The pyrolysis of 3-vinyl-1-pyrazoline and 3-vinyl-1-pyrazoline-5,5-d2, and its relation to the vinylcyclopropane to cyclopentene rearrangement

Abstract
The kinetics and products of the pyrolysis of 3-vinyl-1-pyrazoline (1) are described. The pyrolysis of 3-vinyl-1-pyrazoline-5,5-d2(II) produces vinylcyclopropane-2,2-d2and cyclopentene-4,4-d2. The secondary isotope effect has been measured (kH/kD = 1.21 ± 0.03), and the reaction mechanism is interpreted as proceeding through a nitrogen-free intermediate similar to that suggested for the rearrangement of vinylcyclopropane to cyclopentene. At 170° a dramatic change in the product composition occurs, and evidence is presented for a "hot vinylcyclopropane" being produced.

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