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Author(s):   Sakai, S.
Title:   Theoretical analysis of concerted and stepwise mechanisms of the hetero-Diels-Alder reaction of butadiene with formaldehyde and thioformaldehyde
Journal:   J. Mol. Struct. THEOCHEM
Volume:   630
Page(s):   177 - 185
Year:   2003
Reference type:   Journal article
Squib:   2003SAK177-185

Reaction:   CH2O + 1,3-Butadiene → Thiacyclohex-3-ene
Reaction order:   2
Rate expression:   no rate data available
Category:  Theory
Data type:   Ab initio
Comments:   No rate constants provided. Ab initio study only with barrier heights. Report CAS-MP2/6-31G(d,p) energies based on CASSCF/6-31G(d,p) geometries. Considered stepwise and concerted hetero-Diels-Alder reactions of CH2O and CH2S with 1,3-butadiene. Biradical stepwise channel was on the order of 10 kcal/mol higher. Barrier for CH2S signficantly less than for CH2O.

CH2O + 1,3-Butadiene -> Oxacyclohex-3-ene Ea = 37 kcal/mol Hr = - 49 kcal/mol
CH2S + 1,3-Butadiene -> Thiacyclohex-3-ene Ea = 20 kcal/mol Hr = -52 kcal/mol

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