Patent GB-763085-A (GB)
Title: New colouring matters of the tetra-aza-porphin series
Inventor: PARKINSON ALEXANDER
IPC: C09B47/00
Filed: 1954-01-06
Abstract: The invention comprises new colouring matters of the tetra-aza-porphin series which in one of their tautomeric forms are represented by the formula:- <FORM:0763085/IV(b)/1> wherein Me is a metal or two atoms of hydrogen, R1 represents hydrogen or substituted or unsubstituted alkyl, cycloalkyl, or aralkyl, the other R's are hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aryl, or aralkyl, R1 and R2 may form an alicyclic ring, and any or all of the pairs R3 and R4, R5 and R6, R7 and R8 may form substituted or unsubstituted alicyclic or aromatic rings, provided that at least one of the R's consists of or contains a pendant or condensed aryl nucleus substituted by an acid group.  They are made by (1) heating with urea or a heat decomposition product thereof, a substance consisting of or containing a metal, and a catalyst, for example ammonium molybdate, a mixture of a phthalic acid containing a sulpho or a third carboxy group or functional derivative thereof, e.g. the anhydride, with a maleic acid substituted by one or two substituted or unsubstituted alkyl, cycloalkyl, aryl, or aralkyl radicals and optionally a substituted or unsubstituted tetrahydrophthalic acid and/or a phthalic acid optionally substituted other than by an acid group, or with functional derivatives of any of these acids (the metal-free compounds may be made by heating the magnesium compounds with sulphuric acid); or by (2) first synthesizing the tetra-aza-porphins which are free from acid groups or groups which may be converted thereto by treatment with alkali, and then introducing such groups by known methods, e.g. (a) sulphonation, (b) heating with lactones, polycarboxylic anhydrides, halogenated aliphatic acids, or phosphorus trichloride, and Friedel-Crafts catalyst, (c) heating with phosgene, oxalyl chloride, or sulphuryl chloride in a diluent such as trichlorobenzene or aluminium chloride. The products may be used to make lakes, as direct dyes on textiles or paper, or as vat dyestuffs.  In examples, (1) the following are sulphonated with oleum; (a) nickel tetramethyl-dibenz-tetra-aza-porphin, or the corresponding dimethyl-tribenz-, dicyclohexeno-dibenz-, monocyclohexeno-tribenz, tetramethyl-tetrabenzyl, and tetramethyl-tetraphenyl bodies, (b) magnesium tetramethyl-tetrabenzyl-tetra-aza-porphin or the tetramethyl-tetraphenyl body, the magnesium being removed during sulphonation, (c) cobalt hexamethyl-monobenz-tetra-aza-porphin or the tricyclohexeno-monobenz body, (d) metal-free monocyclohexeno-tribenz tetra-aza-porphin.  Also in examples, (2) cobalt or nickel chloride, urea, ammonium molybdate, and nitrobenzene are heated with the following combinations:-(a) dimethylmaleic anhydride and the monopotassium salt of sulphophthalic acid alone or together with phthalic anhydride; (b) dimethylmaleic anhydride, trimellitic or 5-hydroxytrimellitic acid, and phthalic anhydride; (c) D 1-tetrahydrophthalic anhydride and 4-sulphophthalic acid monopotassium salt, with and without phthalic anhydride; (d) D 1-tetrahydrophthalic anhydride and trimellitic acid.  Specifications 686,395, 688,768, 689,387, 689,388 and 689,389 are referred to.