Patent GB-680637-A (GB)
Title: Process for the production of organic compounds containing sulphur and oxygen and the compounds so produced
Filed: 1949-11-04
Abstract: Organic compounds containing sulphur and oxygen are prepared by passing an amount of oxygen or oxygen-containing gas which is more than that required for catalyzing the addition of mercaptans to unsaturated aliphatic compounds, into a liquid reaction mixture comprising a hydrocarbon mercaptan and an olefinic hydrocarbon in such relative proportions that there is at least 0.1 mol. of mercaptan for each mol. of olefinic hydrocarbon.  The products obtained containing oxygen and sulphur, e.g. sulphones and hydroxy sulphides, generally have as many carbon atoms in the molecule as the total of those in the molecule of each organic reactant. Specified starting materials are methanethiol, eicosanethiol, 1 : 4-butanedithiol, 3 - methylcyclohexanemethanethiol, 1 : 4 : 6 - hexanetrithiol benzenethiol, alkanethiols as octanethiol and 2-methylpropanethiol; and 1-hexene, 1-decene, isobutylene, 1 : 3-pentadiene, cyclohexene, 1-eicosene and styrene.  The reaction may be carried out at any temperature below the decomposition temperature of the reactants, e.g. 0-200 DEG  C.  Superatmospheric pressure is preferably employed.  The mercaptans may be used in amounts up to 10 moles. per mole. of olefine, but equimolar amounts are normally used. Inert solvents may be present such as pentane, nonane, benzene, toluene, cyclohexane, diethyl or diisopropyl ether, anisole, dioxane, methyl acetate, isobutyl butyrate and methyl benzoate.  Catalysts and/or reaction initiators are not essential; however, there may be used as initiators, substances forming free radicals under the conditions of the reaction such as peroxidic compounds, halogen compounds of which one molecule is capable of liberating two atoms of iodine from an iodide solution, metalloalkyl compounds and like compounds which are thermally decomposed into free radicals, and compounds such as aldehydes and ketones, e.g. acetone, which are decomposed into free radicals by the action of light.  The preferred initiators are the organic peroxides, especially those having at least one carbon linked to three carbon atoms and to the peroxy group and having a dissociation temperature within the range about 0-200 DEG  C. such as di-tert.-butyl diperoxalate, di-tert.-butyl dipermalonate, tert.-butyl perbenzoate, di-tert.-butyl peroxide and 2 : 2 - bis - (tert.-butylperoxy) butane.  In examples: (1) oxygen is passed under slight pressure into a solution of equimolar amounts of isobutyl mercaptan and 1-hexene in presence of di-tert.-butyl diperoxalate as initiator for 24 hours at 10 DEG  C. and the products are fractionally distilled yielding isobutyl hexyl sulphone, isobutyl 2-hydroxyhexyl sulphide and isobutyl hexyl sulphide; (2) similar products are obtained by passing oxygen under atmospheric pressure into a solution of equimolar amounts of n-octyl mercaptan and 1-decene at 60 DEG  C.  Data is given showing rate of oxygen absorption when oxygen is passed into a solution of 1-decene and n-octyl mercaptan at a temperature of 90-115 DEG  C.  The Specification as open to inspection under Sect. 91 relates to a process for the production of organic compounds containing oxygen and sulphur comprising passing oxygen or an oxygen containing gas into a liquid wherein are present a compound containing one or more thiol groups and an olefinically unsaturated compound.  Additional reactants mentioned are 3-chlorobutanethiol, 4-bromocyclohexanemethanethiol, 2 - mercaptoethanol, gamma - mercapto - alpha, beta - dimethyl butyric acid, 2 - mercaptoethyl sulphone and 4-methoxybenzenethiol, and diallyl ether, triallyl glyceryl ether, divinyl ether, 3-pentenyl butyl ether, b -allyl glycerol ether, vinyl octyl ether, vinyl oxybenzene, vinyl acetate, allyl chloride, 1 : 3-dichloropropene, allyl alcohol, diallyl sulphide, allyl mercaptan, 1-cyclohexenol and 3-propenylphenol.  This subject-matter does not appear in the Specification as accepted.