Silicon Effects. IV. Solvolysis of 1-(Pentamethyldisilanyl)-2-phenylcyclopropyl Bromide in 2,2,2-Trifluoroethanol via .SIGMA.(CC)-Assisted and -Unassisted Ionization Processes.
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The rates of solvolysis of 1-(pentamethyldisilanyl)-, 1-trimethylsilyl-, and 1-methyl-substituted 2- phenylcyclopropyl bromides (<B>4a</B>, <B>4b</B>, and <B>4c)</B> were measured in 2,2,2-trifluoroethanol at 100 °C: The relative rates for <I>trans</I>-<B>4a</B>, <I>trans</I>-<B>4b</B>, and <I>trans</I>-<B>4c</B> were 3.48 : 1.0 : 10.7, respectively; the trans/cis isomeric rate ratios (<I>k</I><SUP>t</SUP>/<I>k</I><SUP>c</SUP>), which were determined by competition experiments, were 2.99 for <B>4a</B> and 1.70 for <B>4b</B>. The solvolysis of <I>trans</I>-<B>4b</B> yielded only open allylic ethers, consistent with a σ-assisted mechanism (<I>k</I><SUB>Δ</SUB>); the <I>trans</I>-<B>4a</B> predominantly, however, gave a cyclopropyl ring-retained compound, dimethyl[<I>trans</I>-2-phenyl-1-(trimethylsilyl)cyclopropyl](2,2,2-trifluoroethoxy)silane, indicative of σ-unassisted (<I>k</I><SUB>c</SUB>) solvolysis.
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