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Contents Vol 66(8)

Chemical Activation in Azide and Nitrene Chemistry:
Methyl Azide, Phenyl Azide, Naphthyl Azides, Pyridyl Azides, Benzotriazoles, and Triazolopyridines

Curt Wentrup A
+ Author Affiliations
- Author Affiliations

A School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.
Email: wentrup@uq.edu.au

Australian Journal of Chemistry 66(8) 852-863 https://doi.org/10.1071/CH13283
Submitted: 2 June 2013  Accepted: 24 July 2013   Published: 8 August 2013

Abstract

Chemical activation (the formation of ‘hot’ molecules due to chemical reactions) is ubiquitous in flash vacuum thermolysis (FVT) reactions, and awareness of this phenomenon is indispensable when designing synthetically useful gas-phase reactions. Chemical activation is particularly prevalent in azide chemistry because the interesting singlet nitrenes are high-energy intermediates, and their reactions are highly exothermic. Consequently, chemical activation is observed in the isomerization of methylnitrene CH3N to methylenimine (methanimine) CH2=NH, facilitating the elimination of hydrogen to form HCN or HNC. Rearrangements of phenylnitrene, 1- and 2-naphthylnitrenes, and 2-, 3- and 4-pyridylnitrenes afford cyanocyclopentadiene, 3- and 2-cyanoindenes, and 2- and 3-cyanopyrroles, all showing the effects of chemical activation by undergoing facile interconversion of isomers. Chemical activation can often be reduced or removed entirely by increasing the pressure, thereby promoting collisional deactivation. Larger molecules having more degrees of freedom are better able to dissipate excess energy; therefore the effects of chemical activation are less pronounced or completely absent in the formation of 3-cyanoindole and 1-cyanobenzimidazoles from 3- and 4-quinolylnitrenes and 4-quinazolinylnitrenes, respectively. In compounds possessing nitro groups, chemical activation can cause the loss of the nitro group at nominal temperatures far below those normally needed to cleave the C-NO2 bond.


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