Patent GB-452203-A (GB)
Title: New anthraquinone dyestuffs
IPC: C09B1/58
Filed: 1934-11-14
Abstract: New dyestuffs are made by replacing one halogen atom in a 2 : 3-dihalo-geno-1 : 4-diaminoanthraquinone by an alkylphenoxy, alkyloxyphenoxy, alkylthiolphenoxy, alkylphenylthiol, alkyloxyphenylthiol or alkylthiolphenylthiol substituent and replacing the other halogen atom by one of the same substituents or by an alkylthiol substituent (the alkyl groups throughout containing 4 to 7 carbon atoms), and finally sulphonating, the replacement by the aromatic substituents being effected by treating with the corresponding phenol or thiophenol and that by the alkylthiol substituent by first treating with an alkali metal sulphide or disulphide and then alkylating The dyestuffs may be further substituted in the nuclei by methyl, chlorine or bromine. The dyestuffs dye animal fibres from neutral or slightly acid baths and preferably in presence of an assistant such as cetyl sodium sulphate or Glauber's salt, violet to green-blue shades, specially fast to washing and milling.  The treatment with the phenol or mercaptan may be effected in water, pyridine, or alcohol or in excess phenol or mercaptan in presence of caustic alkali. The following examples are specified: (1) Sodium-2-chloro-1 : 4-diamino-3-mercaptoanthraquinone (cf. Specification 387,765) is condensed with n-butyl bromide and the 2-chloro- 1 : 4-diamino-3-n-butyl-thiolanthraquinone so obtained is condensed with p-n-butylphenol to give 1 : 4-diamino-2-p-n-butylphenoxy - 3 - n - butylmercaptoanthraquinone, which is then sulphonated; p-n-butyl bromide may be replaced by isoamyl bromide and the p-n-butyl phenol by p-isoamylphenol; (2) Woollen yarn is dyed a bright violet, fast to washing, milling and light, by treatment in a dyebath, brought to the boil and so maintained for 1 hour, containing sodium cetyl sulphate; (3) 2 : 3-Dichloro-1 : 4-diaminoanthraquinone is condensed with p-n-butyl- or p-iso-amylphenol and the product sulphonated; (4) 2 - Chloro - 1 : 4 - diamine - 3 - isoamylthiol - anthraquinone is condensed with p-n-butylphenylmercaptan and the 1 : 4-diamino-2-p-n-butyl - phenylthiol - 3 - isoamylthiolanthraquinone so obtained is sulphonated; similarly 2 - chloro - 1 : 4 - diamino - 3 - n - butylthiol - anthraquinone may be condensed with p-isoamylphenylmercaptan and the product sulphonated; (5) 2 : 3-Dichloro-1 : 4-diaminoanthraquinone is condensed with p-n-butylphenylmercaptan to obtain 1 : 4-diamino-2 : 3-bis-p-n-(butylphenylthiol)-anthraquinone which is then sulphonated; (6) 2 : 3 - Dichloro - 1 : 4-diaminoanthraquinone is condensed with p-isoamyloxyphenylmercaptan to obtain 1 : 4-diamino - 2 : 3 - bis - p - (isoamyloxyphenylthiol) anthraquinone, which is then sulphonated; (7) 2-Chloro-1 : 4-diamino-3-n-butylthiol anthraquinone is condensed with p-isoamyloxyphenyl-mercaptan and the product sulphonated; (8) The p-n-butyl-phenylmercaptan of example 5 is replaced by p-n-butylthiolphenyl mercaptan; (9) 1 : 4-diamino-2 : 3-dichloro-anthraquinone is treated with p-n-butylphenol to replace one chlorine atom and then successively with sodium disulphide solution and butyl bromide to produce the product of (1). Specification 26944/11, [Class 2 (iii)], also is referred to. Thiophenol derivatives.--p-n - Butylphenylmercaptan is obtained from p-n-butylaniline by diazotization, coupling with potassium ethyl xanthate and hydrolyzing with caustic soda; p-isoamylphenylmercaptan, p-isoamyloxy-phenylmercaptan and p-butylthiolphenylmercaptan are obtained similarly from p-isoamylaniline, p-isoamyloxyaniline and p-aminophenyl - butyl sulphide respectively.  Specification 430,160 also is referred to.