Theoretical investigation of the oxidation pathways of the Cl-initiated reaction of 2-methyl-3-buten-2-ol

The mechanism and products of the reaction of 2-methyl-3-buten-2-ol (MBO232) with Cl atoms in the presence of O-2 have been elucidated by performing high-level quantum chemistry calculations. The geometries of the reactants, intermediates, transition states, and products are optimized at the MP2(full)/6-311G(d, p) level, and their single-point energies are refined at the CCSD(T)/6-311+G(d, p) level. The potential energy surface profiles have been constructed at the CCSD(T)/6-311+G(d, p)//MP2(full)/6-311G(d, p) + 0.95 x ZPE level of theory, and the possible channels involved in the reaction are also discussed. The calculations indicate that the reaction predominantly proceeds via the addition of Cl atoms to the double bond rather than the direct abstraction of the H atoms in MBO232. The nascent adducts (CH3)(2)C(OH) CHCH2Cl (IM1) and (CH3)(2)C(OH) CHClCH2 (IM2) do not undergo subsequent isomerization and dissociation reactions, but rather react with O-2. The theoretical results show that the major products are CH2ClCHO and CH3C(O)CH3 for the reaction of MBO232 + Cl in the presence of O-2, which is in good agreement with the experimental finding.