Patent GB-511614-A (GB)
Title: Production of organic compounds containing sulphur, chlorine and oxygen
Filed: 1938-04-04
Abstract: 511,614. Sulphochlorides. JOHNSON, G. W. (I. G. Farbenindustrie Akt.-Ges.). April 4, 1938, Nos. 10319, 22977 and 22978. [Class 2 (iii)] Organic compounds containing sulphur, chlorine and oxygen are manufactured by bringing saturated aliphatic or cycloaliphatic hydrocarbons into contact with sulphur dioxide and chlorine in the liquid phase, if necessary in the presence of a solvent, e.g., carbon tetrachloride or chloroform, while irradiating with short-wave light, preferably of a wave-length of 1800-5000 A. The process may be carried out by leading a gaseous mixture of sulphur dioxide and chlorine, the latter preferably being in at most equimolecular proportion to the former, through suitable dispersal means, .e.g., a filter-nozzle, into a vessel of enamelled iron, stoneware or other ceramic material filled with the liquid or liquefied hydrocarbon, which is preferably stirred, the gases being admitted near the bottom of the vessel or at various points simultaneously. The irradiation may be effected by admitting light from a source such as a mercury vapour lamp or an electric arc through a window permeable to short-wave light, e.g., of quartz, or by producing the rays within the liquid by means of immersion lamps. Suitable starting materials are paraffin waxes, petroleums and their hydrogenation products, hydrogenation products of coals and tars, mixtures of paraffinic and unsaturated hydrocarbons, hydrocarbons obtained by catalytic hydrogenation of the oxides of carbon and freed from unsaturated and oxygen-containing compounds by further hydrogenation or by other methods, e.g., by treatment with concentrated sulphuric acid or with liquid sulphur dioxide or by extraction with selective solvents, dehydration products of oxygen compounds obtained in the catalytic hydrogenation of oxides of carbon or the polymerization products from these dehydration products which have been converted into saturated hydrocarbons by hydrogenation, and cyclic saturated hydrocarbons, especially those having long saturated aliphatic side-chains, e.g., mono- or dibutyldecahydronaphthalene or dodecylcyclohexane. The products are mono- or polysulphochlorides, or in some cases chlorinated sulphochlorides, depending on the proportions of sulphur dioxide and chlorine employed. In examples : (1) an oil obtained by hydrogenation of carbon monoxide at atmospheric pressure is treated at room temperature with chlorine and sulphur dioxide while irradiating with light from a mercury vapour lamp ; the starting material may be replaced by the product obtained by hydrogenating carbon monoxide at atmospheric pressure and then hydrogenating the resulting oil under 200 atmospheres pressure in the presence of a nickel sulphide-tungsten sulphide catalyst, or the product obtained by separating from the carbon monoxide hydrogenation product a fraction consisting mainly of isoheptyl alcohol, dehydrating this by-passing it over an aluminium oxide catalyst, polymerizing the product and then hydrogenating it to produce mainly isotetradecane ; (2) an oil similar to the first starting material of (1) but containing 13-15 per cent. of constituents soluble in phosphorus pentoxide and sulphuric acid, or a material similar to the second starting material of (1) but in which the after-treatment has been carried out with sulphuric acid instead of by hydrogenation, or a product obtained by treatment of a carbon monoxide hydrogenation product with liquid sulphur dioxide, is treated as in (1) ; (3) butyldecahydronaphthalene is treated with sulphur dioxide and chlorine at room temperature while irradiating with ultraviolet light ; (4) brown coal hard paraffin wax is dissolved in carbon tetrachloride and similarly treated ; (5) a mixture of propane, sulphur dioxide and chlorine is led into carbon tetrachloride while irradiating with ultra-violet light ; (6) a mixture of isobutane, sulphur dioxide and chlorine is led into carbon tetrachloride while irradiating with light from a carbon arc lamp ; (7) a mixture of n-butane, sulphur dioxide and chlorine is led into carbon tetrachloride while irradiating with short-wave light; (8) a mixture of ethane, sulphur dioxide and chlorine is led into carbon tetrachloride while irradiating with light from a mercury vapour lamp.