Patent GB-711583-A (GB)
Title: Ditertiary diamines and diquaternary diammonium salts and processes for their production
Filed: 1952-07-04
Abstract: The invention comprises diquaternary ammonium salts of formula <FORM:0711583/IV (b)/1> and amines of formul  <FORM:0711583/IV (b)/2> and <FORM:0711583/IV (b)/3> where Ph is an o- or p-phenylene radicle, X is O or S, n is 2 or 3, R is an alkyl radicle of up to 4 carbon atoms and An#q is a monovalent anion in particular of a hydrohalic acid, of a methyl or ethyl sulphuric acid or of an aryl monosulphonic acid or the equivalent of a polyvalent anion.  The amines may be made by reacting compounds of formula HX-Ph-SH or their salts with 2 mols. of tertiary aminoalkyl halides of formula Hal-(CH2)n-N(CH3)2 or <FORM:0711583/IV (b)/4> where Hal is Cl, Br or I, preferably in the presence of a solvent and a base.  Sodium amide, hydride and methylate and potassium hydroxide are representative of bases specified.  When amides are used neutral or non-hydroxy group containing solvents should be used representative being dibutyl ether, dioxan, toluene and paraffin hydrocarbons, alcohols, e.g. butanol may be used if alcoholates are used and water is suitable with alkali metal hydroxides.  Temperatures of 0-150 DEG  C. may be used. Representative of many specified amines are 1 - (b  - dimethylamino - ethoxy) - 2 - and - 4 - (b  - dimethylamino - ethylmercapto)-benzene, 1,2- and 1,4-bis-(g -dimethylaminopropylmercapto) - benzene and 1 - (b  - butylmethylamino - ethoxy) - 4 - (b  - butylmethylamino - ethylmercapto) benzene.  Salts of the amines with e.g. hydrochloric, sulphuric, acetic and citric acids are mentioned. The amines may be alkylated to the final quarternary ammonium compound.  Representative of many specified alkylating agents are methyl chloride, dimethyl sulphate, p-toluene sulphonic acid methyl ester, ethyl iodide, allyl bromide and isobutyl iodide. Solvents may be present and temperatures of up to about 100 DEG  C. employed.  Quaternary salts may be converted into salts of a different anion by double decomposition, e.g. iodides to sulphates by treatment with silver sulphate. Representative of many specified quaternary ammonium salts are the dimethiodides of 1-(b (dimethylaminoethoxy) - 4 - (b  - dimethylamino - ethylmercapto) - benzene and 1,4 - bis - g  - dimethyl amino - propylmercapto) - benzene and the diethochloride, diethosulphate, di-isobutoiodide and di-allylo - bromide of 1 - (g  - dimethylamino - propoxy) - 4 - (g  - dimethylaminoethylmercapto) - benzene and 1,4 - bis - (g -dimethylamino - propylmercapto) - benzene.  In examples: (1) monothiohydroquinone is reacted with g -dimethylamino propyl chloride in toluene under nitrogen at 40-50 DEG  C. in the presence of sodium amide to yield 1-(g -dimethylamino - propoxy) - 4 - (g  - dimethylamino - propylmercapto) - benzene from which the quaternary salt is formed by treatment with methyl iodide and in (2) monothiocatechol is refluxed with dimethylaminoethyl chloride in toluene under nitrogen to yield 1-(b -dimethyl - amino - ethoxy) - 2 - (b  - dimethylamino - ethylmercapto) - benzene from which the dimetho and dietho-iodides are produced.  The products affect the muscle tonus.