Patent GB-500471-A (GB)
Title: Improvements in the manufacture and production of halogenated dyestuffs of the phthalocyanine series
IPC: C09B47/10
Filed: 1937-08-04
Abstract: 500,471. Dyes. JOHNSON, G. W. (I. G. Farbenindustrie Akt.-Ges.) Aug. 4, 1937, No. 21500. Samples furnished. [Class 2 (iii)] Halogenated dyestuffs of the phthalocyanine series are manufactured by treating phthalocyanines with halogenating agents in the presence of organic acid hatides (or compounds yielding them under the reaction conditions) or aromatic compounds which are halogenated in a side chain, e.g. mono- or polybasic carboxylic acid halides and sulphohalides, such as acetyl chloride or bromide, chloracetyl chloride, propiony chloride, oxalyl chloride, benzoyl chloride, or bromide, 2 : 5-dichlorobenzoyl chloride, phthalyl, isophthalyl or terephthalyl chloride, benzenesulphochloride or p-toluenehulphochloride, mixtures of compounds forming acid halides under the reaction conditions, e.g. a mixture of phthalic anhydride, thionyl chloride (or benzotrichloride) and zinc chloride, also benzal chloride, benzotrichloride, 2 : 4- dichlorobenzotrichloride or 2 : 6-dichlorobenzal chloride. The reaction may be carried out at 150-250‹ C. at atmospheric or increased pressure, and, if desired, in the presence of additional diluents, e.g. trichlorobenzene, nitrobenzene or trichloracetic acid, and advantageously in the presence of halogen transferrers, e.g. anhydrous ferrous or ferric chloride, copper chloride, zinc chloride, antimony trichloride or pentachloride or trisulphide. The colour strength of the products may be increased by dissolving them in concentrated sulphuric acid, oleum or chlorsulphonic acid and pouring the solution into water. In examples : (1) chlorine is passed into a heated suspension of copper phthalocyanine and antimony trisulphide in benzene- or p-toluenesulphochloride; (2) the reaction of (1) is carried out in the of 2 : 5- or 3:4- dichlorobenzoyl chloride; (3) a mixture of phthalyl chloride and commercial trichlorobenzene is employed as the diluent; (4) the trichlorobenzene in (3) is replaced by an additional quantity of phthatyl chloride ; the phthalyl chloride may be replaced by isophthalyl or terephthalyl chloride ; (5) chlorine is passed into a heated suspension of metal-free phthalocyanine and antimony trisulphide in phthalyl chloride ; (G) chlorine is passed into a mixture of copper phthalocyanine, zinc chloride and phthalic anhydride with simultaneous addition of thionyl chloride ; (7) chlorine is passed into a heated suspension of copper phthalocyanine and antimony trisulphide in benzotrichloride, 2 : 4-dichlorobenzotrichloride, benzal chloride, 2 : 6-dichlorbenzal chloride or benzyl chloride or its substitution products; (8) bromine is dropped, or led in vapour form into a suspension of metal-free phthalocyanine and antimony trisulphide in phthalyl chloride or benzenesulphochloride ; metal-containing phthalocyanines may be similarly brominated; (9) the reaction of (6) is performed under different conditions; the thionyl chloride may be vaporized and led in with the chlorine ; (10) chlorine is passed and thionyl chloride simultaneously allowed to drop into a mixture of disodium phthalocyanine, phthalic anhydride and antimony trichloride ; metal-free phthalocyanine or magnesium phthalocyanine may be similarly treated ; (11) nickel, zinc or other metal phthalocyanines are treated as in (1); chlorine is pressed into a heated pressure vessel containing copper phthalocyanine, antimony trisulphide and oxalyl chloride ; bromine may be employed instead of chlorine. Samples have been furnished under Sect. 2 (5) of phthalocyanines containing both chlorine and bromine prepared by passing a mixture of chlorine gas and bromine vapour into heated suspensions of (A) copper phthalocyanine and (B) nickel phthalocyanine in phthalyl chloride in the presence of antimony trisulphide.