The structure of delphidine, a diterpenoid alkaloid from Delphinium staphisagria

Phytochemistry
1977.0

Abstract

We wish to report the structure of delphidine (1), a C,,H,,NO, [3], mp 98-100" (with slight softening at 90'). [a];' + 16.6" (C _ 1.3 EtOH) shows broad absorption at 3600 _ 3000 (H-bonded OH group), 1720 (MeCO group) and 1100 (ether linkage) cm-' in its IR spectrum. The 'H NMR spectrum shows absorption for an N-CH&& group (3H triplet, J 7 Hz) centred at δ1.13, one acetoxyl group (δ2.00, as +H singlet) and three OMe groups (3H singlets at δ.26, δ3.31 and δ5.34). The IR and 'H NMR spectra of this new alkaloid show some similarity with those of the known alkaloids delphisine (2) and neoline (3) [2, 4]. Hydrolysis of delphidine with a solution of K&O, in aqueous MeOH afforded a triol, C,,H,,NO,, mp 159-161", which was identical (IR, 'H and 13C NMR) with neoline (3). Treatment of delphidine with Ac,O and pyridine at room temperature overnight yielded a compound which proved to be identical with neolinetriacetate (4) (delphisine 1a-monoacetate), C,,H,,NO,, mp 149-151". These results confirm the presence of two free secondary hydroxyl groups in delphidine 1. The identical triacetate (4) (IR, NMR, mp, mmp) was also obtained by the hydrolysis of delphidine to the triol 3, followed by acetylation of the latter with Ac,O and p-toluenesulfonic acid at 100". On the basis of the above chemical studies, it is clear that the acetyl group in delphidine is present at the C-8 position. We, therefore, assign the structure of 8-acetylneoline (1) to delphidine. Because delphidine (1) has been related to delphisine (2) and neoline (3), the absolute configuration of delphisine derived by an X-ray analysis applies to delphidine as well. It is interesting to note that the C-1 proton signal in delphidine appears as a multiplet at δ3.82, an observation consistent with ring A in a boat conformation, as in the case of delphisine (2) [2]. When delphisine (2) is allowed to stand in hexane over a column of alumina (Activity III) for three days, and is eluted subsequently with 3% ethanol in hexane, it furnished an almost quantitative yield of delphidine (1). The selective hydrolysis of the 14-acetyl group of delphisine by an alumina column suggests that delphidine (1) might be an artefact formed during chromatographic separation of the alkaloid mixture. We have not been able to rule out this possibility yet [5].

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