Patent GB-532676-A (GB)
Title: A process for the production of thio-ethers and/or mercaptans
Filed: 1939-07-19
Abstract: 532,676. Thio-esters and mercaptans. FIFE, J. G. (Naamlooze Vennootschap de Bataafsche Petroleum Maatschappij). July 19, 1939, No. 21008. [Class 2 (iii)] Thio-ethers and mercaptans are prepared from unsaturated hydrocarbons by interaction with compounds of the general formula R.SH where R may be hydrogen or an organic radical in the presence of peroxides as catalysts and of iron, chromium, magnesium, aluminium, thorium, uranium, cerium, lantharum, beryllium, osmium, molybdenum, vanadium and magganese salts of strong inorganic acids as activators. The peroxides are active in very small amounts, and may be added to the initial material but in most cases they are naturally present therein. They may also occur in the reaction media used, such as in technical ethers and technical dioxane. The peroxides occurring in dioxane are particularly active. Suitable peroxides mentioned include olefine peroxides, ketone peroxides, ether peroxides, and aromatic peroxides and as benzoyl and tetraline peroxides. The preferred inorganic acid from which the metal salts are derived is hydrochloric acid, but sulphuric, phosphoric and nitric acid salts may also be used. In the case of the halides of aluminium and trivalent iron, it is necessary that water should be present, the anhydrous salts being ineffective. The preferred activates are the halides of iron, chromium, magnesium, aluminium, thorium and uranium. The metal salts may be used in finely divided form or in the form of lumps or grains, or in combination with other substances, if necessary in the form of complex or double compounds, e.g. AlCl 3 . BaCl 2 , AlBr 3 -KCl, FeCl 3 .NaCl, MgCl 2 .CaCl 2 , CrCl 3 .NaCl, and Cr 2  (SO 4 ) 3 .BeCl 2 . They may also be employed on inert carriers such as pumice, silica gel, kieselguhr or chrome. The process is preferably carried out below 100‹C. and in the liquid state. Solvents employed are hydrocarbons such as hexane, octane, benzene and toluene, ethers such as di-ethyl ether and dipropyl ether, dioxane, organic acids and esters such as glacial acetic acid and ethyl acetate, and halogenated hydrocarbons such as chloroform and carbon tetrachloride. Hydrocarbons mentioned as starting materials include ethylene, butene-1, butene-2, hexene-1, cetene acetylene, hexyne-1, cetyn-2, styrene, phenyl acetylene, cyclohexene, butadiene and pinene. Mixtures of unsaturated hydrocarbons may also be used, such as a vapour phase crack gasoline produced by cracking paraffin wax. Mercaptans mentioned as starting materials include hydrogen sulphide, methyl-, ethyl-, propyl-, isopropyl-, tertiary butyl-, allyl-, and cetyl-mercaptans, thiophenol, thiocresol, benzyl-mercapton, monothio-glycol, di-thio-glycol, thio-glycollic acid and ethylene thiochlorhydrine. Mixtures of mercaptans may also be used such as the crude mercaptan mixture obtained in the lye treatment of crack distillates of some crude oils. In examples : (1) cetene-1, which had been allowed to stand in air and so form peroxide is mixed with ethyl mercaptan in the presence of anhydrous ferrous chloride. A spontaneous reaction takes place to form catyl ethyl sulphide. (2) Peroxide containing octene-2 is reacted with isopropyl mercaptan in the presence of ferrous chloride to give cetyl isopropyl sulphide. (3) Propene and ethyl mercaptan are reacted in the presence of peroxide containing dioxane and anhydrous magnesium chloride, to give ethyln-propyl sulphide. (4) Peroxide containing hexene-1 is reacted with thiophenol in the presence of dry ferrous chloride to give n-hexylphenyl sulphide. (5) Butadiene-1:3 and ethyl mercaptan are reacted in peroxide containing dioxene in the presence of dry ferrous chloride to give a mixture of the reaction products of one and two molecules of ethyl mercaptan respectively with one molecule of butadiene. (6) Ethylene thiochlorhydrin is added to a mixture of peroxide containing cyclohexane in peroxide containing dioxane solution in the presence of chromium trichloride to give cyclohexyl chlorethyl sulphide. (7) Peroxide containing hexyn-1 is added to a mixture of ethyl mercaptan and magnesium chloride to give a mixture of reaction products of hexyn-1 with one and two molecules of ethyl mercaptan respectively. (8) Hydrogen sulphide is passed into a mixture of peroxide containing cetene-1 and magnesium chloride to give di-n-cetyl sulphide.