In order to confirm the structure of menisarine (Ia or Ib), the alkaloid of Formosan Menispermaceous plant,
Cocculus sarmentosus DIELS (Japanese name “Hohzan-tsuzura-fuji”, Chinese name “Te-niu-zu-su”) by synthesis, condensation of 2, 7-bis(2-amino-ethyl)-4, 9-dimethoxydibenzo-
p-dioxin (II) and 2-methoxy-5-chlorocarbonylmethyl-phenyl
p-chlorocarbonylmethylphenyl ether (VII) was carried out. The bis-acetamide (VIII) thereby formed was submitted to the Bischler-Napieralski reaction to effect isoquinoline cyclization and reduction of its product gave 1, 2, 3, 4-tetrahydroisoquinolinetype base (X). This base X was N-methylated with formic acid and formaldehyde to 2-methyl-1, 2, 3, 4-tetrahydroisoquinoline derivative (XII), m.p. 180-183°, whose infrared spectrum (in CHCl
3) agreed with that of N-methyldihydromenisarine, obtained by N-methylation of dihydromenisarine (XIa or XIb) derived from the natural product (Fig. 1).
dl-N-Methyldihydromenisarine (XII) thereby synthesized was submitted to the first Hofmann degradation and the infrared spectrum (in CHCl
3) and ultraviolet spectrum (in EtOH) of the methine base so obtained were identical with those of the optically inactive N-methyldihydromenisarine methylmethine (XIII) derived from natural menisarine. These experimental evidences have confirmed that menisarine would be represented by the structural formula of Ia or Ib.
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