Patent GB-589118-A (GB)
Title: New phthalocyanine derivatives
IPC: C09B56/14
Filed: 1945-03-26
Abstract: Phthalocyanine derivatives of the general formula A(XArNH2)n, wherein A represents a metal or metal-free phthalocyanine nucleus, Ar represents a substituted or unsubstituted arylene nucleus, e.g.-C6H4-, -C6H3(CH3)- or -C10H6-, n represents a whole number not exceeding 4, and X represents a simple linkage or a bridging atom or group of atoms, e.g. -S-, -CH2-, -NH-, -S-CH2-, -SO2-CH2-, -CH2-S-, -CH2-O-, -SO2-O-, -SO2-NR-, -NR-SO2- or -NR-CO- (R being hydrogen or a hydrocarbon radical), or (when n is 1, 2 or 3) also -O-, -SO2- or -CO-, are manufactured by reducing compounds of the formula A(XArNO2)n by known methods for the reduction of aromatic nitro compounds to the corresponding amines (the subject-matter of Specification 569,200 being disclaimed).  When n is less than 4, the benzene nucleus or nuclei of the phthalocyanine nucleus not carrying -XArNO2 radicals may contain other nuclear substituents, e.g. chlorine atoms or phenyl or benzoyl groups, whilst when n is greater than 1, X and Ar may be the same or different in the several -XArNO2 groups.  Suitable reducing agents include those of the alkali sulphide class, e.g. sodium sulphide, sodium hydrogen sulphide and the sodium polysulphides, alkali sulphites or bisulphites, alkali hydrosulphites, and tin or zinc or stannous chloride and acid. The products may be diazotized (conveniently in the form of aqueous pastes) and coupled with the usual coupling components to form azo dyestuffs.  Examples describe the reduction of: (1) copper tetra - 4 - (p - nitrobenzoylamino) - phthalocyanine (obtainable by heating copper tetra - 4 - aminophthalocyanine with p - nitrobenzoyl chloride in nitrobenzene); (2) copper tetra - 4 - (m - nitrobenzenesulphonylamino)-phthalocyanine (obtainable from copper tetra-4-aminophthalocyanine and m-nitrobenzenesulphonyl chloride); (3) copper tetra-4-(p-nitrophenylmercapto) - phthalocyanine (obtainable by heating 4-(p-nitrophenylmercapto)-phthalic anhydride with urea, cupric chloride, ammonium molybdate and boric acid in a -chloronaphthalene); (4) copper 3 : 6 : 31 : 61-tetrachloro - 411 : 4111 - di - (p - nitrophenyl mercapto)-phthalocyanine (obtainable similarly from a mixture of equimolecular proportions of 4 - (p - nitrophenylmercapto) - phthalic anhydride and 3 : 6-dichlorophthalic anhydride); (5) copper 3 : 6-dichloro-41 : 411 : 4111-tri - (p - nitrophenylmercapto) - phthalocyanine (obtainable similarly from a mixture of 3 molecular proportions of 4-(p-nitrophenylmercapto)-phthalic anhydride and one of 3 : 6-dichlorophthalic anhydride); (6) copper tetra-4 - (o - nitrophenylmercapto) - phthalocyanine (obtainable similarly from 4-(o-nitrophenylmercapto) - phthalic anhydride); (7) copper phthalocyanine tetra - 4 - sulphon - (p - nitroanilide) (obtained by heating copper phthalocyanine tetra-4-sulphochloride with p-nitraniline and quinoline in nitrobenzene); (8) copper phthalocyanine tetra-4-sulphonic acid p-nitrophenyl ester (obtained by treating copper phthalocyanine 4-sulphochloride similarly with p-nitrophenol); (9) and (10) the corresponding anilide and ester obtained similarly from copper phthalocyanine - trisulphochloride; (11) copper tetra - 4 - (41 - nitro - 31 - methylphenylmercapto) - phthalocyanine (obtainable by heating 4 - (41 - nitro - 31 - methylphenylmercapto) - phthalic anhydride with urea, cupric chloride, ammonium molybdate and boric acid in a -chloronaphthalene); (12) copper tetra-4-(41-nitro - 21 : 51 - dimethoxyphenylmercapto) - phthalocyanine (obtainable similarly from 4-(41 - nitro - 21 : 51 - dimethoxyphenylmercapto) phthalic anhydride); (13) the product obtained by heating chloromethylated copper phthalocyanine (containing 4 chloromethyl groups per molecule) with p-nitrothiophenol and a solution of sodium in excess of b -ethoxyethanol; (14) the product obtained by replacing the greater part of the p-nitrothiophenol in (13) by potassium p-nitrophenate and omitting the sodium.  4 - (p- and o - Nitro-, 41 - nitro - 31 - methyl- and 41 - nitro - 21 : 51 - dimethoxy - phenylmercapto)-phthalic anhydrides are obtainable by condensing p- and o-chloronitrobenzene, 5-chloro-2-nitrotoluene and 4-bromo-2 : 5-dimethoxy-1-nitrobenzene respectively with the tripotassium salt of 4-mercaptophthalic acid, and crystallizing the products from acetic anhydride.