Studies on Hydrogenolysis. LVI. The Effect of Solvent and Additive on the Stereochemistry of Catalytic Hydrogenolysis of 2-Methyl-2-phenylaziridine Derivatives

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  • Yoshihiro Sugi
    Department of Applied Science, Faculty of Engineering, Tohoku University
  • Sekio Mitsui
    Department of Applied Science, Faculty of Engineering, Tohoku University

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<jats:title>Abstract</jats:title> <jats:p>In order to assess the effects of solvent and additive on the stereochemical course of the catalytic hydrogenolysis of styrene imine derivatives, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (Ia), 1,2-dimethyl-2-phenylaziridine (Ib), and l-acetyl-2-methyl-2-phenylaziridine (Ic) was carried out under various conditions. The hydrogenolysis of la and Ib over palladium hydroxide occurred preferentially with an inversion of the configuration in ethanol, but with a retention in benzene. Moreover, Ia was hydrogenolysed with a predominant inversion of the configuration in n-hexane, and the inverted product increased with a decrease in the adsorption strength of the hydrocarbon solvent. The hydrogenolysis of Ic, however, occurred with a significant inversion of the configuration in both ethanol and benzene. The addition of sodium hydroxide to the reaction mixture strongly promoted a retention of the configuration in the hydrogenolysis of Ia over palladium hydroxide, and finally Ia was hydrogenolysed with a stereospecific retention. In contrast, no such variations could be observed in the cases of Ib and Ic. The stereoselectivity was not affected significantly by the addition of sodium hydroxide in the Raney nickel-catalyzed hydrogenolysis of Ia. However, the addition of sodium hydroxide prompted a retention of the configuration in the case of Ib. These results can be explained consistently by the previously-proposed mechanism.</jats:p>

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