Kinetics and Mechanism of Aziridine Synthesis from Ketoxime with Lithium Aluminum Hydride

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The stoichiometry and rate of the reaction of dibenzyl ketoxime (1) with lithium aluminum hydride in tetrahydrofuran leading to cis-2-benzyl-3-phenylaziridine (2, 92%) and 2-amino-1,3-diphenylpropane (3, 8%) were determined by gas meter and vpc. It was found that the aziridine formation proceeds with an immediate evolution of 1 mole of hydrogen followed by a slow liberation of a second mole of hydrogen and an accommodation of 1 equiv. of hydride into the molecule. Also, the formation has an induction period and there is a catalytic acceleration effect by the concurrently-formed minor product 3. Combination of the previously-reported results and the present findings leads us to propose a mechanism by which an aluminum derivative rapidly obtained on addition of 1 to the solution of lithium aluminum hydride undergoes slow hydrogen elimination to afford an azirine intermediate, followed by reduction to the aziridine. Making use of the catalytic effect discovered, the reaction rate and yield of aziridine were increased by the addition to the reaction mixture of an amine, particularly a secondary amine such as n-butylmethylamine.
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