title: Mechanistic studies of a linear trisazoalkane, a new azimine, and a bicyclic triaziridine. Azoalkane homolysis into seven fragments
abstract: An aliphatic azo compound containing three azo groups (1) has been prepared by IF(5) oxidation of beta-azoamine 3. The thermolysis kinetics of this vicinal trisazoalkane were investigated above 155 degrees C, leading to a rate constant only 5.5 times faster than that of the simple model, azo-tert-butane. Because thermolysis to form seven stable products proceeds stepwise, the rate is hardly affected by the high exothermicity of the overall reaction (-93.4 kcal/mol). Oxidation of amine 3 also afforded a cyclic azimine 5 that underwent photolysis to yield a highly strained triaziridine 9 plus an unusual triazane 10, whose structures were elucidated by detailed NMR studies. On standing at ambient temperature, 9 reverted to 5 with a half-life of about an hour.
authors.affiliation: Department of Chemistry, Texas Christian University, Fort Worth, Texas 76129, USA.
authors.initials: PS
authors.lastname: Engel
authors.initials: L
authors.lastname: Pan
authors.initials: KH
authors.lastname: Whitmire
authors.initials: I
authors.lastname: Guzman-Jimenez
authors.initials: MR
authors.lastname: Willcott
authors.initials: WB
authors.lastname: Smith