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The regioselective pyrolysis of (trithio)carbonate: A computational study

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Abstract

The regioselective pyrolysis of sec-butyl methyl (trithio)carbonate was calculated at the MP2/6-31G(d) level in the Gaussian program. Twelve possible pathways were calculated. Nine of them gave the desired alkene products, 1-butene, E-butene, and Z-butene, and the other three, the rearrangement products, sec-butyl methyl ether and butanone for sec-butyl methyl carbonate and sec-butyl methyl thioether and butane-2-thione for sec-butyl methyl trithiocarbonate. It was shown that the two-step mechanism, including the carbonyl oxygen- or thion sulfur atom-involved six-membered ring transition state, as rate-determining step, is a preferred mechanism of the pyrolysis. The calculated product distribution is consistent with the experimental data on the pyrolysis of sec-butyl methyl carbonate. The product distribution for sec-butyl methyl trithiocarbonate was also predicted by the MP2/6-31G(d) method.

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Authors and Affiliations

  1. Department of Chemical Engineering, Yancheng Institute of Industry Technology, Yancheng, Jiangsu, 224005, P. R. China

    X. Zhu, X. Zhou, W. Zhang & D. Xiang

  2. Key Laboratory of Coordination Chemistry and Functional Materials in Universities of Shandong, Dezhou College, Dezhou, Shandong, 253023, P. R. China

    P. Wu

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  1. X. Zhu
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Correspondence to X. Zhu.

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Zhu, X., Zhou, X., Zhang, W. et al. The regioselective pyrolysis of (trithio)carbonate: A computational study. Russ J Gen Chem 85, 2399–2407 (2015). https://doi.org/10.1134/S107036321510028X

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  • DOI: https://doi.org/10.1134/S107036321510028X

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