Patent GB-904332-A (GB)
Title: Improvements in or relating to sensitized photographic emulsions and to new sensitizing dyes
Inventor: NYS JEAN MARIE
IPC: C09B23/02
Filed: 1957-07-05
Abstract: Quaternary salts of heterocyclic nitrogen bases having an a - or g -methyl group are prepared by treating the base with a compound of the formula X-A-W-NH-V-B where A is a methylene, ethylene, propylene or butylene radical, B is an alkyl, amino or substituted amino group or, when V is a single bond, B may be hydrogen, W and V are each a -CO-or -SO2- radical or a single bond but at least one of them must be a -SO2-radical, and X is halogen.  The heterocyclic nitrogen base may be a 2-methyl derivative of a benzthiazole, benzoxazole, benzselenazole, benzimidazole, naphthothiazole or quinoline, the benzene rings of which may have methyl, phenyl or chloro substituents or it may be 2;4-dimethylthiazole.  The substituted amino group represented by B may be dimethylamino or diacetylamino.  Examples also are given of the preparations of the intermediates of formula X-A-W-NH-V-B.  Thus 3-bromo-propane-sulphonamide is obtained by treating 3-bromo-propane sodium sulphonate with phosphorous pentachloride and reacting the sulphonyl chloride formed with ammonia gas.  The product may be acetylated to give N-acetyl-3-bromo-propane sulphonamide.  4-Bromo-butane-sulphonamide and its N-acetyl derivative are similarly prepared. N-ethyl-4-bromo-butane-sulphonamide is obtained by using ethylamine instead of ammonia in the above preparation. Similarly, N-methylsulpho-3-bromo-propane sulphonamide is obtained by reacting methane sulphonamide with 3-bromopropane sulphonyl chloride. Compounds where W is -CO- and V is -SO2- are obtained by heating methane sulphonamide with bromo-acetyl bromide or with B-bromo-propionyl chloride.  Similarly, bromo - acetyl bromide is reacted with ethane sulphonamide or with N;N-dimethylsulphonamides. N-(b -bromo-ethyl) methane sulphonamide is obtained by adding methane sulphonyl chloride to b -bromo-ethylamine hydrobromide. 4-Bromo-butane-sulphohydrazide is obtained by adding hydrazine to 4-bromo-butane sulphonyl chloride.  The product may be treated with acetic anhydride to give the N;N-diacetyl derivative.ALSO:Cyanine, merocyanine, polymerocyanine, rhodacyanine and styryl dyes are described which contain at least one heterocyclic residue of one of the following formulae:- <FORM:0904332/IV (b)/1> <FORM:0904332/IV (b)/2> wherein A is a methylene, ethylene, propylene or butylene radical, B is an alkyl, amino or substituted amino group or, when V is a single bond, B may be hydrogen, W and V are each a -CO- or -SO2- radical or a single bond but at least one of them is a -SO2- radical, n is 1 or 2, X is an anion and Z completes a 5- or 6-membered heterocyclic ring.  The dyes are prepared by standard methods from cyclammonium salts having the group -A-W-NH-V-B on the nitrogen atom. The polymerocyanines and rhodacyanines may be prepared from the merocyanine dyes. Thus, in Example 35, a rhodacyanine dye is prepared by heating {2-[3-(B-methyl-sulphonyl-amino-ethyl) benzthiazole]}- [5-(3-alkyl-rhodanine)] dimethine merocyanine with dimethyl sulphate and condensing the methylmercapto salt so formed with 2 : 6-dimethyl-3-(sodium sulphocarbomethoxy-methyl) benzthiazolium bromide.  The heterocyclic nucleus completed by Z may be benzthiazole, benzoxazole, benzselenazole, benzimidazole or quinoline, the benzene rings of which may have methyl, phenyl or chloro substitutents, or Z may complete a 4-methyl-thiazoline residue.  The substituted amino group represented by B may be dimethylamino or diacetylamino.