title: Five-to-six membered ring-rearrangements in the reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine and methylhydrazine.
abstract: The hydrazinolysis reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine or methylhydrazine as bidentate nucleophiles has been investigated. The reaction occurred through the addition of the bidentate nucleophile to the C(5)-N(4) double bond of the 1,2,4-oxadiazole followed by ring-opening and ring-closure (ANRORC) involving the second nucleophilic site of the reagent. This ring-closure step could involve either the original C(3) of the 1,2,4-oxadiazole (giving a five-to-five membered ring rearrangement) or an additional electrophilic center linked to it (exploiting a five-to-six membered ring rearrangement). An alternative initial nucleophilic attack may involve the additional electrophilic center linked at C(3), that is the carbonyl group, leading to the formation of the hydrazones which undergo the Boulton-Katritzky rearrangement (BKR). The chosen reaction path is a function of the used nucleophile and of the nature of the substituent at C(3). At variance with previous hypotheses, when methylhydrazine was used, the observed regiochemistry always showed the preferred initial attack by the less hindered NH(2) end of the nucleophile on C(5). Moreover, new spectroscopic evidence allowed the assignment of correct structures to the products formed by reaction of 5-perfluoroalkyl-3-phenyl-1,2,4-oxadiazoles with methylhydrazine.
authors.affiliation: Dipartimento di Chimica Organica E. Paterno, Università degli Studi di Palermo,Viale delle Scienze-Parco d'Orleans II, I-90128 Palermo, Italy. sbuscemi@unipa.it
authors.forename: Silvestre
authors.initials: S
authors.lastname: Buscemi
authors.forename: Andrea
authors.initials: A
authors.lastname: Pace
authors.forename: Antonio Palumbo
authors.initials: AP
authors.lastname: Piccionello
authors.forename: Ivana
authors.initials: I
authors.lastname: Pibiri
authors.forename: Nicolò
authors.initials: N
authors.lastname: Vivona
authors.forename: Gianluca
authors.initials: G
authors.lastname: Giorgi
authors.forename: Andrea
authors.initials: A
authors.lastname: Mazzanti
authors.forename: Domenico
authors.initials: D
authors.lastname: Spinelli