Isomerization and rearrangement of ( E )‐ and ( Z )‐phenylhydrazones of 3‐benzoyl‐5‐phenyl‐1,2,4‐oxadiazole: evidence for a ‘new’ type of acid‐catalysis by copper(II) salts in mononuclear rearrangement of heterocycles

Abstract A kinetic investigation in methanol of the title reaction has evidenced the occurrence of two processes: the 1‐ E $ \mathbin{\lower.3ex\hbox{$\buildrel\textstyle\rightarrow\over {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}}$}} $ 1‐ Z isomerization and the rearrangement of the ( Z )‐isomer into the relevant 4‐benzoylamino‐2,5‐diphenyl‐1,2,3‐triazole ( 1‐ Z  →  T ). The latter reaction is in line with the ability of the ( Z )‐phenylhydrazones of 3‐benzoyl‐1,2,4‐oxadiazoles to undergo the so called mononuclear rearrangement of heterocycles (MRH). The occurrence of both the examined reactions is dependent on a Lewis‐acid‐catalysis. The obtained results have shown the possibility of a ‘new’ type of acid‐catalysis (bifunctional catalysis by Lewis salts) in the MRH. This catalysis operates through a completely different mechanism with respect to the one recently observed, and deeply investigated, in the presence of protic acids for the ( Z )‐phenylhydrazone of 5‐amino‐3‐benzoyl‐1,2,4‐oxadiazole, in both dioxane/water and toluene, for which the catalytic process was dependent on the protonation of N(4) ring‐nitrogen of the 1,2,4‐oxadiazole. As a matter of fact, the copper salts seem able to interact with the >CNNHC 6 H 5 moiety, yielding adducts which, in some cases, are prone to both isomerize and rearrange. Therefore, a similar behaviour in some manner parallel to that already observed in benzene in the presence of aliphatic amines (base‐catalysis) has been evidenced. Copyright © 2008 John Wiley & Sons, Ltd.