Patent GB-649135-A (GB)
Title: Improvements in or relating to the production of cyclic sulphur-containing organic compounds
IPC: C07D335/02
Filed: 1948-01-28
Abstract: Sulphonium compounds which are germicides and/or surface-active agents are obtained by reacting a heterocyclic polymethylene sulphide with a long-chain alkyl halide.  Preferred alkyl halides are those containing at least 8 carbon atoms, especially those containing 14-16 carbon atoms/molecule.  If desired, a mixture of alkyl halides, e.g. a mixture obtained by the halogenation of the hydrocarbon fraction obtained by the distillation of crude mineral oil, or the mixture obtained by halogenating a kerosine fraction boiling in the range 175 DEG  to 320 DEG  C. may be used.  Suitable heterocyclic polymethylene sulphides can be extracted from recovered oil obtained from spent sulphuric acid used in the treatment of sulphur-containing mineral oil or mineral oil fractions by fractional distillation, steam distillation or extractive distillation in the presence of a polar solvent, or a combination of these.  A suitable recovered oil is obtained as a by-product in the refining of aromatic concentrates from petroleum oil and polymethylene compounds which may be isolated from it by fractional distillation include tetramethylene sulphide, methyltetramethylene sulphides, pentamethylene sulphide and methyl pentamethylene sulphides.  The reaction may be carried out by refluxing the reactants in a suitable solvent, e.g. methyl or ethyl alcohol.  If desired, a catalyst, e.g. iodine, may be used. The cyclic sulphides used as starting materials may be obtained from a feedstock consisting of a benzene extract tar oil obtained by sulphur dioxide treatment of a straight-run benzine cut of petroleum having a boiling range of 100-160 DEG  C. followed by acid-refining of the benzine extract with 96-98 per cent sulphuric acid, dilution of the spent acid and recovery of the oil layer.  The benzine extract tar oil is distilled and cuts containing sulphides and hydrocarbons are dissolved in concentrated sulphuric acid, diluted and steam distilled. Tetramethylene sulphide, methyltetramethylene sulphide, pentamethylene sulphide and methylpentamethylene sulphide are isolated from the crude sulphide fractions.  In the examples: (1) pentamethylene sulphide and cetyl bromide are heated together in the presence of ethyl alcohol; (2) a fraction boiling in the range 100-180 DEG  C. from a benzine extract tar oil obtained by extracting a straight benzine cut with liquid sulphur dioxide is heated with cetyl bromide in the presence of ethyl alcohol; (3) pentamethylene sulphide is heated with cetyl bromide in the presence of methyl alcohol to give cetyl thiacyclohexane sulphonium bromide; (4) cetyl thiacyclohexane sulphonium bromide is dissolved in a mixture of water, alcohol and acetone giving a solution which has good germicidal properties.ALSO:New compounds, stated to have germicidal properties, are prepared by heating a heterocyclic polymethylene sulphide with an alkyl halide having at least 8 carbon atoms in the molecule.  A composition of one of these compounds, cetylthiacyclohexane sulphonium bromide, dissolved in a mixture of water, alcohol and acetone, is stated to have very good germicidal properties.  The preparation of these compounds is described, (see Group IV(b)).