THERMAL STEREOMUTATIONS OF 1-ETHYL-2-METHYL-1,2,3-TRIDEUTERIOCYCLOPROPANES

被引：12

作者：

BALDWIN, JE

SELDEN, CB

机构：

[1] Department of Chemistry, Syracuse University, Syracuse

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 06期

关键词：

D O I：

10.1021/ja00059a021

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(-)-(1R,2R,3S)-1-Ethyl-2-methyl-1,2,3-trideuteriocyclopropane and (-)-(1S,2R,3R)-1-ethyl-2-methyl-1,2,3-trideuteriocyclopropane were synthesized and heated at 380-degrees-C in the gas phase; the thermal stereomutations shown by these substrates were followed as a function of time by gas chromatography, H-1 NMR spectroscopy, and polarimetry. From the rate constants measured it was found that one-center epimerizations at C(3) are kinetically competitive and inferred that, for the trans (1R,2R,3S) substrate, (k1 + k2):k12 almost-equal-to 2:1. For the thermal stereomutations interconverting the eight isomeric 1-ethyl-2-methyl-1,2,3-trideuteriocyclopropanes, the most substituted bond hypothesis is not valid and two-center epimerizations corresponding to concerted electrocyclic processes are not kinetically dominant.

引用

页码：2239 / 2248

页数：10

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