THE ALKALOIDS OFLYCOPODIUMSPECIES: XI. NATURE OF THE OXYGEN ATOM IN LYCOPODINE; SOME REACTIONS OF THE BASE
作者:
R. H. F. Manske,
Léo Marion,
David B. MacLean,
期刊:
Canadian Journal of Research
(NRC Available online 1950)
卷期:
Volume 28b,
issue 8
页码: 460-467
ISSN:1923-4287
年代: 1950
DOI:10.1139/cjr50b-056
出版商: NRC Research Press
数据来源: NRC
摘要:
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 the quaternary salt by the elements of methyl bromide, and to the same neutral product obtainable from α-cyanobromolycopodine by the action of methanolic potassium hydroxide.
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