Bulletin of the Chemical Society of Japan p. 680 - 683 (1983)
Update date:2022-08-30
Topics:
Yoshimura, Yosuke
Osugi, Jiro
Nakahara, Masaru
A high pressure kinetic study was made of the 1,3-dipolar cycloaddition reaction of Ph2CN2 with dimethyl maleate (DMM), dimethyl fumarate (DMF), methylacrylate (MA), maleonitrile (MN), fumaronitrile (FN), and acrylonitrile (AN) in toluene at 25 deg C.The activation volumes (ΔV*) 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*/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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