MOLECULAR-ORBITAL STUDY OF THE BENZENE OXIDE-OXEPIN VALENCE ISOMERIZATION
MOLECULAR-ORBITAL STUDY OF THE BENZENE OXIDE-OXEPIN VALENCE ISOMERIZATION
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DOI：
10.1021/ja00524a007
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
KOLLMAN, PA
中科院分区：
文献类型：
--
作者：
HAYES, DM;NELSON, SD;KOLLMAN, PA
利用从头算自洽场和半经验（MINDO/3）分子轨道理论，对各种取代苯氧化物(1)与相应的氧杂素(2)的价异构化进行了理论计算。MINDO/3计算成功地再现了已知的取代基在环位置X2和X3的效应，并给出了1 - bbb2的活化能的合理估计。对其他取代基对氧化苯-氧平平衡的影响作了一些预测。此外，还提出了一些取代模式，这些取代模式可能使平衡完全向奥西平或氧化苯同分异构体靠拢。我们还计算了氧化苯和氧平（CshUO）的结构，并将它们与环氧乙烷（C2H40）、苯亚胺（CeHsNH）和北卡二烯（C6H6CH2）的结构进行了比较。
Theoretical calculations on the valence isomerization of various substituted benzene oxides (1) to the corresponding oxepins (2) have been carried out using ab initio self-consistent-field and semiempirical (MINDO/3) molecular orbital theory. The MINDO/3 calculations successfully reproduce the known substituent effects at ring positions X2 and X3 and give a rea-sonable estimate of the activation energy for 1—> 2. Several predictions are made concerning the effect of other substituents on the benzene oxide-oxepinequilibrium. Additionally, some substitution patterns are suggested which may “drive” the equi-librium completely toward either the oxepin or benzene oxide isomers. We also presentcalculated structures for benzene oxide and oxepin (CshUO) and compare them with the structures of ethylene oxide (C2H40), benzenimine (CeHsNH), and norcara-diene (C6H6CH2).