GB797383A - New anthraquinone dyestuffs - Google Patents

Abstract

The invention comprises dyes of the formula <FORM:0797383/IV (b)/1> where R is hydrogen, methyl, or methoxy, X is a direct link or -CnH2nCO2-, Y is a direct link or -(CmH2m-O)p-, and Z is a direct link or -CqH2q-, where n and q are 1, 2, 3 or 4, m is 2 or 3, and p is 1, 2 or 3, provided that X, Y and Z are not all simultaneously direct links. The dyes are made by treating the sulphide of the formula <FORM:0797383/IV (b)/2> with an oxidizing agent such as hydrogen peroxide or manganese dioxide, suitably by heating the reactants in glacial acetic acid. Sulphides specified include 4-m-methylanilino-1-hydroxy-2 - hydroxyethyl -, 4 - p - methoxyanilino - 1 - hydroxy - 2 - b - (b 1 - ethoxy - ethoxy) - ethyl -, and 4 - o - methylanilino - 1 - hydroxy - 2 - b butoxyethyl - mercapto anthraquinones. The dyes containing a glycol ester grouping, i.e. dyes of the above general formula where X is -CnH2nCO2- and Y is -(CmH2m-O)p-, may be made by heating a dye containing an alkyl ester group, i.e. a dye of the above formula where X is -CnH2nCO2-, Y is a direct link and Z is -CqH2q-, with at least one molecular proportion of a glycol or glycol ether in the presence of an ester-interchange catalyst such as p-toluene sulphonic acid. Mixtures of alkyl esters or of glycols may be used. Glycols and glycol ethers specified include mono-, di- and tri-ethylene glycols, propylene and trimethylene glycols, b -hydroxy-ethyl ether, b -(b 1-isopropoxy-ethoxy)-ethanol, and g ,g 1,g 11-methoxypropoxy-propoxy propanol. The dyes dye acetate rayon and polyester fibres reddish-blue and blue shades. The sulphides of the above formula are made by reacting the corresponding 2-bromo-4-anilino - 1 - hydroxy - anthraquinone with sodium polysulphide and treating the sodium mercaptide so formed with a compound of the formula H-Z-Y-X-halogen, where X, Y and Z are as above. Halogen compounds mentioned are butyl bromide, b -butoxyethyl bromide, ethylene chlorohydrin, b -(b 1-ethoxyethoxy)-ethyl chloride, hydroxyethyl chloroacetate and isopropyl - b - chloropropionate. In examples: (1) 4-anilino-1-hydroxy-2-n-butyl-, -2-b - (carboethoxy)ethyl -, - 2 - carboethoxy-methyl-, and -2-b -hydroxyethyl-sulphonyl anthraquinones and 4 - p - methoxyanilino - 1 - hydroxy - 2 - b - hydroxyethyl - sulphonyl - anthraquinone are made by oxidizing the corresponding mercapto-anthraquinones; (2) a mixture of the propylene and diethylene glycol esters of 4-anilino-1-hydroxy-2-carboxymethyl-sulphonyl-anthraquinone is made by heating the corresponding ethyl ester with propylene glycol and diethylene glycol in the presence of p-toluene sulphonic acid; the ethylene glycol ester and a mixture of ethylene and diethylene glycol esters are similarly made by using ethylene glycol or a mixture of ethylene and diethylene glycols respectively.