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New examples of specific base catalysis in mononuclear rearrangements of heterocycles found via a designed modification of the side chain structure

  • Autori: D'Anna, F.; Frenna, V.; Guernelli, S.; Lanza, C.; Macaluso, G.; Marullo, S.; Spinelli, D.
  • Anno di pubblicazione: 2009
  • Tipologia: Articolo in rivista (Articolo in rivista)
  • Parole Chiave: Mononuclear rearrangement of heterocycles, base catalysis, kinetic measurements
  • OA Link:


To select suitable candidates for the occurrence of specific-base-catalysis in MRH of (Z)-hydrazones of 3-benzoyl-5-phenyl-1,2,4-oxadiazole we have designed a modification of the side-chain structure by linking a strong electron-withdrawing system to the hydrazono group. Thus we have synthesized the (Z)-semicarbazone (3d), the (Z)-phenylsemicarbazone (3e), and the (Z)-acetylhydrazone (3f) of the above oxadiazole and examined their kinetic behavior in dioxane/water in a large range of proton concentrations (pS + 4.0 14.5). In all the pS+ range examined only a base-catalyzed process has been evidenced (no uncatalysed path occurs). The behavior at the largest pS+ values (the reactivity tends to a limiting rate constant) and that at variable concentrations of buffer have furnished clear evidence for the occurrence of a specificbase- catalysed process, thus reaching the target proposed and confirming the prevision.