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Aylward N, Kvaskoff D, Becker J, et al. Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis. J Org Chem. 2016;81(11):4609-15doi: 10.1021/acs.joc.6b00444.
Aylward, N., Kvaskoff, D., Becker, J., & Wentrup, C. (2016). Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis. The Journal of organic chemistry, 81(11), 4609-15. https://doi.org/10.1021/acs.joc.6b00444
Aylward, Nigel, et al. "Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis." The Journal of organic chemistry vol. 81,11 (2016): 4609-15. doi: https://doi.org/10.1021/acs.joc.6b00444
Aylward N, Kvaskoff D, Becker J, Wentrup C. Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis. J Org Chem. 2016 Jun 03;81(11):4609-15. doi: 10.1021/acs.joc.6b00444. Epub 2016 May 13. PMID: 27152548.
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J Org Chem. 2016 Jun 03;81(11):4609-15. doi: 10.1021/acs.joc.6b00444. Epub 2016 May 13.

Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis.

The Journal of organic chemistry

Nigel Aylward, David Kvaskoff, Jürgen Becker, Curt Wentrup

Affiliations

  1. School of Chemistry and Molecular Biosciences, University of Queensland , Brisbane, Qld 4072, Australia.
  2. Fachbereich Chemie, Philipps-Universität , D-35037 Marburg, Germany.

PMID: 27152548 DOI: 10.1021/acs.joc.6b00444

Abstract

The relationship between 4-quinolylcarbene 17, 3-quinolylcarbene 21, 2-quinolylcarbene 25, and 1-naphthylnitrene 35 has been explored experimentally and computationally. The diazomethylquinolines generated from (5-tetrazolyl)quinolines or 1,2,3-triazolo[1,5-a]quinoline by conventional flash vacuum pyrolysis (FVP) were observed by IR spectroscopy. The carbenes were generated by falling solid flash vacuum pyrolysis (FS-FVP). 4-Quinolylcarbene 17 was found to rearrange to 3-quinolylcarbene 21 and then to 2-quinolylcarbene 25, and finally via 1-naphthylnitrene 35 to 1-cyanoindene 36, which then isomerizes to 3- and 2-cyanoindenes 12 and 13. The thermal rearrangement of 2-quinolylcarbene to 1-naphthylnitrene was verified by ESR spectroscopy. The reaction mechanism has been elucidated with the help of calculations of the structures and energies of the quinolylcarbenes and 1-naphthylnitrene and the intervening aza-benzobicyclo[4.1.0]heptatrienes, aza-benzocycloheptatetraenes, and aza-benzocycloheptatrienylidenes and the transition states connecting them at the B3LYP/6-31G* level. The nonobserved 1,2-hydrogen shifts in aza-benzocycloheptatetraenes/aza-benzocycloheptatrienylidenes are found to have very high activation barriers.

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