Orientinine and dehydroisothebaine ? New alkaloids fromPapaver orientale

Chemistry of Natural Compounds
1984.0

Abstract

Continuing the separation of the combined alkaloids of Papaver orientale L., two new bases, orientinine (I) and dehydroisothebaine (II), were isolated from the phenolic fraction. Orientinine, an amorphous base with [α]_D +62° (c 0.18; methanol), showed UV absorption maxima at 275 nm and 315 nm (inflection) (characteristic of 1,2,9-trisubstituted aporphine alkaloids), mass spectrum ions at m/z 311 (M+), 310, 296, 294, 281, 280, 268, and 155.5 (M++), and PMR signals (in deuterochloroform) including three-proton singlets at 2.50 ppm (N-methyl), 3.76 and 3.82 ppm (two methoxy groups), a one-proton singlet at 6.53 ppm, a one-proton doublet at 8.36 ppm (J = 10 Hz), a multiplet at 6.70-6.95 ppm (two protons), and signals for methylene/methine protons at 2.6-3.7 ppm. Methylation with diazomethane gave O-methylorientinine identical to orientine. Dehydroisothebaine, optically inactive and green, had UV maxima at 267, 340, 391, and 438 nm, mass spectrum ions at m/z 309 (M+), 294, and 154.5 (M++), and PMR signals including a three-proton singlet at 3.00 ppm (N-methyl), a six-proton singlet at 3.92 ppm (two methoxy groups), one-proton singlets at 6.40 and 6.97 ppm, aromatic protons at 6.75-7.25 ppm (3 H), and a broadened singlet at 3.22 ppm (four protons). Adams hydrogenation gave a product identical to (±)-isothebaine. For Glaucium oxylobum Boiss. et Buhse (an endemic Central Asian plant), alkaloid composition was investigated in plants collected in the Kara-Kala region of the Turkmen SSR during different vegetation periods. Vegetation-stage plants yielded 0.27% alkaloids, from which nine alkaloids (corydine, dehydrocorydine, isocorytuberine, isoboldine, norisocorydine, N-methylcoclaurine, protropine, allocryptopine, domesticine) were isolated via silica gel column chromatography and identified by spectral characteristics and comparison with authentic samples. Fruit-bearing plants contained 0.09% alkaloids, yielding additional alkaloids isocorydine and glaufidine. The main alkaloids in both stages were corydine (46% and 36%), protopine (13% and 17%), and allocryptopine (14% and 12%). This is the first isolation of isocorydine, glaufidine, isocorytuberine, norisocorydine, N-methylcoclaurine, and dehydrocorydine from G. oxylobum, and its qualitative alkaloid composition differs from previously studied samples.

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