Patent GB-437266-A (GB)
Title: New colouring matters
IPC: C09B1/60
Filed: 1934-03-19
Abstract: Anthraquinonyl alkyl sulphides, containing 8--20 carbon atoms in the alkyl groups and containing also one or more auxochromic groups, such as amino, alkylamino, hydroxyalkylamino, arylamino, hydroxy, aryloxy, or benzylmercapto groups, are prepared, (1) by causing a mono- or poly-mercaptoanthraquinone containing one or more auxochromic groups, with or without chlorine or bromine atoms, to react with an alkyl chloride or bromide containing 8--20 carbon atoms, or (2) by causing a mono- or poly-chloro- or bromoanthraquinone containing one or more auxochromic groups to react with an alkyl mercaptan containing 8--20 carbon atoms.  The products are useful for colouring oils, spirits, waxes and rubber, or they may be converted into acid dyes by sulphonation or (if chlorine or bromine is present) by reaction with alkali sulphite; the acid dyes are also obtainable (1) by treating mercaptoanthraquinone sulphonic acids containing one or more auxochromic groups with alkyl chlorides or bromides containing 8--20 carbon atoms, or (2) by treating chloro- or bromo-anthraquinone sulphonic acids containing one or more auxochromic groups with alkyl mercaptans containing 8--20 carbon atoms.  The acid dyes have soap-like properties in aqueous solution, and are preferably applied from a bath more weakly acid than usual, e.g. a bath in which ammonium acetate is used as the source of acid.  In the examples, (1) 1 : 4-diamino-2-mercaptoanthraquinone (from 1 : 4-diamino-2-bromanthraquinone and sodium hydrosulphide) is treated with cetyl bromide to yield 1 : 4-diamino-2-anthraquinonyl cetyl sulphide; (2) 2-chloro-1 : 4-diamino-3-mercaptoanthraquinone (Specification 387,765) and dodecyl bromide yield 2-chloro-1 : 4-diamino-3-anthraquinonyl dodecyl sulphide; (3) 1-amino-5 - mercaptoanthraquinone (from 1 - amino - 5-chloroanthraquinone and sodium disulphide) is treated with dodecyl bromide; (4) 1-bromo-4-methylaminoanthraquinone is treated with cetyl mercaptan to yield 1-methylamino-4-anthraquinonyl cetyl sulphide; (5) 1-amino-4-anilino - 2 - mercaptoanthraquinone (from 2-bromo - 1 - amino - 4 - anilinoanthraquinone and sodium hydrosulphide) is treated with dodecyl bromide or (example 6) with cetyl bromide; (7) 1 : 4 - diamino - 2 - phenoxy - 3 - mercaptoanthraquinone (Specification 387,765) is treated with dodecyl bromide or (example 8) with cetyl bromide; (9) 1 : 4-diamino-2-mercapto-3-benzylmercaptoanthraquinone (from 1 : 4-diamino-2-chloro-3-benzylmercaptoanthraquinone and sodium sulphide, as described in French Specification 668,871) is treated with dodecyl bromide; (10) 2 : 3-dichloro-1 : 4-dianilinoanthraquinone (from 1 : 2 : 3 : 4 - tetrachloranthraquinone and aniline) is treated with sodium hydrosulphide to yield 1 : 4-dianilino-2 : 3-dimercaptoanthraquinone, which is then treated with cetyl bromide; (11) 2-bromo-1-amino - 4 - hydroxyethylanthraquinone (from 1 : 3 - dibromo - 4 - aminoanthraquinone and ethanolamine) is treated with sodium disulphide, and the product is treated with dodecyl bromide; (12), (13), and (14) 1 : 4-diamino-2-p- (or o- or m-) cresyloxy-3-mercaptoanthraquinone, obtainable by the process of Specification 387,765, is treated with dodecyl bromide; (15) 1-amino-4-anilino-2-anthraquinonyl dodecyl sulphide is sulphonated with oleum; (16) 2-bromo-1-amino-4-p-anisidinoanthraquinone is sulphonated with oleum, and the product is treated with sodium hydrosulphide; the 1-amino-4-p-anisidino-2-mercaptoanthraquinonesulphonic acid so obtained is treated with dodecyl bromide; (17) the product of example 6 is sulphonated with oleum; (18) the product of example 11 is sulphonated with sulphuric acid or by heating it with pyridine and sodium pyrosulphate; (19)--(22) the products of examples 12, 13, 14 and 8 are sulphonated with sulphuric acid; (23) the product of example 2 is heated with aqueous sodium sulphite in the presence of phenol to yield a blue acid dye; (24) the process of example 23 is applied to 2-chloro-1 : 4-diamino-3-anthraquinonyl cetyl sulphide; (25) the product of example 9 is sulphonated with sulphuric acid; (26) sodium 2-chloro-1-amino-4-anilinoanthraquinone-p-sulphonate is heated with octadecyl mercaptan in the presence of pyridine and caustic soda; a blue acid dye is obtained.  Specifications 29139/09, 28723/11, and 285,969, [all in Class 2 (iii)], also are referred to. The Provisional Specifications refer to Specification 430,160.