Minor Alkaloids ofCorydalis bulbosa, Structure of Bulbodione

Abstract

As a result of the reinvestigation of the alkaloid content of CORYDALIS BULBOSA (L.) DC. (Papaveraceae), growing in Bulgaria, a new 8,11-dioxoaporphine alkaloid, named bulbodione, together with dihydrosanguinarine, dehydroglaucine, (+/-)-sinactine, glaucinone and bicucullinine were isolated. These six alkaloids had not been detected in our initial study of the plant. The structure of buldodione was elucidated on the basis of spectral data and confirmed by synthesis of the alkaloid by means of Fremy's radical oxidation of bulbocapnine. The identification of the known alkaloids was obtained from their IR and (1)H-NMR spectral data and by direct comparison with authentic samples.

Two p-Quinonoid Aporphine Alkaloids from Fissistigma balansae

“…The 1 H NMR spectrum of 1 revealed three singlets for aryl protons at δ 7.00, 6.94, and 6.05, one methylenedioxy singlet at δ 6.14, one methoxyl signal at δ 3.85, one N -methyl signal at δ 3.23, and two triplets for two vicinally coupled methylenes at δ 3.52 and 3.18 ( J = 6.4 Hz). These data were very similar to those reported for the p -quinonoid, bulbodione ( 3 ), isolated from Corydalis bulbosa and prepared from bulbocapnine by oxidation with Fremy's salt . To delineate the differences between 1 and 3 , bulbocapnine (isolated from Illigera luzonensis ) was treated with Fremy's salt to afford 3 .…”

“…Preparation of p -Quinonoids by Fremy's Radical Oxidation. , N -Methylfissoldine (20 mg) was reacted with Fremy's salt (Aldrich Chemical Co., Inc.). After 10 min, the reaction was quenched, and then 1 (6.5 mg) was obtained by preparative TLC.…”

“…Its molecular formula was established as C 19 H 15 NO 5 by HREIMS (found m / z 337.0948, calcd 337.0950). The UV spectrum exhibited absorptions at 220, 284, 306, 333, and 590 nm, which corresponded to a p -quinonoid type of aporphine nucleus. − The IR spectrum showed a carbonyl absorption at 1670 cm -1 . The 1 H NMR spectrum of 1 revealed three singlets for aryl protons at δ 7.00, 6.94, and 6.05, one methylenedioxy singlet at δ 6.14, one methoxyl signal at δ 3.85, one N -methyl signal at δ 3.23, and two triplets for two vicinally coupled methylenes at δ 3.52 and 3.18 ( J = 6.4 Hz).…”

“…Its HREIMS gave an [M] + ion at m / z 323.0793, which corresponded to the molecular formula C 18 H 13 NO 5 (calcd 323.0794). The UV spectrum exhibited absorptions at 218, 283, 300, 335, and 591 nm, typical of a compound with a p -quinonoid aporphine nucleus. − The 1 H NMR spectrum of 2 showed three singlets for aryl protons at δ 7.00, 6.96, and 6.05, one methylenedioxy at δ 6.14, one methoxyl at δ 3.85, and two triplets for two vicinally coupled methylenes at δ 3.55 and 3.15 ( J = 6.4 Hz). Comparison of the 1 H NMR spectra of 2 and 1 (Table ) showed the same patterns except for the absence of the N -methyl group.…”

Aporphinoid Alkaloids, IV

“…C19H1904N 325.1313 SOURCES: Fumariaceae: Corydalis bulbosa (136), Corydalis gortschakovii (116), Corydalis solida…”