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Theoretical investigation on mechanism for OH-initiated oxidation of CH2=C(CH3)CH2OH

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Abstract

The mechanism of the gas-phase reaction OH with CH2=C(CH3)CH2OH (2-methyl-2-propen-1-ol) has been elucidated using high-level ab initio method, i.e., CCSD(T)/6-311++g(d,p)//MP2(full)/6-311++g(d,p). Various possible H-abstraction and addition–elimination pathways are identified. The calculations indicate that the addition–elimination mechanism dominates the OH+MPO221 reaction. The addition reactions between OH radicals and CH2=C(CH3)CH2OH begin with the barrierless formation of a pre-reactive complex in the entrance channel, and subsequently the CH2(OH)C(CH3)CH2OH (IM1) and the CH2C(OH)(CH3)CH2OH (IM2) are formed by OH radicals’ electrophilic additions to the double bond. IM1 can easily rearrange to IM2 via a 1,2-OH migration. Subsequently, rearrangement of IM2 to form (CH3)2C(OH)CH2O (IM11) followed by dissociation to HCHO + (CH3)2COH (P21) is the most favorable pathway. The decomposition of IM2 to CH2OH + CH2=C(OH)CH3 (P16) is the secondary pathway. The other pathways are not expected to play any important role in forming final products.

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Acknowledgments

This work is supported by the Natural Science Foundation of Xuzhou Normal University (07XLA05). The authors express their gratitude to the referees for their valuable comments.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Xuzhou Normal University, 221116, Xuzhou, Jiangsu, People’s Republic of China

    Weichao Zhang & Benni Du

  2. College of Chemistry and Chemical Engineering, Xuzhou Institute of Technology, 221008, Xuzhou, Jiangsu, People’s Republic of China

    Changjun Feng

Authors
  1. Weichao Zhang
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  2. Benni Du
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  3. Changjun Feng
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Correspondence to Weichao Zhang.

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Zhang, W., Du, B. & Feng, C. Theoretical investigation on mechanism for OH-initiated oxidation of CH2=C(CH3)CH2OH. Theor Chem Acc 125, 45–55 (2010). https://doi.org/10.1007/s00214-009-0657-2

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