摘要：

The addition of dichlorocarbene to bicyclo [2.2.1]heptene gives the expected exo dichlorocyolopropane adduct which readily rearranges to exo-3,4-dichlorobicyclo[3.2.1]octene-2. The dibromocyclopropane formed upon addition of dibromocarbene to bicyclo [2.2.1]heptene must rearrange directly, since the product isolated was shown to be exo-3,4-dibromobicyclo[3.2.1 ]octene-2. The latter has been converted to several derivatives of bicyclo[3.2.1]octane. Addition of dibromocarbene to bicycloheptadiene gives mainly exo-3,4-dibromobicyclo[3.2.1]octadiene along with smaller amounts of the endo epimer and exo-3,6-dibromotricyclo[3.2.1.02,7]octene-3. The former two compounds rearrange to the latter on standing. All three compounds are reduced by lithium aluminum hydride to 3-bromobicyclo[3.2.1]octadiene. This vinyl bromide, which can be further reduced to bicyclo[3.2.1]octadiene, upon treatment with aqueous sulfuric acid gave tricyclo[3.2.1.02,7]octanone-3 and 3-bromotricyclo[3.2.1.02,7]octene-3. Mechanistic interpretations of several of these transformations are presented.

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