モルフィンアルカロイドに関する研究 (第11報)

Abstract

The main product from catalytic reductive amination of the 6-ketone compound of morphine alkaloid, and that of catalytic reduction and reduction of its enamine (I) with sodium borohydride and formic acid were found to have the 6α-amino group through the consideration of their reaction mechanism, synthesis of isomers by a different route, and by comparison of their nuclear magnetic resonance spectra (Chart 1 and Tables I and II).In the 14-hydroxy system, nucleophilic substitution reaction with secondary amine was found to be unaccompanied by reversion, contrary to the 14-H system (Chart 2). Addition of amine to the α, β-unsaturated ketone (XIII) was proved to form 8β-amino group by synthesis (Chart 4).