Details

Autor(en) / Beteiligte

• Varga, Katarina
• Vančik, Hrvoj

Titel

Topochemical effect in thermal E-Z isomerization of azodioxides in solid state

Ist Teil von

• Journal of physical organic chemistry, 2016-05, Vol.29 (5), p.214-220

Ort / Verlag

Bognor Regis: Blackwell Publishing Ltd

Erscheinungsjahr

2016

Quelle

Access via Wiley Online Library

Beschreibungen/Notizen

• The thermally induced E–Z isomerization of the benzeneazodioxide derivatives is studied in the solid polycrystalline state. The reactions are studied from the kinetic and mechanistic aspects. In contrast to the solution, where isomerizations of azodioxides occur through the formation of corresponding nitroso monomers, the topochemical effect in solid state lead to the mechanism that includes formation of the “torsional” transition state, as it is the case in other known cis–trans isomerizations. It is proposed that both the reactions in solid state, the nitroso monomer–dimer equilibrium, and isomerization about the azodioxide NN bond tentatively involve similar transition states. Copyright © 2015 John Wiley & Sons, Ltd. The topochemical effect in thermally induced E–Z isomerization of the benzeneazodioxide derivatives is investigated in the solid polycrystalline state. The reactions of Z‐m‐halogenobenzeneazodioxides are studied from the kinetic and mechanistic aspects. Because the isomerization is the concurrent reaction to the nitroso dimerization–dissociation process, it is proposed that both of the reactions in the solid state tentatively involve similar transition state.