The structure of podecdysone B, a new phytoecdysone

Journal of the Chemical Society D: Chemical Communications
1969.0

Abstract

We previously reported the isolation of podecdysones A, B, and C—three new steroids with insect moulting hormone activity—from an extract of Podocarpus elatus bark and suggested structure (I) for podecdysone A. We have since isolated three additional compounds, podecdysones D, E, and F, from the same extract and propose structure (II) for podecdysone B. Comparison of podecdysone D with an authentic sample of makisterone A (isolated from P. macrophyllus) revealed their identity. In the CalZiphora bioassay for moulting hormones, podecdysone B exhibits approximately one-fifth the activity of crustecdysone. This relatively high activity is notable because, unlike all previously reported active compounds, podecdysone B lacks a 7-en-6-one grouping, though its activity may stem from in vivo isomerisation to such a moiety. A structure analogous to that proposed for podecdysone B has been assigned to a product (IV) from acid treatment of ecdysone, and podecdysone B may be biosynthesised from crustecdysone (another extract constituent) via dehydration. Podecdysone B has a melting point of 125–127°C, with λmax (ethanol) 244 nm (ε 13,200), νmax (KBr) 3490, 1705, 1650 cm⁻¹, and molecular formula C₂₇H₄₂O₆ (confirmed by microanalysis and mass spectral peak at m/z 444, corresponding to M⁺ − H₂O). Its mass spectrum shows further water loss and side-chain fragmentation peaks (m/z 99, 81). NMR spectra of podecdysone B (methyl signals, vinylic C-15 proton) were compared with crustecdysone. The structure was confirmed by: (1) refluxing known methyl ketone (VII) in 0.5M ethanolic HCl to yield products (VIII, IX) analogous to acid-dehydrated ecdysone; (2) selectively acetylating podecdysone B to the 2-acetate, oxidising with periodic acid to an acetoxymethyl ketone, and hydrolysing to a diol-dione identical (via spectral properties, TLC, mass spectrum) to compound (VIII). Podecdysone B is unlikely an artefact from crustecdysone dehydration during work-up, as expected 7,15-dien-6-one by-products were absent, mild extraction yielded podecdysone E (similar chromatography), and bark from young trees had no phytoecdysones—indicating P. elatus phytochemical variability.

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