Cyclic Polyolefins. XXV. Cycloöctanediols. Molecular Rearrangement of Cycloöctene Oxide on Solvolysis<sup>1</sup>
作者:Arthur C. Cope、Stuart W. Fenton、Claude F. Spencer
DOI:10.1021/ja01143a018
日期:1952.12
HCOOH of cis-cycloacctene oxide, yielded more 1, 4-cycloacctanediol than the expected product, trans-1, 2-cycloacctanediol. The structure of 1, 4-cycloacctanediol was established by conversion to cycloacctane through the diacetate and cycloacctadiene, and by Oppenauer oxidation to 1, 4-cycloacctanedione, which by an intramolecular aldol condensation formed the known ketone, bicyclo (3.3.0) - 1 (5)-octen-2-one
摘要 : 顺式环戊二烯与过甲酸羟基化,顺式环戊二烯氧化物用HCOOH水解,得到的1, 4-环辛二醇比预期的产物反式1, 2-环辛二醇多。1, 4-环辛二烯二醇的结构是通过二乙酸酯和环辛二烯转化为环辛烷,并通过Oppenauer氧化为1, 4-环辛二酮,通过分子内醛醇缩合形成已知的酮,双环(3.3.0)- 1 (5)-octen-2-one。导致形成 1, 4-乙二醇的分子重排被解释为一种化学跨环效应,它允许通过 CH 键参与环氧化物的溶剂分解,CH 键是空间相邻的,因为它位于紧密的 8 元环上。8 元环状 acyloin suberion 和 cis-1,