Patent GB-553144-A (GB)
Title: Improvements in and relating to dyestuffs, especially for use as photographic sensitising dyestuffs
IPC: C09B23/08
Filed: 1941-11-06
Abstract: 553,144. Methine dyes; photographic silver halide emulsions. KENDALL, J. D., WOOD, H. W., and MAJER, J. R. Nov. 6, 1941, No. 14313. Samples furnished. [Class 2 (iii)] [Also in Group XX] Methine dyes are prepared by condensing a dye intermediate of formula (where D, is the residue of a 5- or 6-membered heterocyclic nitrogen nucleus, R, is alkyl, hydroxyalkyl, or aralkyl, R 2  is hydrogen or alkyl or aralkyl, R 3  is alkyl, R 5  is alkyl or aralkyl, A is an acid residue, and n is 0 or 1) with a cyclic compound containing a reactive methylene group. The dye intermediates may be prepared as described in Specification 553,143. The cyclic compound may be (a) a five-membered ring compound containing the system where D is the residue of a 5-membered heterocyclic nitrogen keto-methylene ring and R is hydrogen or a hydrocarbon group ; (b) a quaternary salt of a heterocyclic nitrogen compound having a reactive methyl group, mono-substituted methyl group, or external methylene group in the α- or γ-position to a heterocyclic nitrogen atom ; (c) a carbocyclic compound containing a keto-methylene group. If the ring in (a) corresponds with the formula (R being hydrogen or a hydrocarbon group and X an oxygen or sulphur atom), the resulting product may be treated with an alkyl or aralkyl salt and condensed with any of the compounds (a), (b), or (c). This process may be repeated. Compounds of type (a) are rhodanic acid, 2 - thio - 4 - keto - tetrahydro - oxazole, the N- hydrocarbon derivatives thereof, oxindoles, pyrazole - 5 - ones, hydantoin, thiohydantoin, # - hydantoin, and # - thiohydantoin. Compounds of type (b) are thiazoles, oxazoles, selenazoles, their polycyclic homologues, e.g. of the benzene, naphthalene, acenaphthene, or anthracene series, pyridine and its polycyclic homologues, e.g. quinoline and α - and # - naphthaquinolines, lepidines, indolenines, diazines, e.g. pyrimidines and quinazolines, diazoles, e.g. thio - ##<SP>1</SP> - diazole, oxazolines, thiazolines, and selenazolines. The polycyclic compounds may be substituted in the carbocyclic rings with one or more groups, e.g. alkyl, aryl, amino, hydroxy, alkoxy, or methylenedioxy groups or with halogen atoms. Compounds of type (c) are 1 : 3 - indane - dione and the hydrindones. The dyes are prepared by heating the reagents together in the presence of a solvent and a base, e.g. pyridine, piperidine, diethylamine, triethylamine, triethanolamine, or a solution of sodium or sodium acetate in ethyl alcohol. Quaternary salts of compounds of type (b) may be formed in situ by heating together the intermediate, the heterocyclic compound of type (b), and sufficient of an alkyl or aralkyl ester to convert the compound to the quaternary salt. A dye obtained as a sulphate or alkyl - p - toluenesulphonate may be converted to another salts by treatment with a solution of the appropriate alkali salts, e.g. potassium chloride, bromide, iodide, or perchlorate. 3 : 3<SP>1</SP> : 11-trimethylthiadicarbocyanine iodide is prepared by boiling together 1 - (# - methyl - # - ethylthio - butadienyl) - benzthiazole methochloride and 1 - methylbenzthiazole methiodide in ethyl alcohol, adding sodium acetate, and boiling. 3 : 11 - Dimethyl - 3<SP>1</SP> - ethylthiaselenadicarbocyanine iodide is similarly prepared using 1 - methylbenzselenazole ethiodide. Dyes are similarly obtained from 2 - (# - methyl - # - ethylthio - butadienyl) - 1 : 3 : 3 - trimethylindolenine chloride and 1 - methylbenzthiazole methiodide, from 2 - (# - methyl - # - ethylthio - butadienyl) - 1 : 3 : 3 - trimethylindolenine chloride and 1 - methylbenzselenazole ethiodide, from 2 - (# - methyl - #) - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine chloriie and 1 - methyl - 5 : 6 - naphthathiazole ethiodide, from 2 - (# - methyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine chloride and p - toluquinaldine ethiodide, from 2 - (# - methyl - # - ethylthiobutadienyl) - 6 - methylquinoline methochloride and 1 - methylbenzthiazole ethiodide, from 2 - (# - methyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and 