ケテンおよびその誘導体の研究(第20報) : Diketeneと2-Pyridylacetonitrileとの反応

概要

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The reaction of 2-pyridylacetonitrile (I) and diketene gives 2-(2-pyridyl)-2-acetoacetylacetonitrile (II) and 4-methyl-2-oxo-(2H)-quinolizine-1-carbonitrile (III). II transits to III when heated with acid or alkali. Hydrolysis of III gives 4-methyl-2-oxo-(2H)-quinolizine-1-carboxamide (IV) while a more drastic condition results in the hydrolysis of III to 4-methyl-(2H)-quinolizine-2-one (VI). The carboxylic acid (V), obtained by treatment of IV with nitrous acid, also afforded VI on being heated in quinoline. Catalytic reduction of VI over platinum oxide affords 4-methyl-(2H)-6,7,8,9-tetrahydroquinolizine-2-one(VII) whose further high-pressure reduction over Raney nickel gives 2-hydroxy-4-methyl-(2H)-octahydroquinolizine (VIII). Oxidation of VIII with chromium trioxide gave a compound which was assumed to be 4-methyl-(2H)-octahydroquinolizine-2-one (IX). Catalytic reduction of III over palladium-carbon affords 4-methyl-2-oxo-(2H)-6,7,8,9-tetrahydroquinolizine-1-carbonitrile (X) whose hydrolysis gives the amido compound (XI). Reduction of the latter with lithium aluminum hydride gave a compound corresponding to 2-hydroxy-4-methyl-(2H)-6,7,8,9-tetrahydroquinolizine-1-carboxamide (XII).
公益社団法人日本薬学会の論文
1967-08-25