ISSN:
0192-8651
Keywords:
Computational Chemistry and Molecular Modeling
;
Biochemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
The MINDO/3 calculations were performed on the potential energy profile involved in the equilibrium \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm crotonic acid \rightleftharpoons isocrotonic acid \rightleftharpoons but-3-enoic acid} \\ {\rm (III)\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,(II)\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,(I)} \\ {\rm } \,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\,\to {\rm propene + CO}_{\rm 2} \\ \end{array} $$\end{document}Optimized structures of stable molecules and transition states have been determined; thermodynamic stabilities of pure acids and barriers indicated that the equilibrium can be set up from any acids. It was argued that direct decarboxylation is only conceivable from (I), since in this process a 1, 5-hydrogen shift is involved, whereas a higher barrier process of 1, 3-hydrogen shift is required in direct decarboxylations from other acids. Direct interconversion of (I) and (III) was found to be unfavorable due to a high barrier involved.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jcc.540050302
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