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Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform

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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 (H2O). The calculations showed that both mechanisms are possible and are exothermic, but have markedly different activation energies.

Mechanistic pathways for the reaction of cyclohexanone with bromoform and PE map for ionic mechanism (path 2).

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Acknowledgments

This work has been financially supported by Ministry of Education and Science, Republic of Serbia, under Grant No. 172035, and by High-Performance Computing Infrastructure for South East Europe’s Research Communities European project.

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Authors and Affiliations

  1. Department of Chemistry, IChTM, University of Belgrade, Studentski trg 12-16, 11000, Belgrade, Serbia

    Vesna D. Vitnik & Ivan O. Juranić

  2. Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000, Belgrade, Serbia

    Željko J. Vitnik

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  1. Vesna D. Vitnik
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  2. Željko J. Vitnik
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  3. Ivan O. Juranić
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Correspondence to Vesna D. Vitnik.

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Vitnik, V.D., Vitnik, Ž.J. & Juranić, I.O. Carbenic vs. ionic mechanistic pathway in reaction of cyclohexanone with bromoform. J Mol Model 18, 4721–4728 (2012). https://doi.org/10.1007/s00894-012-1468-2

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  • DOI: https://doi.org/10.1007/s00894-012-1468-2

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