Patent GB-569200-A (GB)
Title: Phthalocyanine derivatives
IPC: C09B47/06
Filed: 1943-09-20
Abstract: Metal phthalocyanines containing four aminophenyl groups attached to the nucleus by links -O-, -SO2- or -CO-, and useful as diazo components for the manufacture of azo dyes, are obtained by heating a corresponding tetra-(nitrophenyl) derivative of phthalic acid, phthalic anhydride, phthalimide or phthalamide with urea and a metal-containing substance and thereafter reducing the nitro groups. The heating is advantageously effected in presence of a substance containing an element of the 5th or 6th group of the periodic table having an atomic number between 15 and 23 or between 33 and 92 inclusive, optionally in conjunction with boric acid.  Specified starting-materials are 4 - (m- or p - nitrobenzoyl) - phthalic acid, 4-(o-, m- or p-nitrobenzenesulphonyl)-phthalic acid, 3- or 4-(p-nitrophenoxy)-phthalic acid, 4 - (p - nitrobenzoyl) - phthalimide, 4 - (m - nitrobenzoyl) - phthalamide, 4 - (p - nitrobenzoyl) - phthalic anhydride and 4-(p-nitrobenzenesulphoyl) - phthalic anhydride, specified metal - containing substances are cupric chloride, nickel chloride, cobaltous chloride and manganese chloride, and specified substances containing the above-defined elements are sodium or ammonium molybdate, diammonium hydrogen phosphate, ammonium vanadate and arsenious oxide.  The reduction of the nitro groups may be effected with sodium hydrogen sulphide, stannous chloride or sodium hydrosulphite.  Examples relate to the production of (1) copper tetra-4-(p-aminobenzoyl)-phthalocyanine by reducing with aqueous sodium hydrogen sulphide the product obtained by heating for 4 hours at 145 DEG  C.  4-(p-nitrobenzoyl)-phthalic acid with urea, anhydrous cupric chloride, ammonium molybdate and boric acid in o-dichlorobenzene; (2) copper tetra-4-(p-aminobenzenesulphonyl)-phthalocyanine by reducing with aqueous stannous chloride the product obtained by heating for 3 hours at 140-145 DEG  C.  4 - (p - nitrobenzenesulphonyl) - phthalic acid with urea, anhydrous cupric chloride and ammonium molybdate; (3) copper tetra - 4 - (p - aminobenzoyl) - phthalocyanine by reducing with aqueous sodium hydrogen sulphide the product obtained by heating for 3 hours at 145-150 DEG  C.  4 - (p - nitrobenzoyl) - phthalic anhydride with urea, anhydrous cupric chloride and ammonium molybdate in o-dichlorobenzene; (4) nickel tetra-4-(p-aminobenzoyl) - phthalocyanine by reducing with aqueous sodium hydrogen sulphide the product obtained by heating for 3 hours at 145-150 DEG  C. 4-(p-nitrobenzoyl)-phthalic acid with urea, anhydrous nickel chloride, ammonium molybdate and boric acid in a -chloronaphthalene; (5) copper tetra - 4 - (p - aminobenzoyl) - phthalo - cyanine by reducing with aqueous sodium hydrogen sulphide or stannous chloride, the product obtained by heating for 2 1/2 hours at 138 DEG  C. 4-(p-nitrobenzoyl)-phthalic anhydride with urea, anhydrous cupric chloride, ammonium molybdate and boric acid in a -chloronaphthalene; (6) copper tetra-4-(p-aminobenzenesulphonyl)-phthalocyanine by reducing with aqueous stannous chloride the product obtained by heating for 2 1/2 hours at 138 DEG  C. 4-(p-nitrobenzenesulphonyl)-phthalic anhydride with urea, anhydrous cupric chloride, ammonium molybdate and boric acid in o-dichlorobenzene; (7) copper tetra-4-(m-aminobenzoyl)-phthalocyanine by reducing with aqueous sodium hydrogen sulphide the product obtained by heating for 2 1/2 hours at 143 DEG  C. 4-(m-nitrobenzoyl)-phthalic acid with urea, anhydrous cupric chloride and ammonium molybdate in o-dichlorobenzene; (8) copper tetra-4-(p-aminophenoxy)-phthalocyanine by reducing with aqueous stannous chloride the product obtained by heating for 3 hours at 145 DEG  C.  4-(p-nitrophenoxy)-phthalic acid with urea, anhydrous cupric chloride and ammonium molybdate.  Specification 529,847 is referred to.  4-(m-Nitrobenzoyl)-phthalic acid is obtained by oxidizing with nitric acid and then with potassium permanganate the product of condensation of benzoyl chloride with tetrahydronaphthalene in presence of aluminium chloride and nitrating the product. 4-(p-Nitrobenzoyl)-phthalic acid is obtained by oxidizing with nitric acid and then with potassium permanganate the product of condensation of p-nitrobenzoyl chloride with tetrahydronaphthalene in presence of aluminium chloride.  4-(o- and p - Nitrobenzenesulphonyl)-phthalic acid are obtained by oxidizing with hydrogen peroxide in acetic acid the products of condensation of 4-mercaptophthalic acid with o-and p-nitrochlorobenzenes respectively. 4-(m-Nitrobenzenesulphonyl)-phthalic acid is obtained by nitrating the product of condensation of benzenesulphonyl chloride with tetrahydronaphthalene in presence of aluminium chloride and oxidizing the nitration product with nitric acid and then with potassium permanganate.  3-(p-Nitrophenoxy)-phthalic acid is obtained by heating potassium phenate with the dipotassium salt of 3-chlorophthalic acid in molten phenol and nitrating the product. 4-(p-Nitrophenoxy)-phthalic acid is obtained by condensing p-nitrochlorobenzene with 4-hydroxy-1 : 2-dimethylbenzene and oxidizing the product with nitric acid and then with potassium permanganate.  4-(p-Nitrobenzoyl)-phthalimide is obtained by heating the corresponding acid with urea.  4-(m-Nitrobenzoyl)-phthalamide is obtained by heating the corresponding acid with urea to produce the phthalimide and heating this with aqueous ammonia. 4-(p-Nitrobenzoyl)-phthalic anhydride is obtained by heating the corresponding acid with acetic anhydride.  4 - (p - Nitrobenzenesulphonyl) - phthalic anhydride is obtained by heating the corresponding acid with acetic anhydride.