THE ALKALOIDS OF LYCOPODIUM SPECIES: XI. NATURE OF THE OXYGEN ATOM IN LYCOPODINE; SOME REACTIONS OF THE BASE

Lycopodine gives rise to a hydrazone, is reduced to a secondary alcohol, and reacts with phenyl-lithium to form a tertiary carbinol; hence, the oxygen atom of the base is present in a keto group. The base reacts with cyanogen bromide to form two cyanobromolycopodines, α and β. α-Cyanobromolycopodine is converted by potassium acetate in alcohol to α-cyanoacetoxylycopodine, hydrolyzable to α-cyanohydroxylycopodine, which can be oxidized to an acid. The action of methanolic potassium hydroxide on α-cyanobromolycopodine gives rise to a nonoxidizable, nonreducible neutral compound, while a similar isomeric and equally inert substance is produced by the action of a boiling ethanolic solution of potassium acetate on β-cyanobromolycopodine. Both α- and β-cyanobromolycopodines are hydrogenated catalytically to two isomeric products C17H26ON2. α-Cyanobromolycopodine with trimethylamine forms of quaternary salt which, when subjected to the conditions of the Hofmann degradation, gives rise to a base differing from th...