Patent GB-532098-A (GB)
Title: Improvements in photographic sensitising dyes
IPC: G03C1/22
Filed: 1939-04-14
Abstract: 532,098. Photographic sensitizing dyes. KODAK, Ltd. (Eastman Kodak Co.). April 14, 1939, No. 11306. Drawings to Specification. [Class 2 (iii)] [Also in Group XX] In a photographic element having at least two light-sensitive silver halide emulsions coated adjacent to one another, at least one of the emulsions is sensitized by a dyestuff of the general formula where L is an open chain of at least seven non- metallic atoms, which may have attached to the other end thereof a similar grouping to the grouping shown attached to L, Z represents the residue of a 5-membered ring, A is oxygen or sulphur, n is 1, 2, or 3, D is vinylene or phenylene, R is alkyl, and Q is the residue of a five- or six-membered ring. The atoms forming the chain L may consist entirely of carbon atoms, or may include oxygen, sulphur, or nitrogen atoms ; examples of such chains are n-heptyl, n-amyloxymethyl,n-amylthiomethyl, 3-methyl-n-heptyl, n-butylcarbamylmethyl, npentadecyl, stearyl, and lauryl. Q may be a thiazole, oxazole, selenazole, thiazoline, quinoline or pyridine nucleus, and Z may be a rhodamine, oxazoledione, thiohydantoin, thiazoledione, imidazoledione or pyrazolone nucleus. The dyes are made by condensing a compound of the general formulae where P represents an open chain of at least 7 carbon atoms, with a quaternary salt of a heterocyclic compound having a thio-ether group, an arylaminovinyl group or an arylaminobutadienyl group in the α- or γ- position to the nitrogen atom. In examples dyes are prepared from the following components : 3-n-heptyl (octyl, decyl or lauryl)-rhodanine, 3-n-heptyl-2-thiohydantoin, 3-n-heptyl (nonyl or decyl)-1-phenyl-2-thiohydantoin, 3-n-heptyl (octyl or lauryl )-2-thio-2:4-oxazoledione or decamethylene-bis-3:3<SP>1</SP>-rhodanine ; and 1-(#-acetanilidovinyl)-benzoxazole ethiodide, 2-anilidovinyl-thiazoline methiodide, 1-(4-acetanilido- 1:3-butagienyl) - benzoxazole ethiodide, 1- phenylmercaptobenzthiazole ethiodide, 1-(4- acetanilido - 1:3 - butadienyl) - benzthiazole ethiodide, 1 - (# -acetanilidovinyl) - benzthiazole ethiodide, and 2- or 4-acetanilidovinylquinoline ethiodide. Sensitizing data and spectrograms are given. Specifications 426,718, 428,222, 428,359 , 428,360, 500,611, 500,826, and 503,752, [all in Group XX], are referred to. 3-n-Heptyl rhodanine is made by reacting n-heptylamine with carbon disulphide and chloracetic acid. The octyl, decyl and lauryl rhodanines are similarly prepared. 3-n- Heptyl-2-th,io-2:4-oxazoledione is made by condensing n-heptylamine with acetamidocarbo-thiolonglycollic acid (NH 2 ÀCOÀCH 2 ÀSÀCSÀ- OÀCH 2 ÀCOOH). The octyl and lauryl compounds are similarly prepared. 3-n- Heptyl-2-thiohydantoin is made from glycine and n-heptyl isothiocyanate. 3-n-Nonyl-1-phenyl-2-thiohydantoin is made from nonyl isothiocyanate and N-phenyglycine ethyl ether. The n-heptyl and n-decyl compounds are similarly made. Decamethylene-bis-3:3<SP>1</SP>-rhodanine is made from decamethylene diamine, carbon disulphide and chloracetic acid. n-Heptyl isothiocyanate is made by reacting n-heptylamine with carbon disulphide and treating the ammonium n-heptyl dithiocarbonate thus formed with lead nitrate. n-Nonyl isothiocyanate is similarly obtained from n-nonylamine. n-Decyl isothiocyanate is made from sym.- di-n-decylthiocarbamide and phosphorus pentoxide.