Patent GB-637648-A (GB)
Title: Merocyanine and oxonol dyes and process for their preparation
IPC: C09B23/02
Filed: 1946-11-25
Abstract: Compounds of the general formula <FORM:0637648/IV (b)/1> wherein Z represents the non-metallic atoms to complete a heterocyclic nucleus, are prepared by reacting an amine compound of the general formula <FORM:0637648/IV (b)/2> with ethyl malonate.  Amino compounds specified are 2-aminothiazoline, 2-aminoselenazole, 2-aminodihydrothiazine, 2-amino-5-methylthiazoline, 2-amino-4-phenylthiazoline, 2-aminohexahydrobenzthiazole, 3-phenyl-5-aminopyrazolone, and 2-aminopyridine.ALSO:A cyanine dye is derived from the nucleus <FORM:0637648/IV (c)/1> wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus. The dye may have one of the following formul  <FORM:0637648/IV (c)/2> <FORM:0637648/IV (c)/3> <FORM:0637648/IV (c)/4> wherein X and Z represent the non-metallic atoms necessary to complete heterocyclic nuclei, n is 0, 1 or 2, and R represent an aliphatic, cycloaliphatic, aryl or aralkyl group.  X may complete a benzoxazole, benzthiazole, benzselenazole, thiazoline, selenazoline, pyridine, benzoquinoline, or 3 : 3-dimethylindolenine nucleus, and Z a thiazoline, selenazoline, hexahydrobenzthiazole, 3 - phenylpyrazolone, pyridine, quinoline, or thiazine nucleus.  The nucleus I may be derived from 2-aminothiazoline, 2 - aminoselenazoline, 2 - aminodihydrothiazine, 2 - amino - 5 - methylthiazoline, 2 - amino - 4 - phenylthiazoline, 2 - aminohexahydrobenzthiazole, 3 - phenyl - 5 - aminopyrazolone, and 2 - aminopyridine, and may be condensed with (a) a cyclammonium quaternary salt having in the 2- or 4-position an iodo, cyano, or aryl- or alkyl-mercapto substituent; (b) a heterocyclic compound having in the 2- or 4-position an acetanilidomethylene, formyl, or methyl substituent, or (c) a cyclammonium quaternary salt having in the 2- or 4-position a b -anilinovinyl, b -acetanilidovinyl, acetylmethylene, b -alkylmercaptovinyl, or b -alkylmercapto-b -alkylvinyl substituent.  Alternatively, an acetanilidomethylene derivative of a compound having the structure (I) may be condensed with a cyclammonium quaternary salt having a methyl group in the 2- or 4-position.  A condensing agent such as acetic, propionic, or butyric anhydride; triethyl, tributyl, or triethanol amine; N-methylpiperidine; pyridine; sodium or potassium acetate; or sodium ethylate or propionate may be used. In examples, dyes are formed by refluxing together (1) thiazolopyrimidinedione, 2 - (b  - acetanilidovinyl) - 6-methylbenzthiazole ethiodide, isopropyl alcohol, and triethylamine; (2) thiazolopyrimidinedione, 2 - (b  - acetanilidovinyl) - benzthiazole ethiodide, isopropyl alcohol, and triethylamine; (3) phenylthiazolopyrimidinedione, 2 - (b -methylmercapto - b  - ethylvinyl) - 6 - methoxybenzselenazole ethiodide, n-propyl alcohol, and triethylamine; (4) thiazinopyrimidinedione, 2 - (b  - acetanilidovinyl) - 6 - methoxybenzselenazole, ethiodide, n-propyl alcohol, and triethylamine; (5) hexahydrobenzthiazolopyrimidinedione, 2 - (b  - acetanilidovinyl)benzthiazole ethiodide, isopropyl alcohol, and triethylamine; (6) methylthiazolopyrimidinedione, 2 - (b  - acetanilidovinyl) - benzoxazole ethiodide, isopropyl alcohol, and triethylamine; (7) thiazinopyrimidinedione, 2 - thio - 3 - ethyl-5 - acetanilidomethylenedihydrothiazolidone-4, pyridine, and triethylamine; (8) 2 : 3 : 6 : 7-tetrahydro - 5 : 7 - dioxo - 5 - thiazolopyrimidine, 2 - phenylmercaptobenzthiazole ethidide, isopropyl alcohol, and triethylamine; (9) 2 : 3 : 6 : 7 - tetrahydro - 5 : 7 - dioxo - 5-thiazolopyrimidine, 2 - (4 - acetanilidobutadienyl) - benzthiazole ethiodide, triethylamine, and ethyl alcohol; and (10) the compound produced by reacting together 2 : 3 : 6 : 7-tetrahydro - 5 : 7 - dioxo - 5 - thiazolopyrimidine and diphenylformamidine in the presence of acetic anhydride, 2 - methylbenzthiazole ethiodide iso propyl alcohol, and triethylamine.