Abstract
Abstract A high pressure kinetic study was made of the 1,3-dipolar cycloaddition reaction of Ph2CN2 with dimethyl maleate (DMM), dimethyl fumarate (DMF), methyl acrylate (MA), maleonitrile (MN), fumaronitrile (FN), and acrylonitrile (AN) in toluene at 25 °C. The activation volumes (ΔV\eweq) at 1 bar obtained for DMM, DMF, MA, MN, FN, and AN are −23.4±0.5, −22.3±0.2, −19.8±0.4, −21.5±0.6, −21.0±1.1, and −23.9±0.5 cm3 mol−1, respectively. The reaction volume (ΔV) for the reaction between Ph2CN2 and DMM was determined dilatometrically by taking advantage of supersaturation of the cycloadduct in solution; ΔV=−24.5±0.5 cm3 mol−1 and ΔV\eweq⁄ΔV=0.955. The present volumetric information coupled with a kinetic analysis shows that Firestone’s biradical mechanism is not the case; the concerted mechanism is supported. The experimental result is compared with that of a recent ab initio molecular orbital calculation with respect to the activation and reaction volumes.
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