Patent GB-586340-A (GB)
Title: Phthalocyanine derivaties
IPC: C09B47/12
Filed: 1944-11-17
Abstract: Phthalocyanine derivatives which, depending on the reaction conditions employed, contain a varying number of chloromethyl or bromomethyl groups, are manufactured by heating a metal or metal-free substituted or unsubstituted phthalocyanine with aluminium chloride and with sym.-dichloro- or -dibromo-dimethyl ether or paraformaldehyde, preferably in the presence also of a tertiary amine not itself susceptible of chloro- or bromo-methylation.  The process may be carried out by mixing together aluminium chloride, the tertiary base and the chloro-or bromo - methylating agent, adding the phthalocyanine derivative and heating the mixture, usually for about an hour to about 20-95 DEG  C. or higher.  The products (which, when starting with metal-free phthalocyanines, contain a proportion of aluminium phthalocyanine derivatives) may be reacted with tertiary amines to produce quaternary ammonium salts, with mercaptans to give sulphides and with thiourea to give isothiouronium salts, and are thus of value as intermediates in the manufacture of further dyestuffs and pigments.  In examples: (1) copper phthalocyanine is heated to about 60 DEG  C. with a mixture of anhydrous aluminium chloride, triethylamine and sym.-dichlorodimethyl ether, producing mainly copper tri-(chloromethyl)-phthalocyanine; (2) the triethylamine in (1) is omitted, the product being mainly copper di - (chloromethyl) - phthalocyanine; (3) the heating in (1) is effected at 85-90 DEG  C., yielding mainly copper tetra-(chloromethyl)-phthalocyanine; (4) the triethylamine in (1) is replaced by pyridine, the product being similar to that of (3); (5) the sym.-dichlorodimethyl ether in (1) is replaced by paraformaldehyde, the quantity of aluminium chloride being increased and that of triethylamine reduced, to produce a mixture of copper di- and tri-(chloromethyl)-phthalocyanines; (6) the sym.-dichlorodimethyl ether in (1) is replaced by sym.-dibromodimethyl ether and heating is effected at 75-80 DEG  C., the product being mainly copper tri-(bromomethyl)-phthalocyanine, but containing also a small proportion of chlorine; (7) nickel phthalocyanine is treated as in (1), yielding a mixture of nickel di- and tri-(chloromethyl)-phthalocyanines; (8) metal-free phthalocyanine is treated as in (1), the product being mainly tri-(chloromethyl)-phthalocyanine but containing some aluminium; (9) copper tetra-4-benzoyl-phthalocyanine is treated as in (1), producing mainly copper tetra - (chloromethyl) - tetra - 4 - benzoylphthalocyanine; (10) copper tetra-4-phenylphthalocyanine is stirred with excess of sym.-dichlorodimethyl ether and anhydrous aluminium chloride at 20-30 DEG  C., yielding mainly copper octa - (chloromethyl) - tetra - 4 - phenylphthalocyanine; (11) copper tetra-4-thiocyanophthalocyanine is heated to 50-53 DEG  C. with a mixture of anhydrous aluminium chloride, pyridine and sym.-dichlorodimethyl ether, producing mainly copper tri-(chloromethyl)-tetra-4-thiocyanophthalocyanine; (12) the heating in (4) is effected at 65-67 DEG  C. to produce a mixture of copper penta- and hexa-(chloromethyl)-phthalocyanine; (13) copper tetra-4-phenylphthalocyanine is treated with anhydrous aluminium chloride and sym.-dichlorodimethyl ether in nitrobenzene at 25-30 DEG C., producing mainly copper tetra - (chloromethyl) - tetra - 4 - phenylphthalocyanine.  Other starting materials specified are iron and aluminium phthalocyanines and copper octa-3 : 6-chlorophthalocyanine.  The Provisional Specification comprises the use, as chloromethylating agent, of any substance which, in the presence of aluminium chloride, can give rise to sym.-dichlorodimethyl ether.