Patent GB-637295-A (GB)
Title: An improved manufacture of sulphur-bearing alcohols
Filed: 1946-03-27
Abstract: High molecular weight beta (tertiary-alkyl thio) alcohols of the general formula <FORM:0637295/IV (b)/1> where the R groups are alkyl, groups which may or may not be the same and RI, RII, RIII and RIV are hydrogen atoms or alkyl groups, are prepared by the reaction of a high molecular weight tertiary mercaptan, preferably containing 6-20 carbon atoms with an alkylene oxide in the presence of an alkaline compound such as an alkali metal, or alkaline earth metal hydroxide or an alkyl ammonium hydroxide such as tetramethyl ammonium hydroxide as a catalyst.  The reaction temperature may be from 0 DEG  to 150 DEG  C., preferably between 20 DEG  and 100 DEG  C. and the catalyst may be an aqueous solution of say 5-50 per cent of an alkaline compound.  b -Tertiary-alkyl thio ethanols prepared by the reaction include the tertiarybutyl, tertiaryamyl, tertiaryoctyl and tertiarydecyl derivatives of b -thio-ethanol; the tertiarybutyl, tertiaryoctyl and tertiarydodecyl derivatives of b -thio-isopropanol; the tertiarybutyl and tertiarycetyl derivatives of thio-tertiarybutanol and b -(tertiarycetyl thio) secondary-butanol. Chemical derivatives of these compounds such as ethers and esters may be prepared by the usual chemical methods.  The alcohols and their derivatives may be used as plasticizers, antioxidants, wetting agents fungicides and in particular as insecticides.  The halides, prepared by reaction with hydrogen halides, may be reacted with alkali cyanides to give the nitriles, which on hydrolysis give the acids. The nitrates of the alcohols are used as ignition promoters in diesel fuels. In examples: (1) ethylene oxide is passed into diisobutyl mercaptan in aqueous caustic soda to give b -(tertiaryoctyl thio) ethanol; (2) propylene oxide is used instead of ethylene oxide in the process of (1) to give b -(tertiaryoctyl thio) isopropanol; (3) ethylene (oxide is passed into a tertiarydodecylmercaptan in aqueous caustic soda, giving b -(tertiarydodecyl thio) ethanol; (4) propylene oxide is used instead of ethylene oxide in the process of (3) to give b -(tertiarydodecyl thio) isopropanol; (5) b -(tertiaryoctyl thio) ethanol in mineral oil is used as an insecticide, and (6) b -tertiaryoctyl thio) isopropanol is used in the same manner.ALSO:Insecticidal compositions comprise b -(tertiary-alkyl) thio ethanols of the general formula <FORM:0637295/VI/1> where the R groups represent alkyl groups similar or not, and RI, RII, RIII and RIV are hydrogen atoms or alkyl groups, admixed with a carrier. Suitable compositions are those formed with inert carriers such as diatomaceous earth, bentonite, talc, sulphur and wood flours but in the preferred composition the compound is dissolved in mineral oil. The solution in mineral oil may be utilised in aqueous emulsion.  The thio ethanols may also be dissolved in a volatile solvent such as Freon and may be used in combination with other toxicants such as D.D.T., Rotenone and Pyrethrum.  Further possible combinations include admixtures with inorganic pigments, organic dyes, lead arsenate, pyrethrins, cryolite, zinc sulphide, organic thiocyanates and nicotine.  In examples (5) b -(tertiary-octyl thio) ethanol is dissolved in mineral oil to give an insecticidal composition and (6)b -(tertiary-octyl thio) isopropanol is similarly compounded.