环氧化物及相关化合物的热化学研究。
Thermochemical studies of epoxides and related compounds.
机构信息
Department of Chemistry, Xavier University of Louisiana, 1 Drexel Drive, New Orleans Louisiana 70125, United States.
出版信息
J Org Chem. 2013 May 3;78(9):4303-11. doi: 10.1021/jo4002867. Epub 2013 Apr 22.
Abstract
Gas-phase heats of formation for the four butene oxide isomers are reported. They were obtained by measuring the condensed-phase heat of reduction to the corresponding alcohol using reaction calorimetry. Heats of vaporization were determined and allow gas-phase heats of formation to be obtained. The experimental measurements are compared to calculations obtained using a variety of computational methods. Overall, the G3 and CBS-APNO methods agree quite well with the experimental data. The influence of alkyl substituents on epoxide stability is discussed. Comparisons to alkenes, cyclopropanes, aziridines, thiiranes, and phosphiranes are also made. Isodesmic-type reactions were used to determine strain energies of the epoxides and related compounds with various substituents.
摘要
报告了四种丁烯氧化物异构体的气相生成热。它们是通过使用反应量热法测量相应醇的冷凝相还原热来获得的。测定了蒸发热，从而可以获得气相生成热。实验测量结果与使用各种计算方法获得的计算结果进行了比较。总体而言，G3 和 CBS-APNO 方法与实验数据非常吻合。讨论了烷基取代基对环氧化物稳定性的影响。还对烯烃、环丙烷、氮丙啶、噻吩和磷杂环戊烷进行了比较。使用等电子型反应来确定具有各种取代基的环氧化物和相关化合物的应变能。
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