VINYLIC CATIONS FROM SOLVOLYSIS .2. STEREOCHEMISTRY OF SN1 REACTION OF 1,2-DIANISYL-2-PHENYLVINYL HALIDES

被引：75
作者：
RAPPOPOR.Z
APELOIG, Y
机构：
[1] Department of Organic Chemistry, Hebrew University, Jerusalem
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1969年 / 91卷 / 24期
关键词：
D O I：
10.1021/ja01052a033
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
cis- and trans-1,2-dianisyl-2-phenylvinyl bromide and chloride were prepared and their stereochemistry determined. Solvolysis in the presence of benzylthiolate and p-toluenethiolate ions in 80% ethanol, chloride ion in acetic acid and in dimethylformamide, and acetate ion in acetic acid gave cis and trans products derived from capture of the intermediate cation by the nucleophile, in 1:1 ratios. 1,2-Dianisyl-2-phenylethanone is formed on solvolysis in aqueous ethanol, formic acid, and dimethylformamide. Predictions regarding the stereochemistry of the Sn1 vinylic substitution are discussed and it is concluded that the product-forming intermediate is a linear sp hybridized dissociated vinyl cation. © 1969, American Chemical Society. All rights reserved.
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页码：6734 / +
页数：1
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