Azulenylcarbene and naphthylcarbene isomerizations. falling solid flash vacuum pyrolysis

Kvaskoff, David, Becker, Jurgen and Wentrup, Curt (2015) Azulenylcarbene and naphthylcarbene isomerizations. falling solid flash vacuum pyrolysis. Journal of Organic Chemistry, 80 10: 5030-5034. doi:10.1021/acs.joc.5b00412

Author Kvaskoff, David
Becker, Jurgen
Wentrup, Curt
Title Azulenylcarbene and naphthylcarbene isomerizations. falling solid flash vacuum pyrolysis
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 1520-6904
Publication date 2015-05-15
Sub-type Article (original research)
DOI 10.1021/acs.joc.5b00412
Volume 80
Issue 10
Start page 5030
End page 5034
Total pages 5
Place of publication Washington, DC United States
Publisher American Chemical Society
Collection year 2016
Language eng
Formatted abstract
1-Azulenylcarbene 18 has been generated from 5-(1-azulenyl)tetrazole and the sodium salt of azulene-1-carbaldehyde tosylhydrazone using the falling solid flash vacuum pyrolysis (FS-FVP) method. The principal products, which are also formed from both 1- and 2-naphthylcarbenes, cyclobuta[de]naphthalene 6, cyclopenta[cd]indene 16, and benzofulvenallene 17, are explained in terms of two reaction paths, (a) a rearrangement to benzofulvenyl-7-carbene 13 and (b) a rearrangement to 1-naphthylcarbene 1. Moreover, 16 is also formed from 2-azulenylcarbene 30, thereby indicating the occurrence of a 2-azulenylcarbene–1-azulenylcarbene rearrangement. The reaction mechanisms are supported by density functional theory calculations at the B3LYP/6-31G** level, which indicate that all the rearrangements have activation barriers of <35 kcal/mol, thus making them readily achievable under FVP conditions.
Keyword Carbene rearrangements
Naphthalene rearangement
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
School of Chemistry and Molecular Biosciences
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