New Thermal Routes to ortho-Benzyne

Abstract

There is experimental evidence that intermediate ortho-benzynes can be made by intramolecular [2 + 4] cycloaddition of a 1,3-diyne with an alkyne. Computations by several groups support a concerted mechanism for the cycloaddition of butadiyne with acetylene. High temperature benzyne cycloreversion has also been demonstrated experimentally; this may in fact be a common reaction in hydrocarbon fuel combustion. Following leads from earlier pyrolysis experiments, herein we predict that cycloaddition of benzyne with butadiyne can proceed by a stepwise mechanism to 2,3-naphthyne. However, a slightly lower energy path leads to a benzocyclobutadiene. ortho-Benzyne can be generated by solution-phase and solid-phase reaction in a microwave reactor. We have developed the method of microwave flash pyrolysis (MFP) for high temperature solid-phase microwave reactions. MFP reaction of phthalic anhydride, a classic benzyne precursor, results in a typical suite of products expected from a relatively high concentration of benzyne.