Patent GB-558710-A (GB)
Title: Improvements in and relating to sensitive photographic materials
IPC: B65B19/10
Filed: 1942-01-07
Abstract: 558,710. Ammonium, sulphonium and phosphonium derivatives. KODAK, Ltd. (Eastman Kodak Co., Carroll, B. H., and Allen, C.F.H.). Jan. 7, 1942, No. 271. [Class 2 (iii)] [Also in Group XX). Photographic material comprises a lightsensitive silver halide emulsion sensitized with a polyonium salt (other than methenyl-tristriethylphosphonium iodide) containing a quaternary ammonium, ternary sulphonium, or quaternary phosphonium salt linked through the onium atom, by at least one bivalent organic radical, to the onium atom of another quaternary ammonium, ternary sulphonium, or quaternary phosphonium salt group, neither onium atom being attached directly to an aromatic ring. General formulae for particularly suitable types of polyonium salts are given, including symmetrical and unsymmetrical types. Numbers of linking bivalent organic radicals are also specified. The polyonium salt may contain more than two onium atoms, as in the polysulphonium compound of the general formula, wherein R and R<SP>1</SP> represent alkyl or other hydrocarbon groups and X represents an acid radical. Two onium salt groups may be linked by more than one bivalent organic radical, as in compounds of the type Poly quaternary ammonium or phosphonium salts can be prepared by reacting a tertiary amine (e.g. pyridine, α-picoline, α-(n-nonyl)- pyridine, N-methylpiperidine, 1-phenyl-3:5-dimethylpyrazole, 2-phenylpyriminazole, di-nbutyl - # - hydroxyethylamine, dimethyl - benzylamine, diethylbenzylamine or triethylamine) or a tertiary phosphine (e.g. a trialkylphosphine) with an ester of a polyhydric alcohol, e.g. a polyhalide (e.g. methylene, ethylene, or decamethylene dibromide ; ethylene-bis-oxymethyl chloride ; decamethylene - bis oxymethyl chloride ; #:#<SP>1</SP> - di - chlorodiethylether; chloromethyl - # - chlor - ethylether ; chloromethyl - y - chloropropyl ether ; xylylene dichloride ; dichlorodiacetyl; #:#<SP>1</SP> - di-(chloromethoxy) - diethylsulphide; #:#<SP>1</SP> - dichlorodiethylsulphide : or α:#:γ - trichloropropane) or a poly-p-toluenesulphonate. Poly quaternary ammonium salts can also be prepared by reacting a poly tertiary amine with an alkyl ester of a monohydric alcohol. N: N<SP>1</SP> - Ethylene bis - (oxymethylpyridinium perchlorate) is prepared by adding ethylene-bisoxymethyl chloride to pyridine at 0‹C., and mixing the ethyl alcohol solution of the product with aqueous NaC10 4 . N:N<SP>1</SP>-Decamethylene - bis - (oxymethylpyridinium perchlorate), N: N<SP>1</SP>- hexamethylene - bis - (oxymethylpyridinium perchlorate), N : N<SP>1</SP> - decamethylene - bis - (thiomethylpyridinium perchlorate), N: N<SP>1</SP> - ethylene - bis - (oxymethyl - (α -nonylpyridinium) - perchlorate), N: N<SP>1</SP> - ethylene - bis - oxymethyldimethylbenzyl - ammonium perchlorate), and N: N<SP>1</SP> - ethylene - bis - (oxymethyl - 2 - phenylpyriminazolium perchlorate) are similarly prepared. α - (n - Nonyl) - pyridine is prepared by reacting α-picoline and octyl chloride in presence of sodamide. Chloromethyl - α - chloropropyl ether is prepared by reacting trimethylene chlorohydrin and trioxymethylene. #:#<SP>1</SP> - Di - (chloromethoxy) - diethyl sulphide is prepared by reacting #:#<SP>1</SP>-dihydroxydiethyl sulphide and trioxymethylene in benzene and passing in HC1. Di - n - butyl - #- -hydroxyethylamine is prepared from di-n-butylamine and ethylene oxide. 1:3 - Dioxolane - 2 - α - ethoxy - # - hydroxy - propyldimethylbenzylammonium - 5 - methyl - ammonium dichloride is prepared by heating together 2-#-(α-chloro-#-hydroxypropoxy)-ethyl - 5-chloromethyl-1:3-dioxolane and dimethylbenzylamine, 1:3 - dioxolane - 2 - α - (# - propoxy) - # - hydroxypropylpyridinium - 5 - methyl - pyridinium dichloride is similarly prepared. Bis - (n - nonylmethylsulphonium - p - toluenesulphonate) - methane is prepared by heating together dinonylthiomethane and methyl p - toluenesulphonate. Other analogous bis substituted alkanes are similarly prepared. 1:2 - Di - (laurylthio) - ethane is prepared by dissolving sodium in methyl alcohol, adding lauryl mercaptan, and then adding ethylene dibromide and refluxing. Other di(alkylthio)- alkanes and p - di - - (n - nonylthiomethyl) - benzene, #:#<SP>1</SP> - di - (decylthio) - ethyl sulphide, and bis - (n - nonylthiomethylthio) - decane (from decamethylene dithiol and nonylthiomethyl chloride) are similarly prepared. Bis - (laurylmethylsulphonium - p - toluene - sulphonate) - 2:3 - diketo - butane - 1:4 is prepared by mixing together bis-(laurylthio) - 2:3-diketobutane-1:4 and methyl p-toluenesulphonate and allowing to stand. Bis - (laurylthio) - 2:3 - diketobutane - 1:4 is prepared by adding first lauryl mercaptan and then symm-dichlorodiacetyl to methyl alcohol containing sodium. 