Pressure-selected reactivity between 2-butyne and water induced by two-photon excitation

Abstract

High-pressure photochemistry between 2-butyne (H3CC≡CCH3) and trace amount of H2O was investigated at room temperature using multiline UV radiation at λ ≈ 350 nm and monitored by FTIR spectroscopy. Instead of the expected polymerization of 2-butyne, the IR spectral analysis suggests the formation of cis- and trans-2-butene, as well as 2-butanone, as the primary products. The possible reaction mechanisms and production pathways of these products were examined, where the dissociation of water molecule as the other reactant is believed as the essential step of the photochemical reaction. We further found that initial loading pressure of the mixture can not only substantially influence the reaction kinetics, but also regulate the accessibilities to some reaction channels, which was evidenced by quantitative analysis of the characteristic IR bands of 2-butene and 2-butanone. The relative abundance of two products is found to be highly dependent on pressure and radiation time. This study provides attractive physical routes in the absence of solvents, catalysts, and radical initiators, to synthesis the relevant products with a great selectivity and feasibility.