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- Title
Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform.
- Authors
Vitnik, Vesna; Vitnik, Željko; Juranić, Ivan
- Abstract
The extensive computation study was done to elucidate the mechanism of formation dibromoepoxide from cyclohexanone and bromoform. In this reaction, the formation of dihaloepoxide 2 is postulated as a key step that determines the distribution and stereochemistry of products. Two mechanistic paths of reaction were investigated: the addition of dibromocarbene to carbonyl group of ketone, and the addition of tribromomethyl carbanion to the same (C=O) group. The mechanisms for the addition reactions of dibromocarbenes and tribromomethyl carbanions with cyclohexanone have been investigated using ab initio HF/6-311++G** and MP2/6-311+G* level of theory. Solvent effects on these reactions have been explored by calculations which included a continuum polarizable conductor model (CPCM) for the solvent (HO). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies. [Figure not available: see fulltext.]
- Subjects
CYCLOHEXANONES; BROMOFORM; CHEMICAL reactions; EPOXY compounds; STEREOCHEMISTRY; CARBONYL group
- Publication
Journal of Molecular Modeling, 2012, Vol 18, Issue 10, p4721
- ISSN
1610-2940
- Publication type
Article
- DOI
10.1007/s00894-012-1468-2