Improvements in and relating to polymethine dye intermediates and to the production of polymethine dyes

摘要

556,266. Polymethine dyes and intermediates. KODAK, Ltd. Sept. 26, 1941, No. 12486. Convention date, Oct. 18, 1940. Samples furnished. [Class 2 (iii)] [Also in Group XX] A compound of the general formula of Fig. 1 where R represents an alkyl or aryl radical, RSP1/SP represents an alkyl radical, X represents an acid radical, and Z the non-metallic atoms necessary to complete a 5- or 6- membered heterocyclic nucleus is prepared by condensing a #-alkoxyacrolein acetal with a cyclammonium quaternary salt containing a methyl group in the α-position to the nitrogen atom and employing as the reaction medium substantially anhydrous acetic acid not containing more than 1 per cent. of water. From 1 ¢ to 3 molecular proportions of acrolein acetal may be used for each molecular proportion of cyclammonium quaternary salt. The cyclammonium quaternary salt may be a quinoline, benzoxazole, naphthoxazole, benzthiazole, naphthathiazole, benzselenazole, or thiazoline derivative. The reaction medium may be glacial acetic acid and the quaternary salt an iodide. 2-(4-Ethoxy- #SP1/SP:SP3/SP-butadienyl)-benzthiazoleethiodide is prepared by reacting 2-methylbenzthiazole ethiodide and #-ethoxyacrolein diethyl acetal in glacial acetic acid. 2-(4-Ethoxy-#SP1/SP:SP3/SP-butadienyl)-benzoxazole ethiodide, 2-(4-etlaoxy-#SP1/SP:SP3/SP- butadienyl)-#-naphthathiazole ethiodide, 2-(4- ethoxy-#SP1/SP:SP3/SP-butadienyl)-α-naphthoxazole ethiodide, 2-(4-ethoxy-# SP1/SP:SP3/SP-butadienyl)-#-naphthoxazole ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl)-quino line ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl)-benzselenazole ethiodide, 2-(4-ethoxy- #SP1/SP: SP3/SP-butadienyl). thiazoline ethiodide, 2-(4-ethoxy-#SP1/SP:SP3/SP-butadienyl). benzthiazolepheniodide, and 2-(4-ethoxy-#SP1/SP:SP3/SP- butadienyl) 3:4 - - trimethylene benzthiazolium iodide are similarly prepared. Polymethine dyes are prepared by condensing a compound of the general formula shown in Fig. 1 with a cyclammonium alkyl quarternary salt containing a methyl group in the α or y position to the nitrogen atom. Pyridine or trialkylamines dissolved in acetic anhydride may be used as condensing agents. 3 : 3SP1/SP- Diethylthiadicarbocyanine iodide is prepared by refluxing together 2 - (4 - ethoxy - # SP1/SP : SP3/SP - butadienyl) - benzthiazole ethiodide and 2 - methylbenzthiazole ethiodide in pyridine. 1SP1/SP: 3- Diethyloxa - 2SP1/SP - dicarbocyanine iodide is similarly prepared using as condensing agent acetic anhydride containing triethylamine. 1SP1/SP : 3 - - Diethylthia - 2SP1/SP dicarbocyanine iodide, 1SP1/SP : 3 - diethylthia - 4SP1/SP - dicarbocyanine iodide 3 : 3SP1/SP - diethyl - 4 : 5 benzthiadicarbocyanine iodide, 3 : 3 - diethyl - 4 5 : 4SP1/SP: 5SP1/SP - dibenzthiadicarbocyanine iodide, 1 : : 1SP1/SP - diethyl 2 : : 2SP1/SP- dicarbocyanine iodide, 3 : 3SP1/SP - diethyloxadi - carbocyanine iodide, 3 : 3SP1/SP - . diethyloxathiadicarbonyanine isodide, 1SP1/SP : 3 - diethyloxa - 4SP1/SP - dicarbocyanine iodide, 3 3SP1/SP - diethylselena - dicarbocyanine iodide, 3 : 3SP1/SP - diethylselenathiadicarbocyanine iodide, 3 : 3SP1/SP- diethyloxaselena dicarbocyanine iodide, and 3 - ethyl - 3SP1/SP - methylthiathiazolino dicarbocyanine iodide are similarly prepared. Polymethine dyes may also be prepared by condensing the compounds of the general formula of Fig. 1 with a heterocyclic compound having a methylene group adjacent to a carbonyl group. 