthraquinones with mono- or dihalogeno-methanesulphonyl halides or by treating an anthraquinone intermediate carrying a mono- or dihalogeno-methanesulphonylaroylamino group in an a -position and an amino or halogeno group in a second a -position by methods known to be capable of substituting a hydrogen atom of the amino group in the second a -position or forming a condensed ring containing the nitrogen atom of the said amino group or replacing the halogen atom in the second a -position by a substituted amino group or a nitrogen atom forming part of a condensed ring.  The dyes are superior to known products in fastness to alkaline treatments.  Specified values for X are CH2Cl and CHBr2 and as substituents for the 4, 5 and 8 positions acylamino groups derived from mono- and dicarboxylic acids (e.g. m- or p-chloromethanesulphonyl-benzoic acids, benzoic acid, and tere-and iso-phthalic acids), anthrimide groups, carbazole and acridone ring structures.  The products may be converted to their leuco sulphuric acid derivatives.  In examples: (1) 1 : 4 - di - (m - chloromethanesulphonylbenzoylamino)-anthraquinone is made from the corresponding benzoyl chloride and 1 : 4-diaminoanthraquinone; (2) the para-chloro isomer of the product of (1) is made in a similar way; (3) 1 benzoylamino - 4 - m- or p - chloromethane - sulphonylbenzoylamino - anthraquinones are made from the benzoyl chloride and 1-amino-4-benzoylaminoanthraquinone; (4) 51 : 511 - di - aminoterephthal - bis - 11 : 111-anthraquinononylamide is reacted with m- or p-chloromethanesulphonylbenzoyl chloride in nitrobenzene to yield 51 : 511-di-m- or p-chloromethanesulphonylbenzoylamino - terephthal - bis - 11 : 111 - anthraquinonylamide, these products are also made by reacting terephthalyl chloride with the corresponding m- or p-substituted aminoanthraquinone and similar products are made by replacing terephthalyl chloride by isophthalyl chloride; (5) 6-amino-31 : 41-phthaloyl acridone are reacted with p-chloromethanesulphonylbenzoyl chloride in o-dichlorobenzene and pyridine to yield 6-p-chloromethanesulphonylbenzoylamino-31 : 41-phthaloylacridone and the corresponding m isomer made in a similar way; (6) 1 - chloro - 5 - m - chloromethanesulphonyl - benzoylamino - anthraquinone, 1 - amino - 5 - benzoylamino-anthraquinone and fused sodium acetate are reacted in the presence of cuprous chloride, copper acetate and nitrobenzene to yield 5-benzoylamino-51-m-chloromethanesulphonylbenzoylamino -1 : 11 - dianthrimide which is converted to the corresponding carbazole with acid potassium dichromate, the dianthrimide being also made on reacting 1-chloro-5-benzoylamino-anthraquinone with 1-amino-5-m-chloromethanesulphonylbenzoylaminoanthraquinone; and in (7) 1-amino-4-benzoylamino-anthraquinone is reacted with m-dibromomethanesulphonylbenzoyl chloride to yield 1 - benzoylamino - 4 - m - dibromomethanesulphonylbenzoylamino - anthraquinone.  The 1-amino - 5 - m - or p - chloromethanesulphonyl - benzoylanthraquinones of (4) are made by reacting the required benzoyl chloride with 1 : 5-diaminoanthraquinone, the 1-chloro-5-m-chloromethanesulphonylbenzoyl - aminoanthraquinone of (6) is made by acylating 1-chloro-5-aminoanthraquinone with the m-substituted benzoyl chloride and 5-benzoylamino-51-m-chloromethanesulphonylbenzoylamino-1 : 11-dianthrimide is made by reacting 1-chloro-5-benzoylaminoanthraquinone with 1-amino-5-m-chloromethanesulphonylbenzoylaminoanthraquinone.