Dehydroeldelidine ? A new alkaloid fromDelphinium ternatum

Chemistry of Natural Compounds
1985.0

Abstract

Continuing the study of total alkaloids from the epigeal part and roots of Delphinium ternatum Huth. collected in the vegetation (May 12, 1979) and flowering (June 18, 1979) phases in the R. Varzob basin, we isolated dictyocarpine, base I (C₂₅H₃₇NO₇, mp 120-122°C, hexane), base II (C₂₁H₂₅NO₄, mp 104-109°C, ether; hydrochloride mp 243°C), and base B (mp 236-238°C, acetone) in addition to previously isolated alkaloids. Base I was identified as dehydroeldelidine, a diterpene alkaloid with a lycotonine skeleton, via IR (ether C-O bond at 1100 cm⁻¹, five-membered ring carbonyl at 1745 cm⁻¹, hydroxy groups at 3400-3600 cm⁻¹), NMR (tertiary methyl, N-ethyl, three methoxy groups, methine, methylenedioxy group), mass spectrum (m/z 463 [M]⁺), and chemical oxidation (oxidizing eldelidine with chromium trioxide to obtain dehydroeldelidine, which was identical to base I). This is the first time dehydroeldelidine has been isolated from a plant. Base II was identified as glaucine, a 9,10-substituted aporphine, via IR (ether C-O bond at 1100 cm⁻¹, aromatic ring at 1600 cm⁻¹), NMR (N-methyl, four methoxy groups, three aromatic protons), mass spectrum (m/z 355 [M]⁺), UV (maxima at 282 and 304 nm with log ε 4.34 and 4.24), and comparison with an authentic sample. This is the first isolation of glaucine from the Delphinium genus. The spectral characteristics of base B (solubility, IR, mass spectrum) were also described. Additionally, chemical modification (acylation with succinic and acetic anhydrides) was used to study the relationship between the structure and properties of cotton seed 11S globulin (gossypulin). We aimed to investigate the laws of secondary and tertiary structure changes at a minimum modification degree (10-fold excess of acylating agent per mole of lysine) to explore the contribution of specific structural changes leading to quaternary structure disruption. Using gossypol-free (only isolable from fresh cotton seeds) and 0.6% gossypol-containing gossypulin samples, their circular dichroism (CD) spectra differed significantly in the aromatic absorption region (260-280 nm), indicating different tertiary structures. After modification, both secondary and tertiary structures of gossypol-free samples changed, while gossypol-containing samples showed more substantial changes in the 260-280 nm region.

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