Patent GB-637450-A (GB)
Title: Dyes
IPC: G03C1/10
Filed: 1947-05-05
Abstract: Dyes of the general formula <FORM:0637450/IV (c)/1> wherein A represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring, R is H or a heavy metal (e.g. silver, mercury, or lead), n is 1 or 3, and N-X-N is the radical of an aliphatic, aromatic, or heterocyclic diamine containing two primary amino groups and not more than 14 carbon atoms or of hydrazine are prepared by heating, preferably refluxing, with or without a tertiary base, an alcoholic solution of the diamine or hydrazine with a compound of general formula <FORM:0637450/IV (c)/2> and, wherein R is a heavy metal, reacting with a heavy metal salt. Diamines specified include (in addition to those employed in the examples): o-phenylenediamine, 1 : 5-naphthylenediamine, 2 : 21-, 2 : 41-, or 4 : 41- diaminostilbene, 4 : 41 - diamino - 3 : 31 - dichlorodiphenylmethane, 4 : 41 - diaminobenzophenone, 4 : 41 - diamino - 3 : 31 - dimethoxydiphenylmethane, 2 : 5 - diaminothiodiazole, 2 : 4 - diaminoquinoline, or 2 : 4 - diamino - 6-thio - 3 : 5 - thiadiazine, and second reactants include 4 - (g  - acetanilidoallylidene) - 1 - (2)-benzthiazolyl - 3 - methyl - 5 - pyrazolone, 4-acetanilidomethylene - 3 - methyl - 1 - phenyl-5 - pyrazolone, 4 - (g  - acetanilidoallylidene)-3 - methyl - 1 - phenyl - 5 - pyrazolone, 4-acetanilidomethylene - 3 - methyl - 1 - (2)-pyridyl - 5 - pyrazolone, 5 - acetanilidoallylidene - 3 - allylrhodanine, 5 - acetanilidomethylene - 3 - phenylrhodanine, 5 - acetanilidomethylene - 3 - ethylrhodanine, 5 - (g -acetanilidoallylidene) - 3 - ethyl - 2 - thio-2 : 4 - (3 : 5) - oxazoledione, and 5 - (5 - g -acetanilidoallylidene) - 3 - ethylrhodanine.  In examples, dyes are prepared by refluxing together in isopropyl alcohol containing triethylamine 5 - acetanilidomethylene - 3-allylrhodanine, and (1) p-phenylenediamine; (2) benzidine, and (3) 4 : 41-diaminodiphenylmethane; 3 - acetanilidomethylene - 5 - methylthiophen-2-one, and (4) p-phenylenediamine; (5) benzidine, and (6) 4 : 41-diaminodiphenylmethane; p-phenylenediamine, and (7) 4-acetanilidomethylene - 1 - phenyl - 3 - methyl-5 - pyrazolone; (8) 5 - acetanilidomethylene-3 - phenyl - 2 : 4 - thiazoledione, and (9) 5-acetanilidomethylene - 3 - phenyl - 2 - thio-2 : 4 - oxazoledione; 5 - acetanilidomethylene-3 - allylrhodanine, and (10) ethylene diamine (without triethylamine), and (11) hydrazine hydrate; (12) 5 - (g  - acetanilidoallylidene)-2 - diphenylamino - 3 - ethyl - 4 - (5) - thiazolone and p - phenylenediamine; (13) 5-acetanilidomethylene - 3 - ethyl - 2 - thio-2 : 4 - (3 : 5) - oxazoledione and 2 : 6 - diaminopyridine; (14) 5 - (g  - acetanilidoallylidene) - 3 - ethyl - 1 - phenyl - 2 - thiohydantoin and p-phenylenediamine; (15) 5-(g -acetanilidoallylidene) - 2 : 4 : 6 - triketohexahydropyrimidine and hydrazine hydrate, and (16) 5-(g -acetanilidoallylidene) - 2 - thio - 4 : 6 - diketohexahydropyrimidine and p-phenylenediamine.  The dyes may be reacted with a quaternizing compound (e.g. methyl iodide) and then, in presence of a condensing agent, either with 2 mols. of a cyclammonium base or salt having a reactive methyl group in a -position to the nitrogen atom (e.g. N-methyl-2-methylbenzthiazole). Specification 517,769 is referred to.  The Specification as open to inspection under Sect. 91 comprises also dyes obtained by quaternization and reaction with cyclammonium bases or salts having a reactive methyl group in the a -position to a nitrogen atom to obtain dyes in which the two end nuclei are not the same.  This subject-matter does not appear in the Specification as accepted.