1976 年 25 巻 3 号 p. 136-140
In the homogeneous metathesis of 2-heptene catalyzed by WCl6-Et3Al and WCl6-R4Sn systems, the influence of the reaction medium on the conversion was investigated. Many kinds of halogenated hydrocarbon were found to be the more excellent medium than benzene and chlorobenzene. The polychlorinated aliphatic hydrocarbons, and polyhalogenated benzenes such as trichloroethylene, tetrachloroethylene, hexachloro-1, 3-butadiene, hexachlorocyclopentadiene, 1, 1, 2, 2-tetrachloroethane, o- and m-dichlorobenzene and 1, 2, 4-trichlorobenzene gave the good conversions without the formation of the undesirable Friedel-Crafts products. The optimum range of the ratio Et3Al/WCl6 and Olefin/WCl6 shifted depending upon the medium used. In the binary solvent systems of benzene-trichloroethylene, -1, 2, 4-trichlorobenzene and -m-dichlorobenzene, the best conversions were observed at 4045 volume% of the halogenated solvent. The metathesis was significantly inhibited by the addition of the compounds containing oxygen, sulfur, nitrogen and phosphorus atoms to the reaction medium. The mechanisms of the medium effects were discussed.