4-Quinolylnitrene and 2-quinoxalinylcarbene

Addicott, Chris, Luerssen, Holger, Kuzaj, Martin, Kvaskoff, David and Wentrup, Curt (2011). 4-Quinolylnitrene and 2-quinoxalinylcarbene. In: Special Issue: ISRIUM at Pacifichem 2010. Pacifichem 2010 International Symposia of Reactive Intermediates and Unusual Molecules (ISRIUM), Honolulu, HI, United States, (999-1008). 15–20 December 2010. doi:10.1002/poc.1904

Author Addicott, Chris
Luerssen, Holger
Kuzaj, Martin
Kvaskoff, David
Wentrup, Curt
Title of paper 4-Quinolylnitrene and 2-quinoxalinylcarbene
Conference name Pacifichem 2010 International Symposia of Reactive Intermediates and Unusual Molecules (ISRIUM)
Conference location Honolulu, HI, United States
Conference dates 15–20 December 2010
Proceedings title Special Issue: ISRIUM at Pacifichem 2010   Check publisher's open access policy
Journal name Journal of Physical Organic Chemistry   Check publisher's open access policy
Place of Publication Bognor Regis, West Sussex, United Kingdom
Publisher John Wiley & Sons
Publication Year 2011
Sub-type Fully published paper
DOI 10.1002/poc.1904
ISSN 0894-3230
Volume 24
Issue 10
Start page 999
End page 1008
Total pages 10
Collection year 2012
Language eng
Formatted Abstract/Summary
Matrix photolysis of 4-quinolyl azide 22 affords 4-quinolylnitrene 21, identified by electron spin resonance (ESR) and infrared (IR) spectroscopy. Minor absorptions assigned to azirene 23 (1741 cm−1) were also observed. Further photolysis affords strong absorptions at 1902 and 1909 cm−1 ascribed to the cyclic ketenimine 19 as well as weaker absorptions at 2044 cm−1 ascribed to the open-chain ketenimine 26 and at 1982 cm−1 assigned to the open-chain nitrile ylide 25. Both 2-(5-tetrazolyl)quinoxaline 14 and triazolo[1,5-a]quinoxaline 16 give rise to an absorption at 2084 cm−1 because of formation of the diazo compound 15 on mild flash vacuum thermolysis (FVT) with Ar matrix isolation of the product. Matrix photolysis of 16 affords diazo compound 15, cyclic ketenimine 19 and open-chain ketenimine 26. 2-Quinoxalinylcarbene 17 was also formed in the matrix photolysis and identified by its ESR spectrum. FVT of either 22 or 15/16 afforded 4-quinolylnitrene, identified by its Ar-matrix ESR spectrum. A second nitrene ESR signal obtained in several FVT and photolysis experiments from both 22 and 16 is ascribed to the phenylnitrene derivative 24 formed by ring opening of 2-quinoxalinylcarbene 17. FVT of 14, 16, and 22 affords 3-cyanoindole 27 as the major product. Minor amounts of 2-cyanoindole 28, 4-aminoquinoline 29 and 4,4′-azoquinoline 30 are also formed. Preparative photolysis of 22 in solution in the presence of dialkylamines leads to trapping of the azirene 23 to afford 5-dialkylaminobenzo[e]-1,4-diazepines 35.
Keyword Azides
Flash vacuum thermolysis
Matrix isolation
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Special Issue: ISRIUM at Pacifichem 2010. Symposium theme “Reactive Intermediates and Unusual Molecules - A Celebration of Bob Moss‘s 70 years”

Document type: Conference Paper
Collections: Official 2012 Collection
School of Chemistry and Molecular Biosciences
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