3 - - Ethyl - 5 - [(3 - - ethyl - 2 - benzthiazolyidene) - butenylidene] - rhodanine is prepared by condensing 2 - (4 - ethoxy - #SP 1/SP : 3- butadienyl) - benzthiazole ethiodide with 3 - ethylrhodanine in the presence of triethylamine and acetic anhydride. The intermediate may also be condensed with 1 - phenyl - 3 - methyl - 5 -.pyrazolone or with 1 - ethyl - 3 - phenyl - 2 - thiohydantoin. Polymethine dyes may also be prepared by condensing the intermediates with primary or secondary aliphatic or aromatic amines. 2 - (4- Piper´dino - #SP1/SP : SP3/SP - butadienyl)- benzthiazole ethiodide is prepared by refluxing together 2 - (4 - ethoxy - #SP1/SP : 3 - butadienyl)- benzthiazole ethiodide and piperidine in ethyl alcohol. The intermediate may also be condensed with aniline. Polymethine dyes may also be obtained by condensing the intermediates with N - alkyl or N - aryl pyrroles. Such dyes may be used as light-screening substances in the preparation of photographic elements, and are bleachable in alkaline developers. (3 - - Ethyl - 2 - benzthiazole) (1 - - heptyl - 2 : 5 - dimethyl - 3 - pyrrole) - tetramethinecyanine iodide is prepared by refluxing together 2 - (4 - ethoxy - #SP1/SP : 3 - butadienyl) - benzthiazole ethiodide and 1 - heptyl - 2 : 5 - dimethylpyrrole in acetic anhydride. (3 - - Ethyl - 2 - benzoxazole) (1 - - heptyl - 2 : 5 - dimethyl - 3 pyrrole-, (3 - - ethyl - 2 - benzoxaozle) (1 - lauryl - 2 : : 5 - dimethyl 3 - - pyrrole) 3 - - ethyl - 2 - benzoxazole)- (1 - ethyl - 2 : : 5 - dimethyl - 3 - pyrrole)-, (1 - cetyl - 2 : 5 - dimethyl 3 - - pyrrole) 3 - - ethyl - 2 - benzoxazole)-, (1 ethyl - 2: 5 - dimethyl - 3 - pyrrole) - (3 - ethyl - 2 - α - naphthoxazole),- (3 - - ethyl - 2 - α - - naphthoxazole) - (1 lauryl - 2 : 5 - - dimethyl 3 - pyrrole)-, (1 - ethyl - 2 : 5 - dimethyl - 3 pyrrole) (1 - - ethyl - 2 - # - naphthoxazole)-, 1 - - ethyl - 2 5 - dimethyl - 3 pyrrole)- (1 - - ethyl 2 - quinoline)-, (3 - - ethyl - 2 - benzthia; zole)- (1 - ethyl - 2 : 5 - dimethyl - 3 pyrrole)-,. (3 - - ethyl - 2 - benzthiazole)- (2 : 5 dimethyl 1- phenyl 3 - - pyrrole)-, (1 - - ethyl - 2 : 5 - dimethyl- 3 - pyrrole) - (3 - - methyl - 2 thiazoline)-, and (3 - - ethyl - 2 - - benzselenazole) (1 - - ethyl - 2 : 5- dimethyl - 3 - pyrrole) tetramethine cyanines are similarly prepared. Samples have been furnished under Sect. 2 (5) of (a) 2SP1/SP - (4 - methoxy - #SP1/SP :SP3/SP -butadienyl)- benzoxazole ethiodide (b) 2SP1/SP - (4-piperidine - # SP1/SP: SP3/SP - butadienyl) - benzthiazole ethiodide: (c) 2SP1/SP - (4 - anilino - #SP1/SP : 3 - butadienyl) - benz - thiazole ethiodide : and (d) 2SP1/SP - (4 - dibutylamino - # SP1/SP : SP3/SP - butadienyl) - benzoxazole ethoper - chlorate. Specification 551,331 is referred to.