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United States Patent Office 3,262,964 United States Patent Office Patented July 26, 1966 2 The organic moiety of the sulfonyl halide reactant, R, 3,262,964 is aliphatic, including acyclic or alicyclic, or aromatic, HALO-SULFONE PRODUCTION and is Substituted with from 1 to 6 sulfonyl halide sub Frederick F. Rust, Orinda, and Harold W. Moore, Meno stituents. R is a hydrocarbon radical, that is, contains Park, Calif., assignors to Shell Oil Company, New York, 5 only carbon and hydrogen, or is a substituted-hydrocar N.Y., a corporation of Delaware bon radical, with non-hydrocarbon substituents such as No Drawing. Fied Aug. 2, 1963, Ser. No. 30,662 halogen, nitro, acyl, hydrocarbylsulfonyl, sulfo, hydro 10 Claims. (C. 260-465.7) carbyloxy, hydrocarbylsulfonyloxy, hydrocarbylsulfon This invention relates to a novel process for the pro amido, acyloxy, acylamino and the like. In addition, duction of sulfones. More particularly it relates to the O although less preferred for reasons of the diminished addition of a sulfonyl halide to an olefin. reactivity thereof, R is suitably a hydrocarbyl moiety Numerous methods are known for the production of which serves as a monomer in a halosulfonated polymeric sulfones. Typical of these are the oxidation of a sulfide or co-polymeric material, e.g., a halosulfonated ethylene to the corresponding sulfone with hydrogen peroxide or monomer in a polyethylene or ethylene-propylene poly other inorganic oxidizing agents, and the sulfonation of mer. Preferred R groups are those having from 1 to 20 aromatic hydrocarbons with sulfonic acids or sulfonyl carbon atoms and from 1 to 3 sulfonyl halide substituents. halides. These methods are limited by the availability of The term X in the above-depicted formula represents the sulfide reactant in the first instance, and by the limited halogen, that is, fluorine, chlorine, bromine or iodine, applicability of the reaction process in the second in and sulfonyl fluorides, sulfonyl chlorides, sulfonyl bro stance. Such processes are suitable for the production 20 mides and sulfonyl iodides are operable in the process of many dihydrocarbyl sulfones, but have limited utility of the invention. Within a sulfonyl halide molecule, all in the production of sulfones possessing additional re X substituents may be the same, or two or more X active substituents, particularly when the sulfone is ali groups may represent different halogens. Preferred, how phatic. ever, are sulfonyl halides wherein all X groups, if Ladd et al., U.S. 2,606,218, describe the reaction of 25 more than one sulfonyl halide radical is present, rep trichloromethylsulfonyl chloride with styrene in the pres resent the same halogen. Further preferred are the ence of a peroxide catalyst. The product, however, con Sulfonyl halides wherein the halogen has an atomic tains no sulfur, as sulfur dioxide is lost from the sulfonyl number of from 17 to 35, i.e., the middle halogens chloride, and the elements of carbon tetrachloride are chlorine and bromine, and optimum results are obtained added to the olefinic linkage. The U.S. Patents 2,521,068 30 when the sulfonyl halide is a sulfonyl chloride. and 2,573,580 to Ladd describe the production of telomers Aliphatic sulfonyl halides suitable as reactants are by the peroxide-catalyzed reaction of p-chlorobenzene those sulfonyl halides wherein the sulfonyl halide radical sulfonyl chloride with olefins and olefinic esters. is attached to an aliphatic carbon atom, and include cy It is an object of the present invention to provide a cloaliphatic and aromatic-substituted aliphatic sulfonyl novel process for the production of Sulfones. More halides. Although aliphatic sulfonyl halides wherein the particularly, it is an object to provide a process for the aliphatic moiety possesses olefinic or acetylenic unsatu addition of sulfonyl halides to olefins. ration are in part operable, preferred aliphatic sulfonyl It has now been found that these objects are ac halides contain no non-aromatic carbon-carbon unsatura complished by the process of reacting a Sulfonyl halide tion. Illustrative hydrocarbon aliphatic sulfonyl halides with an olefin to produce a 6-halo Sulfone as a 1,2-ad 40 are exemplified by alkyl, including aralkyl, sulfonyl dition product, which process is conducted in the presence halides such as methanesulfonyl chloride, methanedi of certain metallic compounds as catalyst. sulfonyl chloride, methanetrisulfonyl bromide, ethane The metallic compounds which have been found to be sulfonyl chloride, 2-propanesulfonyl fluoride, propane useful catalysts for the process of the invention are cop sulfonyl iodide, hexanesulfonyl fluoride, 1,2-ethanedi per compounds, particularly salts comprising copper cat 45 sulfonyl chloride, 1,1-ethanedisulfonyl bromide, g-phen ions, either in