| Autor: |
Oki, Michinori, Hirose, Takanori, Aki, Michihiko, Morita, Nobuhiro, Nose, Emiko, Kataoka, Yasukazu, Ono, Masaru, Toyota, Shinji |
| Zdroj: |
Bulletin of the Chemical Society of Japan; November 1996, Vol. 69 Issue: 11 p3345-3353, 9p |
| Abstrakt: |
Reactions of the olefinic moiety of the title compounds with chlorine were done as carbon tetrachloride, nitromethane, and acetonitrile solutions. The ap-isomer afforded a mixture of the corresponding addition product and olefins that are derived by deprotonation of the intervening chloro-carbocation. The product distribution was strongly affected by the solvents, although chlorinated olefins are the main products in carbon tetrachloride. The sp-isomer yielded the chloro-olefins that are rotationally isomeric with these compounds in carbon tetrachloride. No cyclized compound, which is expected if the attack of the intermediate cation on a benzene ring closely located to it takes place, was detected under these conditions. By contrast, the reaction in nitromethane resulted in formation of the cyclized compound as a major product from the spisomer. In acetonitrile, the reaction afforded the cyclized compound in a fair yield from the sp, but that of the apisomer gave products that were derived by the Ritter type reactions, in addition to those observed in other solvents. The results are attributed to the stability of the intervening cations in these solvents. In the Ritter type reaction, the first evidence that deprotonation from the intervening acetonitrilium ion to produce a ketene imine was obtained. The bromine addition to the olefinic bond in the sp-isomer of the title compound revealed that the solvent seriously affects the yields of the cyclic compound as well as the ratios of two bromo-olefins. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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