1:2:3 - Tri - (methyllaurylsulphonium - p - toluenesulphonate) - propane is prepared by heating together glycerol trilaurylthioether and methyl p-toluenesulphonate. Glycerol trilaurylthioether is prepared by mixing lauryl mercaptan with a solution of sodium in methyl alcohol, adding 1:2:3-tribromopropane, and refluxing. Ethylene - bis - (oxymethyllaurylmethyl - sulphonium - p - toluenesulphonate) is prepared by heating together ethylene-bis-(oxymethylthiododecane) and methyl p-toluenesulphonate. Ethylene - bis - oxymethylthiododecane is prepared by adding first lauryl mercaptan and then ethylene-bis-oxymethyl chloride to methyl alcohol containing sodium. N: N<SP>1</SP> - 2 - hydroxypropane - 1:3 - pyridinium perchlorate is prepared by heating together pyridine and glycerol α-α-dibromohydrin, and adding aqueous NaC10 4  to a methyl alcohol solution of the reaction product. Oxy - bis - ethylpyridinium perchlorate is prepared by heating together pyridine and #:#<SP>1</SP>-dichlorodiethyl ether, and forming the perchlorate. 1:10 - Decamethylene bis - 1:3:5 - trimethyl - pyrazolium perchlorate is prepared by heating together decamethylene dibromide and 1:3:5- trimethylpyrazole. and forming the perchlorate. Thio - bis - (ethylpyridinium perchlorate) is prepared by refluxing together pyridine and #:#<SP>1</SP>- dichlorodiethyl sulphide, and forming the perchlorate. Ethylene bis - oxymethyltriethylphosphonium chloride is prepared by adding ethylene-bis-oxymethyl chloride to a diethyl ether solution of triethyl phosphine, warming to remove the ether, and refluxing. Decamethylene bis (triethylphosphonium bromide) is prepared by mixing together triethylphosphine and decamethylene dibromide and slightly warming. Trimethylene bis - (oxymethylpyridinium perchlorate) is prepared by mixing together pyridine and trimethylene-bis-oxymethyl chloride and forming the perchlorate. Oxy - bis - (methylpyridinium perchlorate) is prepared by mixing together symm-dichloromethylether and pyridine and forming the perchlorate. 1:4 - Tetramethylene - bis - (2 phenylpyrimin - azolium perchlorate) is prepared from 2-phenylpyriminazole and tetramethylene perchlorate. 1:4 - Tetramethylene - bis - (1 - phenyl - 4 - acetyl - 5 - methylpyrazolium perchlorate) is prepared by heating together 1-phenyl-4- acetyl-5-methyl-pyrazole and tetramethylene dibromide, and forming the perchlorate. 1:10 - Decamethylene - bis - (triethylammonium perchlorate) is prepared by refluxing decamethylene dibromide and triethylamine, adding a further quantity of triethylamine and continuing heating, and precipitating with acetone, and then forming the perchlorate. 1:4 - Tetramethylene bis - (lauryldimethyl - ammonium perchlorate) is similarly prepared. Bis - (laurylmethylsulphonium - p - toluene - sulphonate) - 1:4 - butane is prepared by heating together 1:4-dilaurylthiobutane and methyl p-toluenesulphonate. Bis - (lauryl - methylsulphonium - p - toluenesulphonate) - 1:10-decane, and bis-(nonoxymethylmethyl-sulphonium - p - toluenesulphonate) - 1:10 - decane are similarly prepared. Nonylpiperazinium - p - toluenesulphonate is prepared by heating together nonyl - p - toluenesulphonate and piperazine hydrate. Methylene - (methyldiethylammonium - p - toluenesulphonate) (methylnonylsulphonium - p - toluenesulphonate) is prepared by heating together diethyl - n - nonylthiomethylamine and methyl p-toluenesulphonate. Diethyl - n - nonylthiomethylamine is prepared by allowing a solution comprising diethylamine, n-nonylthiomethyl chloride, and chloroform to stand, heating to boiling, filtering, allowing the chloroform to evaporate, and distilling under reduced pressure. n- Nonylthiomethyl chloride is prepared by reacting an equimolecular mixture of n-nonyl mercaptan and formaldehyde with a molecular equivalent of HCl. 2 - Methyl - 4:5 - dihydroimidazole is prepared by heating ethylene diamine hydrochloride with sodium acetate. Trimethylene - bis - 2 - undecyl - 4:5 - dihydro - imidazolium perchlorate is prepared by heating together undecylimidazoline and trimethylene dibromide, and converting the resulting bromide to the perchlorate. Pentamethylene - bis - 2 - methyl - 4:5 - dihydroimidazolium perchlorate is prepared similarly.