the cuprous or cupric valence state, and ylethanesulfonyl iodide, benzylsulfonyl bromide, 1,5- simple anions, organic or inorganic. Although copper pentanedisulfonyl chloride, 1,2,6-hexanetrisulfonyl bro compounds such as the oxide, carbonate, acetate, Sulfate mide and the like, while acyclic aliphatic sulfonyl halides and the like are operable, best results are obtained when possessing non-hydrocarby substituents include 3-chloro the catalyst employed is a halide, e.g., fluoride, chloride, 50 butanesulfonyl chloride, 5 - carbethoxypentanesulfonyl bromide or iodide. Preferred are copper halides wherein fluoride, 3-dimethylamino-2-methylbutanesulfonyl chlo the halogen has an atomic number from 17 to 35, that ride, 6-acetylhexanesulfonyl bromide and the like. Sul is, the middle halogens, chlorine and bromine. Although fonyl halides suitable as reactants include hydrocarbyl cuprous salts are generally preferred over the corre sulfonyl halides such as cyclohexanesulfonyl chloride, sponding cupric salt, in most cases, cupric salts give satis 55 cyclopentanesulfonyl chloride, 1,4-cyclohexanedisulfonyl factory results. Particularly preferred as catalyst for bromide, tetrahydronaphthalene-1,8-disulfonyl iodide, 2 the process of the invention is cuprous chloride. methylcyclohexanesulfonyl fluoride, and 3-phenylcyclo The copper compounds are employed in catalytic pentanesulfonyl chloride, as well as substituted-hydro carbyl cycloalkyl sulfonyl halides such as 3-chlorocyclo amounts. While the optimum amount of catalyst will 60 hexanesulfonyl chloride, 1,4-(2-diethylaminocyclohex depend upon the particular copper compound, Sulfonyl ane) disulfonyl bromide, 3-carbomethoxycyclopentane halide and olefin employed, amounts of catalyst from sulfonyl chloride and 4-methylsulfonylcycloheptanesul about 0.005 mole to about 0.5 mole per mole of limiting fonyl bromide. reactant are generally satisfactory, although amounts of Aromatic sulfonyl halide reactants have from 1 to 6 catalyst from about 0.05 mole to about 0.2 mole per mole 65 aromatic rings which are fused or non-fused, but prefer of limiting reactant are preferred. ably have from 1 to 2 aromatic rings. Exemplary aro The sulfonyl halide is a mono- or poly-halosulfonated matic sulfonyl haildes include benzenesulfonyl chloride, organic compound. Preferred sulfonyl halides are rep benzenedisulfonyl chloride, p-toluene sulfonyl chloride, resented by the formula R-(-SOX) wherein R is a m-bromobenzenesulfonyl bromide, p-chlorobenzenesulfo mono- to n-valent organic, preferably hydrocarbon, radi 70 nyl chloride, p-tert-butylbenzenesulfonyl iodide, 1-naph cal having up to 40 carbon atoms, X represents halogen thalenesulfonyl fluoride, 1,4-naphthalenedisulfonyl bro and n is a whole number from 1 to 6 inclusive. mide, 4-chlorosulfonylphenyl methanesulfonate, p-meth 3,262,964 3 4. oxybenzenesulfonyl bromide, 2,4-dimethylbenzenesulfonyl reactants, and are substantially inert towards the sulfonyl chloride, N-methyl-N-ethylsulfonyl-p - chlorosulfonylani halide and olefin reactants as well as the sulfones produced line, bis(4-chlorosulfonylphenyl)methane, and di(3-bro therefrom. Preferred solvents for the process of the in mosulfonylphenyl). vention are polar, that is, contain uneven charge distribu Further preferred are organic mono- to trisulfonyl hal tion, Illustrative solvents include the ethers, e.g., acyclic ides, particularly mono, wherein the organic moiety is ethers such as diethyl ether, dibutyl ether and methyl saturated aliphatic, particularly alkyl, having 1 to 18 car hexyl ether, and lower alkyl ethers (full) of polyhydric bon atoms, preferably 1 to 10, or is mononuclear aromatic, alcohols such as ethylene glycol, glycerol, diethylene particularly aryl, having 6 to 10 carbon atoms. glycol and 1,2,6-hexanetriol wherein the alkyl groups have The sulfonylhalides are prepared by conventional meth 0. from 1 to 4 carbon atoms, as well as cyclic ethers such as ods, as by halosulfonation of a hydrocarbon or conversion dioxane, tetrahydrofuran, tetrahydropyran and dioxolane; of the corresponding sulfonic acid to the sulfonyl halide the nitriles, particularly lower alkyl nitriles such as ace by treatment with an inorganic halide, e.g., thionyl halide. tonitrile, propionitrile and butyronitrile; sulfones such as The sulfonyl halide is reacted with an olefin. By olefin dimethyl sulfone, diethyl sulfone, propyl hexyl sulfone, is meant a compound possessing at least one carbon-car diphenyl sulfone and sulfolane; and N,N-dialkylamides, bon double bond, and no carbon-carbon double bonds that such as dimethylformamide and N,N-diethyl acetamide. are conjugated with other carbon-carbon non-aromatic un Preferred solvents comprise the nitriles, especially cyano saturation. Suitable olefins have from 2 to 20 carbon
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