3-キノリンカルボニトリル, 4-イソキノリンカルボニトリルおよびその誘導体とグリニヤール試薬の反応

抄録

3-Quinolinecarbonitrile (I) and 4-isoquinolinecarbonitrile (II) reacted with Grignard reagents, RMgX, (R=C₂H₅, n-C₃H₇, n-C₄H₉, (CH₂)₃OC₂H₅, phenyl, benzyl) to give 4-substituted-1, 4-dihydroquinoline-3-carbonitrile (III) and 1-substituted-1, 2-dihydroisoquinoline-4-carbonitrile (IV) instead of corresponding ketones.
Oxidation of (III) and (IV) with potassium permanganate resulted in the formation of 4-substituted-3-quinolinecarbonitrile (V) and 1-substituted-4-isoquinolinecarbonitrile (VI).
(V) and (VI) were allowed repeatedly to react with Grignard reagents. The former gave 4, 4-disubstituted-1, 4-dihydroquinoline-3-carbonitrile (VII) (R=C₂H₅, n-C₃H₇, n-C₄H₉, benzyl) or 2, 4-disubstituted-3-quinolinecarbonitrile (R=phenyl). The latter gave a mixture of 1, 1-disubstituted-1, 2-dihydroisoquinoline-4-carbonitrile (VIII) and 1, 3-disubstituted-3, 4-dihydroisoquinoline-4-carbonitrile (IX) (R=C₂H₅, n-C₃H₇, n-C₄H₉).