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REGIOSELECTIVITY INVESTIGATION FOR THE PYROLYSIS OF XANTHATES: A COMPUTATIONAL STUDY.
- Source :
-
Journal of Theoretical & Computational Chemistry . Nov2013, Vol. 12 Issue 7, p-1. 14p. - Publication Year :
- 2013
-
Abstract
- MP2/6-31+G(d,p)//MP2/6-31G(d) method was employed to investigate the pyrolyses of O-sec-butyl S-methyl xanthate (Chugeav reaction) and S-sec-butyl O-methyl xanthate, which gave regioselective products of E-butene, Z-butene and 1-butene. Both procedures were found to have 13 possible pathways, of which nine pathways would generate the alkene products. For O-sec-butyl S-methyl xanthate, the computational results indicated that the most favorable three pathways corresponded to a two-step mechanism, with the rate-determining step to be a thion sulfur atom involved six-membered ring transition states. The calculated products distribution was consistent with the experimental observations. However, for S-sec-butyl O-methyl xanthate, thiol-participated four-membered ring transition states were found to be more energetically favored than the six-membered ring transition state to produce 1-butene, which can be attributed to a larger sulfur atomic size than an oxygen atom. As the calculation result, only trace amount of 1-butene could be obtained with a major product being E-butene and Z-butene as a minority. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 02196336
- Volume :
- 12
- Issue :
- 7
- Database :
- Academic Search Index
- Journal :
- Journal of Theoretical & Computational Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 91947596
- Full Text :
- https://doi.org/10.1142/S0219633613500648