A method for the production of nickel - or cobalt tetra - aza - porphines or their alkyl - and cyclo alkyl substituted derivatives

摘要

Dimethylmaleic monoamide mononitrile is obtained by action of ammonia on dimethylmaleic mononitrile monoester. Dimethylmaleic mononitrile monoester is obtained by dehydrating the cyanhydrin of a -methylacetoacetic ester. Methylethylmaleic and methylethylfumaric dinitriles are obtained by dehydration of methylethyl malic dinitrile, i.e. the cyanhydrin of a -ethyl acetoacetonitrile.ALSO:The invention comprises violet colouring matters of the formula FORM:0689389/IV (c)/1 where the R's are hydrogen, alkyl, or cycloalkyl radicals which may be substituted, and Me is nickel or cobalt. They are made by (1) heating maleic dinitrile or an alkyl- or cycloalkyl-substituted maleic or fumaric dinitrile or a mixture of any two or more of these dinitriles with nickel or cobalt or a compound of either, alone or in presence of ammonia or a salt thereof, an amine or a salt thereof, or an amide such as urea, and preferably in presence of a substance consisting of or containing molybdenum or wolfram; or (2) by heating the corresponding metal-free tetra-aza-porphin with a substance consisting of or containing nickel or coba or (3) heating an alkyl- or cycloalkyl-substituted maleic acid or a functional derivative thereof with urea or a nitrogenous heat decomposition product thereof other than ammonia, and nickel or cobalt or a compound of either, preferably in presence of a substance consisting of or containing molybdenum or wolfram, and while passing ammonia through the mixture. Suitable diluents are nitrobenzene, mono- and di-chlorbenzene, chlornaphthalene, quinoline, dimethylaniline, ethyl benzoate, and kerosene. As functional derivatives of the maleic acids are mentioned the amide, imide, dichloride, or ammonium salt, or the mononitrile derived from the acid, amide, or ammonium salt. In examples: (1) dimethylmaleic anhydride, methylethyl maleic anhydride, methyl-isopropyl maleic anhydride, methyl n-butylmaleic anhydride, methylcyclohexylmaleic anhydride, and a mixture of dimethylmaleic and methylethyl maleic anhydrides, or various functional derivatives of dimethyl maleic acid as indicated above, are each heated with urea, nickel, or its chloride or oxide, ammonium molybdate or sodium wolframate and one of the diluents listed above; (2) dimethylmaleic anhydride is similarly heated with cobaltous chloride; (3) dimethylmaleic and dimethylfumaric dinitrile, are each heated with nickel chloride, alone, with urea and ammonium molybdate, and with urea, ammonium molybdate, and nitrobenzene or kerosene; (4) maleic dinitrile, citraconic dinitrile, a mixture of methylethylmaleic and methylethylfumaric dinitriles, and a mixture of maleic dinitrile and dimethylmaleic dinitrile is treated similarly; (5) dimethylfumaric dinitrile is heated with urea, cobaltous chloride, and ammonium molybdate; (6) dimethylmaleic dinitrile is heated with sodium in amyl alcohol, the sodium compound is demetallized with methanol, and the metal-free pigment is heated with nickel or cobalt acetate in quinoline. Specification 689,387 is referred to.