Retro-[3 + 2]-cycloaddition reactions in the decomposition of five-membered nitrogen-containing heterocycles

The Journal of Organic Chemistry
Gabriel da Silva, Joseph W Bozzelli

Abstract

Nitrogen-containing heterocycles form the basis for a new generation of high-energy density materials, and they serve as model compounds for nitrogen-containing fuels, such as coal and biomass, and they form the backbone of ionic liquids. A novel retro-[3 + 2]-cycloaddition to a three-membered diene and a two-membered dienophile, analogous to a retro-Diels-Alder reaction, may constitute an important initial reaction step in the thermal decomposition of these heterocyclic compounds. We investigate the kinetics and thermodynamics of these reactions for the heterocycles pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,5-triazole, 1,3,4,-triazole, 1H-tetrazole, and 2H-tetrazole, using theoretical computational chemistry. The retro-cycloadditions are shown to form one of the three-membered products: hydrazoic acid (NH=N=N), nitrilimine (NH=N=CH), carbodiimide (NH=C=NH), or ketenimine (NH=C=CH2) plus one of the two-membered products acetylene, hydrogen cyanide, or N2. Accurate enthalpies of formation are calculated for the reaction products using the high-level W1 computational protocol, providing the previously undetermined enthalpy values of 70.09, 88.75, 35.03, and 44.28 kcal mol(-1) for hydrazoic acid, nitrilimin...Continue Reading

References

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Nov 1, 2005·Journal of Mass Spectrometry : JMS·Chunxiang YaoFrantisek Turecek
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Feb 24, 2006·The Journal of Physical Chemistry. a·Igor V TokmakovDonald L Thompson
Apr 6, 2006·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Gabriel da SilvaHenning Bockhorn
Jun 15, 2006·The Journal of Physical Chemistry. B·Deborah D ZornMark S Gordon
Jul 11, 2006·The Journal of Physical Chemistry. a·Adam J GianolaW Carl Lineberger
Jul 28, 2007·The Journal of Organic Chemistry·Scott Gronert, James R Keeffe
Aug 19, 2007·The Journal of Physical Chemistry. a·Gabriel da SilvaJoseph W Bozzelli
Nov 7, 2007·The Journal of Physical Chemistry. a·Gabriel da Silva, Joseph W Bozzelli

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Citations

Nov 17, 2012·Chemical Reviews·Roman Bielski, Zbigniew Witczak
May 4, 2018·International Journal of Phytoremediation·Matt A LimmerJoel G Burken
May 13, 2010·The Journal of Physical Chemistry. a·Rubik AsatryanMinh Tho Nguyen
Jul 4, 2009·The Journal of Physical Chemistry. a·Gabriel da SilvaRubik Asatryan
Feb 17, 2011·The Journal of Physical Chemistry. a·Vitaly G KiselevNina P Gritsan
Apr 1, 2020·The Journal of Physical Chemistry. a·Meiheng LuKeli Han

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