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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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