PMID- 27152548
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180516
LR  - 20180516
IS  - 1520-6904 (Electronic)
IS  - 0022-3263 (Linking)
VI  - 81
IP  - 11
DP  - 2016 Jun 3
TI  - Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 
      1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis.
PG  - 4609-15
LID - 10.1021/acs.joc.6b00444 [doi]
AB  - 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.
FAU - Aylward, Nigel
AU  - Aylward N
AD  - School of Chemistry and Molecular Biosciences, University of Queensland , 
      Brisbane, Qld 4072, Australia.
FAU - Kvaskoff, David
AU  - Kvaskoff D
AD  - School of Chemistry and Molecular Biosciences, University of Queensland , 
      Brisbane, Qld 4072, Australia.
FAU - Becker, Jurgen
AU  - Becker J
AD  - Fachbereich Chemie, Philipps-Universitat , D-35037 Marburg, Germany.
FAU - Wentrup, Curt
AU  - Wentrup C
AD  - School of Chemistry and Molecular Biosciences, University of Queensland , 
      Brisbane, Qld 4072, Australia.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20160513
PL  - United States
TA  - J Org Chem
JT  - The Journal of organic chemistry
JID - 2985193R
EDAT- 2016/05/07 06:00
MHDA- 2016/05/07 06:01
CRDT- 2016/05/07 06:00
PHST- 2016/05/07 06:00 [entrez]
PHST- 2016/05/07 06:00 [pubmed]
PHST- 2016/05/07 06:01 [medline]
AID - 10.1021/acs.joc.6b00444 [doi]
PST - ppublish
SO  - J Org Chem. 2016 Jun 3;81(11):4609-15. doi: 10.1021/acs.joc.6b00444. Epub 2016 
      May 13.