Patent GB-800963-A (GB)
Title: Improvements in or relating to sulphonium compounds
Inventor: DOYLE FRANK PETER
Filed: 1955-11-28
Abstract: The invention comprises sulphonium quaternary ammonium compounds of the general formula: <FORM:0800963/IV (b)/1> (wherein R, R1, R2, R3 and R4 are the same or different, each being an alkyl group, and X-is a monovalent anion or 2X- the divalent anion of a dibasic acid, the total number of carbon atoms in the cation being from 11 to 16 inclusive) and the manufacture thereof by treating an appropriate di-N-substituted alkylthioalkylamine (or monoquaternary salt thereof) with an excess of a quaternizing agent alone or in the presence of a diluent such as acetone or alcohol.  The anion X is chosen from the usual non-toxic groupings, such as halide, sulphate or tartrate. Preferred compounds are those in which n is 4 or 5, the total number of carbon atoms in the cation is 13 to 15, and the total number of carbon atoms in R and R1 is not more than 4 and in R3 and R4 not more than 8.  The following compounds are described in the examples: 1-diethylsulphonium-4-triethylammoniumbutane di-iodide and ditartrate, 1 - ethylmethylsulphonium - 4 - triethylammoniumbutane di - iodide, 1 - ethylmethylsulphonium - 4 - ethyldi - n - propylammoniumbutane di - iodide, 1 - dimethylsulphonium - 4 - methyldi - isopropylammoniumbutane di - iodide, 1 - ethylmethylsulphonium - 4 - methyldi - isopropylammoniumbutane di-iodide, 1-methylisopropylsulphonium - 4 - methyldiisopropylammoniumbutane di - iodide, 1 - ethylmethylsulphonium-4 - dimethylethylammoniumbutane di - iodide, 1 - dimethylsulphonium - 4 - diethylmethylammoniumbutane di - iodide, 1 - diethylsulphonium - 4 - dimethylethylammoniumbutane di - iodide, 1 - ethylmethylsulphonium-4 - diethylmethylammoniumbutane di - iodide, 1 - dimethylsulphonium - 4 - di - n - propylmethylammoniumbutane di - iodide, 1 - methyl - n - propylsulphonium - 4 - di - n - propylmethylammoniumbutane di - iodide, 1 - dimethylsulphonium - 4 - di - n - butylmethylammoniumbutane dibromide, 1 - ethyl - n-propylsulphonium - 4 - diethyl - n - propylammoniumbutane di - iodide, 1 - diethylsulphonium - 5 - triethylammoniumpentane diiodide, 1 - ethylmethylsulphonium - 5 - ethyldi-n - propylammoniumpentane di - iodide, 1 - ethylmethylsulphonium - 5 - dimethylethylammoniumpentane di - iodide, 1 - dimethylsulphonium - 5 - diethylmethylammoniumpentane di - iodide, 1 - ethylmethylsulphonium - 5 - diethylmethylammoniumpentane diiodide, 1 - dimethylsulphonium - 5 - di - n - propylmethylammoniumpentane di - iodide, 1 - dimethylsulphonium - 6 - trimethylammoniumhexane di - iodide, 1 - ethylmethylsulphonium - 6 - trimethylammonium - hexane diiodide, 1 - ethylmethylsulphonium - 6 - dimethylethylammonium - hexane di - iodide, 1 - ethylmethylsulphonium - 6 - diethylmethylammonium - hexane di - iodide, 1 - diethylsulphonium - 6 - dimethylethylammoniumhexane di - iodide, 1 - methyl - iso - propylsulphonium - 6 - dimethyl - iso - propylammoniumhexane di - iodide, 1 - methyl - n - propylsulphonium - 6 - dimethyl - n - propylammoniumhexane di - iodide, 1 - methyl - n - butylsulphonium - 6 - n - butyldimethyl - ammoniumhexane di - iodide and 1 - diethylsulphonium - 6 - triethylammoniumhexane diiodide.  Starting materials.  Di-N-substituted alkylthioalkylamines (in which the total number of carbon atoms is 9 to 14) are prepared by reacting the appropriate haloalkylamine hydrohalide with the sodium or potassium salt of an alkanethiol in a solvent, or by converting the appropriate di - N - substituted hydroxyalkylamine to the thioalkylamine by the action of thiourea and hydrobromic acid, basifying and alkylating the thiol group.  The following are prepared by one or other of these methods:-4 - ethylthiobutyldiethylamine, 4 - methylthiobutyldiethylamine (and its styphnate), 4-methylthiobutyldi - n - propylamine, 4 - methylthiobutyldi - isopropylamine, 4 - ethylthiobutyldiisopropylamine, 4 - isopropylthiobutyldi - isopropylamine, 5 - ethylthioamyldiethylamine and 5-methylthioamyldi-n-propylamine.  4 - Chlorobutyldiethylamine, 4 - chlorobutyldi - n - propylamine, 4 - chlorobutyldi - iso - propylamine, 5 - chloroamyldiethylamine and 5 - chloroamyldi-n-propylamine hydrochlorides are prepared by the action of thionyl chloride on the corresponding hydroxy-compounds.  4 - Hydroxybutyldi - n - propylamine and 4-hydroxybutyldi - iso - propylamine are prepared by reacting b -carbomethoxypropionyl chloride with di-n-propylamine and di-isopropylamine respectively and reducing the resulting esteramides with lithium aluminium hydride, and 5 - hydroxyamyldi - n - propylamine is prepared similarly starting from g -carbomethoxybutyryl chloride and di-n-propylamine.