Patent GB-632808-A (GB)
Title: Cyanine dyes derived from 1, 3, 4-triazaindolizines and photographic silver halide emulsions sensitized therewith
IPC: G03C1/83
Filed: 1947-02-13
Abstract: 5 : 7 -Dimethyl - 2 - phenyl - 1 : 3 : 4 - triazaindolizine is prepared by refluxing together 5-phenyl-3-amino-1 : 2 : 4-triazole and acetyl-acetone in ethyl alcohol containing piperidine.  5 : 7 - Dimethyl - 2 - isopropyl - 1 : 3 : 4 - triazaindolizine, 5 : 7 - diethyl - 1 : 3 : 4 - triazaindolizine (using 3-aminotriazole and 3 : 5-heptanedione), and 5-ethyl-7-(4-methoxyphenyl)-2-propyl-1 : 3 : 4-triazaindolizine (using 5-propyl-3-amino-1 : 2 : 4-triazole and 1-(p-methoxyphenyl)-1 : 3-pentanedione) are similarly prepared.  6 - Carbethoxy - 5 - methyl - 1 : 3 : 4 - triazaindolizine is prepared be refluxing ethyl ethoxy methylene-acetoacetate and aminotriazole in glacial acetic acid.  6-Carbethoxy-5 : 7-dimethyl-1 : 3 : 4-triazaindolizine is similarly prepared.ALSO:Mono- and poly-methine unsymmetrical dyes of one of the formul  <FORM:0632808/IV (c)/1> <FORM:0632808/IV (c)/2> wherein R and R7 are alkyl or aralkyl, R2 is H, alkyl, aryl, or carbalkoxy, R3 and R4 are H or alkyl, aryl, aralkyl, alkoxyphenyl, or dialkoxyphenyl, R5 is H or alkyl, R6 is H or methyl, n is 1, 2 or 3, X is an acid radical, and Z represents the atoms to complete a heterocyclic nitrogen ring of the type usual in cyanine dyes are prepared by condensing a quaternary salt of a 1 : 3 : 4-triazaindolizine base of formula <FORM:0632808/IV (c)/3> wherein R1 represents an alkyl group and R2, R2 and R4 are as above with reactive derivatives of quaternary salts of the usual heterocyclic nitrogen bases, e.g. by refluxing together in presence of a condensing agent with or without an additional solvent.  The dyes may be monoto hepta-methine cyanine dyes, including dyes with substituted methine chains, or styryl dyes.  They may be derived from the following 1 : 3 : 4 - triazaindolizines -, 5 : 7-dimethyl -, 5 - methyl - 7 - phenyl -, 5 : 7-dimethyl - 2 - phenyl -, 5 : 7 - dimethyl - 2-isopropyl -, 2 : 5 : 7 - trimethyl -, 6 - carbethoxy - 5 - methyl -, 6 - carbethoxy - 5 : 7-dimethyl -, 5 : 7 - diethyl -, 2 : 5 : 6 : 7-tetramethyl -, 5 : 6 : 7 - trimethyl -, 2 : 5-dimethyl - 7 - phenyl -, 5 - ethyl - 7 - (4-methoxyphenyl) - 2 - propyl -, and 5 - methyl-7-p-tolyl.  Monomethine dyes are obtained by reaction with 2-methylmercapto-, 2-phenylmercapto-, 2-phenylmethylmercapto-, and 2-iodo-derivatives of quaternary salts of the usual bases, trimethine dyes by reaction with 2 - (b  - acetanilidovinyl) derivatives of the quaternary salts of the usual bases and with 2 - (b  - methylmercaptovinyl) - 3 : 3 - dimethylindolenine ethiodide and 2-formylmethyl-1-ethylthiazoline, meso-substituted trimethyl dyes using 2-(b -methylmercapto-b -methyl, ethyl, or propyl-vinyl) derivatives, pentamethine dyes using 4 - anilino - 1 : 3 - butadienyl, 2 - (4-acetanilido - 1 : 3 - butadienyl) -, 2 - (4 - ethoxy-1 : 3 - butadienyl)-, or 2 - (3 - formyl - 2 - propenylidene) - derivatives, chain - substituted pentamethine dyes using 2-(4-anilino-3-methyl, ethyl, propyl, or butyl-1 : 3-butadienyl)- derivatives, heptamethine dyes using 2-(6-anilino-1 : 3 : 5 - hexatrienyl) - or 2 - (5 - formyl-2 : 4-pentadienylidene)-derivatives, chain-substituted heptamethine dyes using 2-(6-anilino-4-methyl, ethyl, propyl, or butyl-1 : 3 : 5-hexatrienyl)-derivatives, and styryl dyes using a dialkylaminobenzene.  The preparation of the following dyes is given: (1) a monomethine dye from 2-isopropyl-5 : 7-dimethyl-1 : 3 : 4-triazaindolizine ethiodide and 2-methylmercapto-6-methoxyquinaldine ethiodide; (2) a substituted monomethine dye from 5-ethyl-7-(4 - methoxyphenyl) - 2 - propyl - 1 : 3 : 4-triazaindolizine ethiodide and 2-methylmercaptobenzthiazole methiodide; (3) a trimethine dye from 5-methyl-7-phenyl-1 : 3 : 4-triazaindolizine ethiodide and 2-acetanilidovinylbenzthiazole ethiodide; (4) a meso-substituted trimethine dye from 5 - methyl - 7 - phenyl-1 : 3 : 4 - triazaindolizine ethiodide and 2-(b  - ethylmethylmercaptovinyl) - 5 - methoxybenzthiazole ethiodide; (5) a pentamethine dye from 2 - phenyl - 5 : 7 - dimethyl - 1 : 3 : 4-triazaindolizine ethiodide and 2-(4-ethoxy-1 : 3-butadienyl)-benzthiazole ethiodide; (6) a chain-substituted pentamethine dye using the first reactant of (5) with 2-(4-anilino-3-methyl-1 : 3 - butadienyl) - benzoxazole ethiodide; (7) a heptamethine dye from 5-methyl-7-p-tolyl - 1 : 3 : 4 - triazaindolizine ethiodide and 2 - (6 - anilino - 1 : 3 : 5 - hexatrienyl) - thiazoline methiodide; (8) a chain-substituted heptamethine dye from 2 : 5 : 7-trimethyl-1 : 3 : 4 - triazaindolizine ethiodide and 2-(6 - anilino - 4 - ethyl - 1 : 3 : 5 - hexatrienyl)-benzthiazole ethiodide, and (9) a chain-disubstituted heptamethine due using the second reactant of (8) with 5 : 7-diethyl-1 : 3 : 4-triazaindolizine ethiodide.  Specifications 354,898, 355,693, 412,309, 423,792, 424,559, 425,609, 434,234, 434,235, [Group XX], 438,420, 438,449, 438,450, 438,484, 454,687, 466,246, and 466,269 are referred to.  The Specification as open to inspection under Sect. 91 comprises also dyes derived from the following 1 : 3 : 4-triazaindolizines: 5 : 7-dimethyl - 2 - propyl -, 5 : 7 - dimethyl - 6-phenyl -, 5 : 7 - diethyl - 2 - phenyl -, 5 : 7-dimethyl - 2 - p - tolyl, 6 - ethyl - 5 : 7 - dimethyl-, 6 - carbmethoxy - 5 - methyl - 2-phenyl -, 5 : 7 - dimethyl - 2 - (2 - methoxyphenyl) -, 5 - methyl - 7 - (4 - methoxyphenyl)-, and 5 - methyl - 7 - (2 : 4 - dimethoxyphenyl).  This subject-matter does not appear in the Specification as accepted.