Patent GB-527627-A (GB)
Title: Improvements in photographic emulsions and manufacture of dyes therefor
IPC: G03C1/83
Filed: 1939-03-07
Abstract: 527,627. Sensitized photographic emulsions. KODAK, Ltd. (Eastman Kodak, Co.). March 7, 1939, No. 7384. Drawings to Specification. [Class 98 (ii)] [Also in Group IV] Trinuclear polymethine dyes are made by condensing a carbocyanine of the general formula where R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> represent alkyl groups on mono-substituted alkyl groups, e.g., isoamyl, benzyl, #-hydroxyethyl or #-ethoxyethyl, X is an acid radicle, and Z, Z<SP>1</SP> represent the same or different groups of non-metallic elements necessary to complete a heterocyclic nucleus, with (1) a cyclammonium quaternary salt containing in α- or γ-position a reactive group which is capable of condensing with R<SP>2</SP> or (2) a heterocyclic compound containing a nuclear carbonyl group adjacent to a nuclear carbon atom attached to which is a reactive group which is capable of condensing with R<SP>2</SP>. R<SP>2</SP> is preferably a methyl group, and Z, Z<SP>1</SP> preferably represent the atoms necessary to complete benzoxazole, benzthiazole, benzselenazole, naphthoxazole or naphththiazole ring. Reactive groups in the α- or γ-position of the cyclammonium salt include alkyl- and aryl-mercapto groups, aryloxy groups, halogen atoms, arylaminovinyl groups or acylated arylamino groups. In examples (1) 3 : 3<SP>1</SP>-diethyl-9-methylthiacarbocyanine-ptoluenesulphonate is condensed with (a) 2- methyl (or phenyl)-mercaptobenzthiazole ethiodide, (b) 2-iodoquinoline, (c) 2-#-acetanilidovinyl-benzthiazole, (d) 5-acetanilidomethylene- 3-ethylrhodanine, and (e) 5-acetanilidomethylene-ethyl-2-thio-2 :4-oxozoledione, (2) 3 : 3<SP>1</SP>- diethyl-9-methyl-4 : 5 : 4<SP>1</SP> : 5<SP>1</SP>-dibenzthiacarbocyanine chloride is condensed with (a) 2- methylmercaptobenzthiazole metho-p-toluenesulphonate and (b) 5-acetanilidomethylene-3- ethyl-rhodanine, (3) 3 : 3<SP>1</SP>-diethyl-9-methylselena-carbocyanine bromide is condensed with (a) 2-methylmercaptobenzthiazole metho-ptoluenesulphonate and (b) 2-phenylmercaptobenzthiazole etho-p-toluenesulphonate, (4) 3:3<SP>1</SP>- diethyl - 9 - methyl - 3<SP>1</SP> : 4<SP>1</SP> - benzooxathiacarbocyanine iodide is condensed with 2-methylmercaptobenzthiaole metho-p-toluenesulphonate, (5) 3 : 3<SP>1</SP>-diethyl-9-methyl-4<SP>1</SP> : 5<SP>1</SP>- benzthiacarbocyanine-p-toluenesulphonate is condensed with (a) 2-phenylmercaptoquinoline etho-p-toluenesulphonate or (b) 2-phenylmercaptobenzthiazole - etho - p -toluenesulphonate, (6) 3 :3<SP>1</SP>-diethyl-9-methyl-4<SP>1</SP> : 5<SP>1</SP>-benzoxathiacarbocyanine iodise is condensed with (a) 2- phenylmercaptoquinoline - etho - p - toluenesulphonate, (b) 4 - n - heptylmercaptoquinoline ethiodide, and (c) 2-phenylmercaptobenzthiazole - etho - p - toluenesulphonate, (7) 3 : 3<SP>1</SP>- diethyl - 9 - methyloxacarbocyanine - p - toluenesulphonate is condensed with (a) 2- phenyl - mercaptobenzthiazole - etho - p - toluenesulphonate and (b) 2 - methylmercaptobenzthiazole metho - p - toluenesulphonate, (8) 5 : 5<SP>1</SP> - dichloro - 3 : 3<SP>1</SP> : 9 - triethylthiacarbocyanine bromide is condensed with 2- methylmercaptobenziazole-metho-p-toluenesulphonate, (9) 3 : 3<SP>1</SP> : 9-trimethyl-thiacarbocyanine-p-toluenesulphonate is condensed with 2-phenylmercaptobenzthiazole etho-p-toluenesulphonate, (10) 3 : 3<SP>1</SP>-dimethyl-9-ethylthiacarbocyanine bromide is condensed with 2 - methylmercaptobenzthiazole metho - p - toluenesulphonate, (11) 3 : 3<SP>1</SP> : 9-triethylthiacarbocyanine iodide is condensed with 2- phenylmercaptobenzthiazole etho-p-toluenesulphonate, and (12) 3 : 3<SP>1</SP> : 9-trimethylthiacarbocyanine-p-toluenesulphonate is condensed with 2 - methylmercaptobenzthiazole metho - p - toluenesulphonate. The products contain three heterocyclic nuclei, but only one quaternary nitrogen atom. Sensitizing data and spectrograms are given. 4-n-Heptylmercaptoquinoline is made by heating 4-chloroquinoline with nheptylmercaptan in n-heptyl alcohol. Specifications 344,409, [Group IV], 466,097, 466,246, 479,970, 483,459, 485,604 and 485,609 are referred to.