Display options
Cite
Burdzinski G, Kubicki J, Sliwa M, et al. Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol. J Org Chem. 2012;78(5):2026-32doi: 10.1021/jo302023a.
Burdzinski, G., Kubicki, J., Sliwa, M., Réhault, J., Zhang, Y., Vyas, S., Luk, H. L., Hadad, C. M., & Platz, M. S. (2013). Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol. The Journal of organic chemistry, 78(5), 2026-32. https://doi.org/10.1021/jo302023a
Burdzinski, Gotard, et al. "Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol." The Journal of organic chemistry vol. 78,5 (2013): 2026-32. doi: https://doi.org/10.1021/jo302023a
Burdzinski G, Kubicki J, Sliwa M, Réhault J, Zhang Y, Vyas S, Luk HL, Hadad CM, Platz MS. Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol. J Org Chem. 2013 Mar 01;78(5):2026-32. doi: 10.1021/jo302023a. Epub 2012 Dec 26. PMID: 23190449.
Copy Download .nbib Format: NLM
Share it on

J Org Chem. 2013 Mar 01;78(5):2026-32. doi: 10.1021/jo302023a. Epub 2012 Dec 26.

Mechanistic aspects of ketene formation deduced from femtosecond photolysis of diazocyclohexadienone, o-phenylene thioxocarbonate, and 2-chlorophenol.

The Journal of organic chemistry

Gotard Burdzinski, Jacek Kubicki, Michel Sliwa, Julien Réhault, Yunlong Zhang, Shubham Vyas, Hoi Ling Luk, Christopher M Hadad, Matthew S Platz

Affiliations

  1. Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University in Poznan, Umultowska 85, 61-614 Poznan, Poland. [email protected]

PMID: 23190449 DOI: 10.1021/jo302023a

Abstract

The photochemistry of diazocyclohexadienone (1), o-phenylene thioxocarbonate (2), and 2-chlorophenol (3) in solution was studied using time-resolved UV-vis and IR transient absorption spectroscopies. In these three cases, the same product cyclopentadienyl ketene (5) is formed, and two different mechanistic pathways leading to this product are discussed: (a) rearrangement in the excited state (RIES) and (b) a stepwise route involving the intermediacy of vibrationally excited or relaxed carbene. Femtosecond UV-vis detection allows observation of an absorption band assigned to singlet 2-oxocyclohexa-3,5-dienylidene (4), and this absorption feature decays with an ∼30 ps time constant in hexane and acetonitrile. The excess vibrational energy present in nascent carbenes results in the ultrafast Wolff rearrangement of the hot species. IR detection shows that photoexcited o-phenylene thioxocarbonate (2) and 2-chlorophenol (3) efficiently form the carbene species while diazocyclohexadienone (1) photochemistry proceeds mainly by a concerted process.

Publication Types