C8H6 thermal chemistry. 7-Methylenecyclohepta-1,3,5- dienyne (heptafulvyne) by flash vacuum thermolysis]matrix isolation. Chemical activation in the rearrangements of phenylenedicarbenes and of benzocyclobutadiene to phenylacetylene

Kuhn, Arvid, Miura, Daisuke, Tomioka, Hideo and Wentrup, Curt (2014) C8H6 thermal chemistry. 7-Methylenecyclohepta-1,3,5- dienyne (heptafulvyne) by flash vacuum thermolysis]matrix isolation. Chemical activation in the rearrangements of phenylenedicarbenes and of benzocyclobutadiene to phenylacetylene. Australian Journal of Chemistry, 67 8-9: 1174-1179. doi:10.1071/CH13670


Author Kuhn, Arvid
Miura, Daisuke
Tomioka, Hideo
Wentrup, Curt
Title C8H6 thermal chemistry. 7-Methylenecyclohepta-1,3,5- dienyne (heptafulvyne) by flash vacuum thermolysis]matrix isolation. Chemical activation in the rearrangements of phenylenedicarbenes and of benzocyclobutadiene to phenylacetylene
Formatted title
C8H6 thermal chemistry. 7-Methylenecyclohepta-1,3,5- dienyne (heptafulvyne) by flash vacuum thermolysis-matrix isolation. Chemical activation in the rearrangements of phenylenedicarbenes and of benzocyclobutadiene to phenylacetylene
Journal name Australian Journal of Chemistry   Check publisher's open access policy
ISSN 1445-0038
0004-9425
Publication date 2014
Year available 2014
Sub-type Article (original research)
DOI 10.1071/CH13670
Volume 67
Issue 8-9
Start page 1174
End page 1179
Total pages 6
Place of publication Clayton, VIC, Australia
Publisher C S I R O Publishing
Collection year 2015
Language eng
Formatted abstract
Methylenecycloheptadienyne 11 (heptafulvyne) is obtained very cleanly by flash vacuum thermolysis (FVT) of the diazobenzocyclobutene precursor 8 at 400°C followed by isolation as a neat solid at 77 K or in an Ar matrix at 7–10 K. Compound 11 is a yellow solid, stable till ~–100°C in the neat state. The diazo compound itself (2) is observable by IR spectroscopy following mild decomposition of the tosylhydrazone salt 1 at 115°C. FVT of 8 at 200°C also generates diazo compound 2 as observed by IR spectroscopy and on-line mass spectrometry. FVT of 8 at 600–800°C causes rearrangement of 11 to phenylacetylene 12 and benzocyclobutadiene 13. Mechanisms for the rearrangements are proposed. Facile rearrangement of benzocyclobutadiene to phenylacetylene is ascribed to chemical activation, which is also seen to be involved in the rearrangement of p-, m-, and o-phenylenebiscarbenes 25–27 to phenylacetylene 12.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
 
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