1 - methylbenzthiazole ethiodide, from 2 - (# - methyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and N - methylrhodanic acid, from 1 - (# - methyl - # - ethylthiobutadienyl) - benzthiazole ethochloride and 1 - methylbenzthiazole ethiodide, from 1 - (# - methyl - # - ethylthiobutadienyl) - benzselenazole methochloride and 1 - methylbenzthiazole ethiodide, from 2 - (# - methyl - # - ethylthiobutadienyl) -1 : 3: 3 - trimethylindolenine chloride and 1 - methylbenzthiazole - # - hydroxyethiodide, from 1 - (# - methyl - # - ethylthiobutadienyl) - benzthiazole - # - hydroxy ethyl chloride and 1 - methylbenzthiazole # - hydroxyethiodide, from 2 - (# - ethyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and 1 - methylbenzselenazole ethiodide, from 2 - (# - ethyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and 1 - methylbenzthiazole methiodide or ethiodide, and from 2 - (# - methyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and 1 : 3 - indanedione. The due prepared from 2 - (# - methyl - # - ethylthiobutadienyl) - 1 : 3 : 3 - trimethylindolenine iodide and N - methylrhodanic acid may be used with 1 - methylbenzthiazole and methyl p - toluenesulphonate to effect a further condensation and poured into aqueous potassium iodide to give the iodide. Sensitizing data are given in respect of the use of certain of the dyes with various silver halide emulsions. Samples have been furnished under Sect. 2 (5) of (a) a dye obtained by heating together the intermediate obtained by the reaction of 1 - diacetyl - 3 - (N - methyldihydrobenzthiazolylidene) - 1 - butene, ethyl mercaptan, and sulphuric acid (Sample B of Specification 553,143), 1 - methylbenzthiazole ethiodide, ethyl alcohol, and triethylamine, and pouring into potassium iodide solution ; (b) the dye obtained by heating together the intermediate obtained by the reaction of 2 - (# - diacetylpropenylidene) - N - methyldihydrothiazoline, ethyl mercaptan, and sulphuric acid (Sample A of Specification 553,143), 1 - methylbenzthiazole ethiodide, ethyl alcohol, and triethylamine, and proceeding as in (a) ; and (c) the dye obtained by heating an intermediate prepared by the reaction of 4 - (# - diacetylmethylenevinyl) - N - methyldihydroquinoline, ethyl mercaptan, and sulphuric acid, with 1 - methylbenzthiazole ethiodide, pyridine, and triethylamine, and pouring into potassium iodide solution. The Provisional Specification describes also the production of dyes by reacting an intermediate of the formula (wherein D is the residue of a heterocyclic nitrogen nucleus, R 1  is an alkyl or aralkyl group, R  2  and R 3  are hydrogen atoms or alkyl, aryl, or aralkyl groups (the same or different), R 4 , R 5  and R 6  are alkyl, aryl, or aralkyl groups, n is 0 or 1, m is 0 or a positive integer, and X is an acid radical) with (a) a five-membered ring compound containing the system (b) a quaternary salt of a heterocyclic nitrogen compound having a reactive methyl, monosubstituted methyl, external methylene, amino, or imino group in the α or γ position to a heterocyclic nitrogen atom ; (c) a compound of formula wherein R 7 , R 8 , and R 9  may be alkyl,. aralkyl, or aryl groups, or R, and R 8  may be part of an arylene ring ; (d) carbocyclic compounds containing a keto-methylene group ; (e) acids or esters of formula wherein R 10  is hydrogen or a monovalent substituent, R 11  is hydrogen or an alkyl or other hydrocarbon group, and n is 0 or 1; (f) anhydrides of acids of formula wherein R 12  is H or a monovalent group, and n is 0 or 1 ; (g) ammonia, amidines, hydrazines, diamines, or their salts ; (h) quaternary salts of formula wherein R 13 , R 14 , R 15  and R 16  are hydrogen atoms or substituent groups (of which two may form part of an aromatic nucleus fused to the benzene ring), R 17 , R 18'  and R 19  are H or hydrocarbon groups, X is Q, S, or Se, and n is a positive integer greater than 1 ; or (i) compounds containing the system wherein R 20  is H or alkyl, aralkyl, or aryl. Polycyclic compounds of type (b) may be substituted in the carbocyclic rings with one or more alkyl, aryl, amino, alkoxy, or methylenedioxy groups or by halogen atoms. Specifications 426,718, 513,170, 513,596 and 546,565 also are referred to.