Theoretical Study of Thermal Rearrangements of 1-Hexen-5-yne, 1,2,5-Hexatriene, and 2-Methylenebicyclo[2.1.0]pentane


Bozkaya U., ÖZKAN İ.

JOURNAL OF ORGANIC CHEMISTRY, cilt.77, sa.5, ss.2337-2344, 2012 (SCI-Expanded) identifier identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 77 Sayı: 5
  • Basım Tarihi: 2012
  • Doi Numarası: 10.1021/jo202645k
  • Dergi Adı: JOURNAL OF ORGANIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.2337-2344
  • Orta Doğu Teknik Üniversitesi Adresli: Evet

Özet

In this research, a comprehensive theoretical investigation of the thermal rearrangements of 1-hexen-5-yne, 1,2,5-hexatriene, and 2-methylenebicyclo[2.1.0]pentane is carried out employing density functional theory (DFT) and high level ab initio methods, such as the complete active space self-consistent field (CASSCF), multireference second-order Moller-Plesset perturbation theory (MRMP2), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. The potential energy surface (PES) for the relevant system is explored to provide a theoretical account of pyrolysis experiments by Huntsman, Baldwin, and Roth on the target system. The rate constants and product distributions are calculated using theoretical kinetic modelings. The rate constant for each isomerization reaction is computed using the transition state theory (TST). The simultaneous first-order ordinary-differential equations are solved numerically for the relevant system to obtain time-dependent concentrations, hence the product distributions at a given temperature. Our computed energy values (reaction energies and activation parameters) are in agreement with Roth's experiments and the product distributions of Huntsman's experiments at 340 and 385 degrees C with various reaction times, while simulated product fractions are in qualitative accordance with Baldwin's experiment.