SOME OXIDATION REACTIONS OF DELCOSINE

Abstract

The alkaloid delcosine was oxidized by chromic acid in acetic acid, and also by the Oppenauer reaction, to dehydrodelcosine in which the carbonyl was shown by infrared absorption to be in a pentatomic ring. Oxidation of the alkaloid with silver oxide gave two products: (a) N-desethyldelcosine, which could be N-acetylated or converted back to the original base by ethylation, thus proving the presence of an N-ethyl group; (b) a compound, C24H37O7N, the properties of which agreed best with those of an internal ether, i.e., anhydrohydroxydelcosine. The action of N-bromosuccinimide on the alkaloid produced the same two compounds as silver oxide, plus a derivative, C22H33O7N, that proved to be N-desethyl-anhydrohydroxydelcosine. Potassium permanganate oxidized delcosine to a product, C22H31O7N, that had lost the N-ethyl group, contained the internal ether, and also a carbonyl in a five-membered ring. This same product was obtained on similar oxidation of N-desethyl-anhydrohydroxydelcosine. Oxidation of delcosine with mercuric acetate gave N-desethyldelcosine and N-desethyl-anhydrohydroxydelcosine, together with a compound that was very soluble in water and proved to be the carbinolamine formed by hydroxylation of the methylene in the N-ethyl group. These results are discussed in terms of a structure that is tentatively advanced for delcosine.