Nitrene-carbene-carbene rearrangement. photolysis and thermolysis of tetrazolo[5,1- a ]phthalazine with formation of 1-phthalazinylnitrene, o-cyanophenylcarbene, and phenylcyanocarbene

Hoj, Martin, Kvaskoff, David and Wentrup, Curt (2014) Nitrene-carbene-carbene rearrangement. photolysis and thermolysis of tetrazolo[5,1- a ]phthalazine with formation of 1-phthalazinylnitrene, o-cyanophenylcarbene, and phenylcyanocarbene. Journal of Organic Chemistry, 79 1: 307-313. doi:10.1021/jo402448u

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Author Hoj, Martin
Kvaskoff, David
Wentrup, Curt
Title Nitrene-carbene-carbene rearrangement. photolysis and thermolysis of tetrazolo[5,1- a ]phthalazine with formation of 1-phthalazinylnitrene, o-cyanophenylcarbene, and phenylcyanocarbene
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2014-01-03
Year available 2013
Sub-type Article (original research)
DOI 10.1021/jo402448u
Open Access Status File (Author Post-print)
Volume 79
Issue 1
Start page 307
End page 313
Total pages 7
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Abstract 1-Azidophthalazine 9A is generated in trace amount by mild FVT of tetrazolo[5,1-a]phthalazine 9T and is observable by its absorption at 2121 cm-1 in the Ar matrix IR spectrum. Ar matrix photolysis of 9T/9A at 254 nm causes ring opening to generate two conformers of (o-cyanophenyl) diazomethane 11 (2079 and 2075 cm-1), followed by (o-cyanophenyl)carbene 312, cyanocycloheptatetraene 13, and finally cyano(phenyl)carbene 314 as evaluated by IR spectroscopy. The two carbenes 312 and 314 were observed by ESR spectroscopy (D|hc = 0.5078, E|hc = 0.0236 and D|hc = 0.6488, E|hc = 0.0195 cm-1, respectively). The rearrangement of 12 â., 13 â., 14 constitutes a carbene-carbene rearrangement. 1-Phthalazinylnitrene 310 is observed by means of its UV-vis spectrum in Ar matrix following FVT of 9 above 550 C. Rearrangement to cyanophenylcarbenes also takes place on FVT of 9 as evidenced by observation of the products of ring contraction, viz., fulvenallenes and ethynylcyclopentadienes 16-18. Thus the overall rearrangement 10 → 11 → 12 â., 13 â., 14 can be formulated.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Published online: 4 December 2013.

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
 
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