Studies on the Alkaloids of Formosan Lauraceous Plants. VIII. : Alkaloids of Cryptocarya chinensis HEMSL. (1). : Structures of the New Alkaloids "Crychine" and "Caryachine"

YAKUGAKU ZASSHI
1966.0

Abstract

Examinations were made on the leaves, tree bark, and wood, treated separately, of Formosan Cryptocarya chinensis HEMSL. (Lauraceae) (Japanese name "Maruba-damo": Chinese name "Hou-Kou-kuei") and the bases listed in Table I were isolated in crystalline form. Base B (crychine) was obtained as its picrate of yellow prisms, m.p. 177° (sint. 162°). C₁₉H₁₇O₄N • C₆H₃O₇N, The free base, [α]D¹⁵ -220.2° (EtOH), UV: λmax^EtOH 296.7 mμ. Its NMR spectrum (Fig. 1) indicated that it is a pavine-type new base possessing 4 aromatic protons, 2 methylenedioxy groups, and 1 N-methyl group. Treatment of crychine (K) with phosphorous pentachloride gave an O-methyl compound (XII) through a phenolic base (X). Base D (caryachine) occurs as colorless needles, m.p. 174~175°, [α]D²¹ -269.6° (EtOH), C₁₉H₁₉O₄N. From its NMR spectrum (Fig. 2), this base was found to possess 4 aromatic protons, 1 methylenedioxy group, 1 methoxyl, and 1 N-methyl group; UV: λmax^EtOH 291.5 mμ. The O-methylated compound of the phenolic base (XIII) obtained by cleavage of methylenedioxy group in O-methylcaryachine with phosphorous pentachloride was found to agree with N-methylpavine (argemonine) (X) derived from papaverine (XIV). In other words, the structure of caryachine can be represented by formula (XVI). On the other hand, O-methylcaryachine agreed with the O-methyl compound of the phenolic base derived from crychine (K) and it follows that the structure of crychine would be 13-methyl-2,3:8,9-dimethylenedioxy-5,6,11,12-tetrahydro-5,11-dibenzo[a,e]cyclooctene (K). Base E, m.p. 241~242°, was identified as dl-caryachine. (Received May 28, 1965)

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