Patent GB-534140-A (GB)
Title: Improvements in and relating to photographic emulsions and layers, and the manufacture of dyes for use therein and intermediates for such manufacture
IPC: C09B23/00
Filed: 1939-05-25
Abstract: 534,140. Dyes and intermediates therefor. KODAK, Ltd., HAMER, F. M., and RATHBONE, R. J. May 25, 1939, Nos. 15590 and 30112. Sample furnished. Drawings to Specification. [Class 2 (iii)] [Also in Group XX] Dye bases containing a hydrogenated 1:3- thiazine ring are prepared by condensing a dihydro-1:3-thiazine, not having the thiazine ring fused to another nucleus but having a methyl group in the 2-position, with the quaternary salt of a heterocyclic compound containing a reactive monovalent substituent such as alkylthiol or iodine or containing a reactive side chain comprising a vinylene group, and treating the product with alkali. Cyanine dyes are prepared by condensing a quaternary salt of a dihydro-1:3-thiazine derivative, not having the thiazine ring fused to another nucleus but having in the 2-position a reactive monovalent substituent or a reactive side chain comprising a vinylene group, with a heterocyclic compound having an intracyclic nitrogen atom with a reactive alkyl group (e.g. a methyl group) in the α- or γ- position thereto, or with a compound containing a reactive methylene group. Dyes specified are [2 (3- methyldihydro -1:3 - - thiazine)] [3-methyl -2 - - benzthiazole] methinecyanine iodide, [2 (3- ethylhydro-1:3-thiazine)] [3-ethyl-2-benzthiazole]- methinecyanine iodide, [2(3-methyldihydro-1:3- thiazine)] [3-ethyl-2-benzthiazole]-methinecyanine iodide, [2 (3-ethyldihydro-1:3-thiazine)] [5-chloro- 3-ethyl-2-benzthiazole]-methinecyanine iodide, [2 (3-ethyldihydro-1:3-thiazine)] [5:6-dimethoxy-3- ethyl - 2 - benzthiazole] - methinecyanine iodide, [2(3-ethyldihydro-1:3-thiazine)] [3-ethyl-2-(6:7- benzbenzthiazole)] - methinecyanine iodide, [2(3 - - methyldihydro 1 : 3 - thiazine)] [(3-- methyl - 2 - (6 : 7 - - benzbenzthiazole)] -methinecyanine iodide, [2(3 - methyldihydro - 1 3 - thiazine)] [(3 - - ethyl 2(6 : 7 - benzbenzthiazole)] - methinecyanine iodide, [2(3 - ethyldihydro 1 : 3 - thiazine)] [(3 - - ethyl - 2(4 : 5 -benzbenzthiazole)] - methinecyanine iodide. [2(3 - - methyldihydro - 1 : 3 - thiazine)] [(3 - - methyl - 2(4 : 5 - benzbenzthiazole)] - methinecyanine iodide, [2(3 - methyldihydro - 1 : 3 - thiazine)] [3 - - ethyl - 2 - benzselenazole] methinecyanine iodide, [2(3 - ethyldihydro - 1 : 3 - thiazine)] [3 - ethyl - 2 - benzselenazole] - methinecyanine iodide, [2(3 - methyldihydro - 1 : 3 - thiazine]) [3 ethyl - 2 - benzoxazole] - trimethinecyanine iodide, [2(3- methyldihydro - 1 : 3 - thiazine)] [3 ethyl - 2 - - benzthiazole] - trimethinecyanine iodide, 3 - - ethyl - 5 : 21 - (3<SP>1</SP> - ethyldihydro - - 1<SP>1</SP> : 3<SP>1</SP> - thiazinylidene) - rhodanine, and 3 - - ethyl - 5 : 21 - (3<SP>1</SP> -methyldihydro - 1<SP>1</SP> : 3<SP>1</SP> - thiazinylidenevinyl) - rhodanine. Dicarbocyanine dyes may also be prepared. Cyanine dyes are also prepared by condensing quaternary salts of 2-methyldihydro-1:3-thiazine with an orthoester. Bis-2-[3-methyldihydro-1:3-thiazine]-trimethinecyanine iodide is so prepared. Cyanine dyes are also prepared by condensing quaternary salts of thio-2-alkyltetrahydro- 1:3-thiazines or the components thereof with quaternary salts of heterocyclic nitrogen compounds containing an alkyl (e.g. methyl) group in the α- or γ-position to the nitrogen atom of the heterocyclic ring or with a compound containing. a reactive methylene group. The dyes [2(3-methyldihydro-1:3-thiazine)] [6-acetylamino - 3 - - ethyl - 2 - - benzthiazole] - methinecyanine iodide, [2(3 - methyldihydro 1 : 3 - thiazine)] [(6 - - chloro 3 - ethyl- 2 - - benzthiazole] - methinecyanine iodide, and [2(3 - methyldidihydro 1 : 3 - thiazine)] [1 - - methyl 2 - - quinolinemethinecyanine iodide are so prepared. 2 - # - Acetanilidovinyldihydro - 1 : 3 - thiazine methiodide is prepared by heating together 2- methyldihydro-1:3-thiazine methiodide and diphenylformamidine, and boiling the product with acetic anhydride. 2-Methylthiodihydro-1:3-thiazine is prepared by adding dimethyl sulphate to an aqueous sodium hydroxide solution of 2 thiodihydro-1:3- thiazine. 2 - - Ethlylthiodihydro - 1 : 3 - thiazine is similarly prepared. 2-Methylthiodihydro-1:3-thiazine methiodide is prepared by heating together 2-methylthiodihydro-1:3-thiazine and methyl iodide in a sealed tube. 2-Ethylthiodihydro-1:3-thiazine ethiodide and 2-ethylthiodihydro-1:3-thiazine methiodide (from 2-methylthiodihydro-1:3-thiazine and ethyl iodide) are similarly prepared. 2 - - Methyldihydro - 1 3 - thiazine methiodide is prepared by reacting 2-methyldihydro-1:3- thiazine with methyl iodide. 2- Thio-3-methyltetrahydro-1:3-thiazine is prepared by refluxing 2-methylthiodihydro-1:3- thiazine methiodide with pyridine, and 2-thio- 3-methyltetrahydro-1:3-thiazine methiodide by reacting this compound with methyl iodide in a sealed tube. The dyes may serve as photographic filter and sensitizing dyes. A sample has been furnished under Sect. 2 (5) of [2(3-methyldihydro-1:3-thiazine)] [1- methyl - 4 - quinoline] - methinecyanine iodide, prepared by boiling together 2-thio-3- methyltetrahydro-1:3-thiazine methiodide, lepidine methiodide, and triethylamine in absolute alcohol. Specifications 450,958, 466,097, 466,244, 470,726, 479,970 and 493,455 are referred to.