Patent GB-533425-A (GB)
Title: Improvements in the production of dyes of the cyanine type and intermediates therefor
IPC: G03C1/12
Filed: 1939-05-09
Abstract: 533,425. Photographic sensitizing dyes ; intermediates. KODAK, Ltd. (Eastman Kodak). Co. May 9, 1939, Nos. 13798 and 32307. [Class 2 (iii)] [Also in Group XX] Halogenovinyl compounds of the general formula where O is phenylene or naphthylene, Q is sulphur or selenium, R is an alkyl or substituted alkyl group (e.g., methyl, ethyl, #-ethoxyethyl, butyl, allyl or benzyl), R<SP>1</SP> is the same as R or an aryl or heterocyclic group (e.g., phenyl, naphthyl or furyl), X is an anion, and X<SP>1</SP> is halogen, are made by treating a ketone of the general formula (see Specifications 466,097 and 466,246) with a phosphorus oxyhalide. The products may be converted into thionies by reaction with a thioamide, or into mercaptovinyl compounds of the general formula where R<SP>11</SP> is alkyl or aryl, by reacting with an alkyl- or aryl-thiol in presence of a base. The halogenovinyl compounds may be converted into chain-substituted carbocyanine and other dyes by condensing them with a compound containing a reactive alkyl (e.g., methyl) group, a reactive methylene group, or a primary or secondary amine. They also undergo autocondensation to form halogeno-thiadicarbocyanines, which react with primary or secondary amines to give the corresponding amino compounds. In examples of the preparation of the halogenovinyl compounds, 2-acetylmethylene- 3 - ethyl - benzothiazoline and 2 - acetylmethylene - 5 - chloro - 3 - ethyl - benzothiazoline are reacted with phosphorus oxychloride, and 2 - acetylmethylene - 3 - ethylbenzoselenazoline and 2 - acetylmethylene - 1 - ethyl - naphthothiazoline are reacted with phosphorus oxybromide. In examples of the preparation of dyes, (1) 5 - chloro - 2 (2 - chloropropenyl) - benzthiazole ethochloride is condensed with 3 - ethylrhodanine, (2) 2 - (2 - chloropropenyl) - naphthothiazole ethochloride is condensed with (a) aniline, (b) benzoylacetonitrile, (c) piperidine, (d) morpholine, (e) thiobarbituric acid, (#) quinaldine - etho - p - - toluene sulphonate, (g) lepidine ethochloride, (h) 1 - phenyl - 3 - methyl - 5 - pyrazolbne, (i) 1 - (2 - benzthiazolyl) - 3 - methyl - 5 -pyrazolone, (j) 2 - methylbenzthiazole ethiodide, (k) 2 - methylnaphthothiazole etho - p - - toluene sulphonate and -(l) thioindoxylic acid, and (3) 2 - (2 - chlorobutenyl) - naphthothiazole ethochloride is condensed with lepidine ethiodine. In an example of autocondensation, 2 - acetylmethylene - 3 - ethylbenzthiazoline is treated with phosphorus oxychloride in diethylaniline ; the product is 9 - chloro - 3 : 31 - diethyl - 11 - methyl - thiadicarbocyanine chloride, and yields the 9- (1-piperidyl) derivative on treatment with piperidine. In examples of the formation of thiones from the halogenovinyl compounds, the following compounds are reacted with thioacetamide in absolute alcohol:-2 - (3 - chlorobutenyl) - benzthiazole methochloride, 2 - (2 - chloropropenyl) - benzthiazole ethochloride, 2 - (2 - chloropropenyl) - # - naphthathiazole ethochloride, and 2 - (3 - chlorobutenyl)- # - naphthathiazole methochloride. In further examples, the preparation of thiols is described from (1) 2 - chloropropenyl - # - naphthothiazole ethochloride and benzyl mercaptan, (2) 2 - (2 - chlorostyryl) - 6 - naphthothiazole ethochloride (made from 1 - ethyl - 2 - benzoylmethylene - # - naphthothiazoline by reaction with phosphorus oxychloride) and benzyl mercaptan, (3) 5 - chloro - 2 (2 - chlorobutenyl) - benzselenazole ethochloride (made by reacting 5 - chloro - 3 - ethyl - 2 - propionylmethylene - benzselenazoline with phosphorus oxychloride) is reacted with thiophenol, and (4) 2 - (2 - chloropropenyl) - benzthiazole ethochloride is reacted with thiophenol. The thiones and the dyes described above are optical sensitizers ; sensitizing data for some of the dyes are given. Specifications 450,958,470,726 and 479,970 also are referred to.