Patent GB-784786-A (GB)
Title: Dyestuffs and intermediates of the anthraquinone series
IPC: C09B1/60
Filed: 1954-06-29
Abstract: The invention comprises (1) dyes of the formula <FORM:0784786/IV (b)/1> in which one Z is hydrogen, and the other is a group of the constitution <FORM:0784786/IV (b)/2> or <FORM:0784786/IV (b)/3> in which both X's are hydrogen or together with the -C-C group represent a carbocyclic ring (e.g. cycloaliphatic, e.g. cyclohexane), or in which one X is hydrogen and the other is alkyl or aryl (e.g. methyl or phenyl), and also (2) compounds of the above formula, except that both X's should not be hydrogen, in which the halogen or -SCN group is replaced by amino, o-acyl, alkoxy, or hydroxy.  The invention also comprises (3) compounds of the formula <FORM:0784786/IV (b)/4> in which one Z is hydrogen, and the other is -S-R3, where R3 is an ethylene-benzene residue bound to the sulphur atom by an ethylene carbon atom.  The invention also comprises a process of preparing compounds such as those numbered (1) by reacting an unsaturated organic compound with a compound Aq-S-Halogen or Aq-S-SCN in which Aq is a vattable residue, e.g. anthraquinone, bound to the sulphur atom by an aryl carbon atom, unsaturated compounds specified being cyclohexene, styrene, 2-methyl-1 - phenylethylene, 1 - methyl - 1 - phenyl-ethylene, allylbromide, isobutylene, and butadiene, and the reaction being preferably carried out at a raised temperature in an organic solvent (e.g. glacial acetic acid, chloroform, or tetrachlorethane).  Sometimes the reaction is accompanied by the splitting off of hydrogen halide to give compounds numbered (3), as in the reaction of anthraquinone 1-sulphenyl bromide with 1-methyl-1-phenyl-ethylene.  Compounds numbered (2) are obtained from those numbered (1) by methods known to be suitable for exchanging halogen for amino, -O-acyl, alkoxy, or hydroxy.  The products dye or print cellulose acetate, nylon, or polyester fibres.  In examples: (1) anthraquinone-1-sulphenyl bromide or the 2-sulphenyl chloride is reacted with cyclohexene in glacial acetic acid to give 1 - (21 - bromo - cyclohexyl - mercapto)-anthraquinone or 2-(21-chlorocyclohexyl-mercapto)-anthraquinone; (2) anthraquinone-1-sulphenyl bromide or the 2-sulphenyl chloride is reacted with styrene; (3) anthraquinone-1-sulphenyl thiocyanate (obtained from the bromide by reaction with potassium thiocyanate) is reacted with cyclohexene; (4) anthraquinone-1-sulphenyl bromide is reacted with 1-methyl-1-phenyl ethylene to give 1-(phenyl-vinyl-mercapto) anthraquinone; (5) anthraquinone-1-sulphenyl bromide is reacted with allyl bromide.  A further example describes the acid pasting of 1-(21-bromo-cyclohexyl-mercapto)-anthraquinone, dispersion of the product with sulphite cellulose waste liquor and use of the dispersion to dye cellulose acetate or nylon; (6) 1-(21-bromo-cyclohexyl-mercapto) anthraquinone is (a) reacted with silver acetate to give 1-(21-acetoxy-cyclohexyl-mercapto)-anthraquinone; (b) reacted with sodium methylate to give 1-(21-methoxy-cyclohexyl)-mercapto-anthraquinone; (7) 1-(21-acetoxy - cyclohexyl) - mercapto - anthraquinone is boiled with alcoholic potash to give 1-(21-hydroxycyclohexyl) - mercapto - anthraquinone.