14-efivincamine, a new alkaloid from L.

Tetrahedron Letters
1963.0

Abstract

Two crystalline alkaloids were obtained from Vinca minor L. via repeated counter-current distribution (benzene-n-butanol-85%-formic acid-McIlvain buffer pH=3.5, ratio 25:5:1:31; 460 and 100 transfers respectively) followed by chromatography on alumina (activity II, benzene + 0.5% MeOH) from fraction P₁ of the alkaloids. The first was identified as vincamine. The second new alkaloid (I) has a melting point of 181-185°, [α]D²² = -36.4 ± 2° (c=1.036, chloroform). Its UV spectrum (λmax^EtOH 226, 276 nm, logε 4.51, 3.93; λmin^EtOH 250 nm, logε 3.57) places it in the indole alkaloid group. IR spectra (KBr, CCl₄) indicate an unconjugated ester (1742 cm⁻¹), hydroxyl (3530 cm⁻¹), no free NH, and a disubstituted benzene ring (745 cm⁻¹). The molecular formula C₂₁H₂₆N₂O₃ was confirmed by analysis and mass spectrometry (molecular ion m/z 354). Its mass spectrum, similar to vincamine but with a peak at m/z 266 (vs. m/z 267 for vincamine), suggests a dihydroeburnamenine skeleton and diastereoisomerism with vincamine. Reduction with LiAlH₄ yielded diol III, whose oxidation with periodic acid gave ketone V identical to (-)-eburnamonine. Heating in HCl-saturated methanol gave apovincamine, identical to the product from vincamine dehydration. These chemical proofs explicitly show the new alkaloid to be 14-epivincamine.

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