Synthesis and Fragmentation of Furoxanaldehydes in the Gas Phase for Nanopatterned Alkyne Formation on a Solid Surface

Abstract

Furoxanaldellydes possessing phenyl or alkenyl groups at the 3- or 4-position of the furoxan ring were designed for alkyne formation on a solid surface. Furoxans 2 and 3 were prepared from the corresponding alkenes 2a and 3a by the reaction with NaNO2 in acetic acid. Furoxan 4, in which the furoxan ring is conjugated with a double bond, was prepared from bis(bromomethyl)benzene 4a in 5 steps using the Wittig reaction of aldehyde I as the key step. The electron beam-mediated fragmentation of furoxanaldehydes 1-4 in a mass spectrometer was exploited by focusing on alkyne formation on the solid surface. The fragmentation of furoxan 3 possessing diaryl groups afforded diaryl-acetylene at high efficiency, suggesting that the aryl group conjugated with the furoxan ring could facilitate alkyne formation with the evolution of NO.