A COMPUTATIONAL STUDY OF THE THERMAL CYCLOREVERSION OF 2,2,6-TRIMETHYL-4H-1,3-DIOXIN-4-ONE AND A RELATED SPECIES - RETRO-DIELS-ALDER REACTION OR CONCERTED NUCLEOPHILIC-ATTACK

被引：25

作者：

EISENBERG, SWE ^{[1
]}

KURTH, MJ ^{[1
]}

FINK, WH ^{[1
]}

机构：

[1] LAWRENCE LIVERMORE NATL LAB,DEPT CHEM,DAVIS,CA 95616

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 12期

关键词：

D O I：

10.1021/jo00117a027

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Calculations up to the MP2/6-31G*//HF/3-21G level have been carried out to study the thermal cycloreversion of 2,2,6-trimethyl-4H-1,3-dioxin-4-one (1) and 2,2,4-trimethyl-6H-1,3-oxazin-6-one (3). At this level of calculation, the enthalpy of activation for the thermal cycloreversion of dioxinone 1 was found to be 31.3 kcal/mol with zero-point vibrational energy correction. The experimental value for the reaction in solution is 30.4 kcal/mol. The enthalpy of activation for the as of yet unsynthesized oxazinone 3 was found to be 44.2 kcal/mol with zero-point correction. Contrasting with the standard view that the thermal cycloreversion of dioxinone 1 is a retro-Diels-Alder reaction is the structural information from the HF/3-21G-optimized transition state 5 which shows the plane of the acetone dienophile tilted roughly 90 degrees to the plane of the acylketene diene.

引用

页码：3736 / 3742

页数：7

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