Alkaloids ofVeratrum lobelianum

Chemistry of Natural Compounds
1983.0

Abstract

Previously, a base with mp 220-222°C was initially characterized as germanitrine, but later confirmed as germitetrine (I) via high-resonance mass spectrometry (molecular weight 793, C₄₁H₆₃NO₁₄) and renewed PMR spectrum analysis. Continuing the separation of total alkaloids from the epigeal part of V. lobelianum collected in the Caucasus using a silica gel column (eluent: benzene-acetone), an alkaloid (II) with the composition C₃₉H₆₁NO₁₄, molecular weight 751, and mp 138-140°C was isolated. Its IR spectrum exhibited absorption bands at 3450 cm⁻¹ (OH), 1745 cm⁻¹, and 1250 cm⁻¹ (ester C=O). On acetylation, alkaloid (II) formed a diacetyl derivative (III, mp 210-212°C, M⁺ 835) and a triacetyl derivative (IV, mp 200-202°C, M⁺ 877), and was found to be identical to germinaline (via melting point and IR spectrum). However, a comparison revealed that the elemental composition of (II) differed from the previously reported germinaline by one oxygen atom. Partial hydrolysis of germitetrine (I) in aqueous methanolic solution yielded deacetylgermitetrine (IX, M⁺ 751), which was identical to alkaloid (II). Thus, germinaline was determined to have the structure of deacetylgermitetrine, specifically 3β-[(1)-3-acetoxy-2-hydroxy-2-methylbutyryl]-15α-[(Z)-2-methylbutyryl]germine derived from germitetrine, correcting the earlier incorrect structural assignment. This marks the first time germinaline has been obtained from a plant.

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