Patent GB-599636-A (GB)
Title: Polymethin dyes and photographic materials containing them
IPC: C09B23/06
Filed: 1944-07-12
Abstract: <PICT:0599636/IV/1> <PICT:0599636/IV/2> <PICT:0599636/IV/3> <PICT:0599636/IV/4> A cyanine dye is produced by reacting a thioketone of the formula shown in any of Figs. 1, 2, 3 or 4, wherein Q is S or Se, D1 represents a phenylene, naphthylene, vinylene or ethylene group, D11 represents a vinylene or substituted vinylene group, R is alkyl or substituted alkyl, R2 and R3 are alkyl groups and wherein either a is O and Z the non-metallic atoms necessary to complete a 5- or 6-membered ring containing the group <FORM:0599636/IV/1> , wherein A and B are H or monovalent substituents or together form a fused-on ring or a is 1 and Z is the group <FORM:0599636/IV/2> , with an alkyl ester and condensing the resulting quaternary salt with a heterocyclic nitrogen quaternary salt having a reactive methyl group in the a - or g -position to the quaternary nitrogen atom or with a compound having a reactive methyl group adjacent to a carbonyl or thiocarbonyl group.  The second component may be derived from a quinoline, pyridine, thiazole, thiazoline, benzthiazole, naphthathiazole, oxazoline, oxazole, benzoxazole, naphthoxazole, selenazole, benz-selenazole, indole, thiazine or benzthiazine, or may be malonic acid or esters, malonamide, ethyl-2-quinolyl pyruvate, acetylacetone, acetoacetamides, cyanoacetamides, benzoylacetonitrile, hippuric acid, aceturic acid, thiazolones (e.g. isothiohydantoin), thiazolidones, thiazolediones, thiothiazolediones (e.g. rhodanines), barbituric acids, thiobarbituric acids, oxazolones, iminazolediones (e.g. hydantoins), thioiminazolediones (e.g. thiohydantoins), pyrazolones, 1 : 3-cyclohexanediones, 2 : 4-dihydroxyquinolines, oxydihydroquinoxalines, dihydrocarbostyrils, coumaranones, oxindoles, ketodihydrobenzparathiazine, benzo - b  - morpho - lones, homophthalimide, succinimide, indanedione, tetronic acid, ketodihydrothionaphthenes (e.g. thioindoxyl), or indoxyls. 1 : 11-Diethyl-10-methyl-2 : 41-carbocyanine perchlorate is prepared by heating together 1-ethyl-2-thioacetylmethylene-1 : 2-dihydroquinoline and methyl p-toluenesulphonate, and refluxing the product in absolute alcohol with lepidine ethiodide and triethylamine, precipitating with ether, dissolving in methyl alcohol and precipitating with sodium perchlorate.  1 : 31-Diethyl-9-methylselena - 21 - carbocyanine iodide, 11 : 3 - diethyl-9-methyloxa - 21 - carbocyanine perchlorate, 11 : 3 - diethyl - 4 : 7 - dimethylthiazolo - 21 - carbocyanine perchlorate, 3 : 31 - diethyl - 9 - methyl - 41 - phenyloxa - thiazolocarbocyanine iodide, 11 : 3 - diethyl - 9 - methyl - 4 : 5 - benzthia - 41 - carbocyanine iodide, 3 : 31 - diethyl - 9 : 10 - dimethyl oxathiacarbocyanine iodide, 2 - ethyl - 5 - [(3 - ethyl - 2 - benzthiazolylidene) - a  : b  - dimethyl - ethylidene] - 2 - thio - 2 : 4 - oxazoledione, 3-ethyl5 - [(3 - ethyl - 2 - benzthiazolylidene) - a  : b  - dimethylethylidene] - rhodanine, 3 - ethyl - 5 -[(3 - ethyl - 4 - phenyl - 2 - thiazolylidene) - isopropylidene] - 2 - thio - 2 : 4 - oxazoledione, and 3-ethyl5 - [(3 - n - propyl - 2 - benzthiazolylidene) - isopropylidene]- 2 - thio - 2 : 4 - oxazoledione are similarly prepared.  Specifications 412,309, 450,958, 466,097, 466,244, 538,857 and 585,666 are referred to.