Germacranolides from Centaurea melitensis

Phytochemistry
1989.0

Abstract

The germacranolides salonitenolide, onopordopicrin and arctiopicrin have been isolated from the ether extract of Centaurea melitensis. No elemanolide has been found. These results are different from those previously reported. As a part of our investigations of the synthesis of sesquiterpene lactones, we had to isolate the elemanolide melitensin (1), which has been described as a constituent of the ethanol extract of Centaurea melitensis L. together with the related compounds melitensin-β-hydroxyisobutyrate (2) and dehydromelitensin-β-hydroxyisobutyrate (3) [1,2]. When the aerial parts of C. melitensis collected in Granada were extracted with ether, the germacranolides salonitenolide (4) (3% of the extract), onopordopicrin (5) (38%) and arctiopicrin (6) (5%), which were not described in the preceding papers, were obtained. The physical and spectroscopic properties of these compounds are identical to bibliographical values [3-5], and the ¹³C NMR data confirm their structures (Table 1). We have not, however, detected any elemanolide in the extract. These contradictory results could be attributed to the different extraction procedures used in this and previous studies. In ref. [1], the plant was extracted with refluxing ethanol and the extract defatted by treatment with lead acetate. A defatting step was not necessary in our workup of the ether extract, since not many fats are extracted under these conditions. Thus, the high temperatures that could cause Cope rearrangements of the germacranolides into their corresponding elemanolides were avoided. These results are similar to those obtained in our study of Centaurea malacitana Boiss. [6]. We suggest that 1 is not a component of C. melitensis as was previously reported [1], but an artefact resulting from the extraction and manipulation process. A new diterpene, distanol, has been isolated from the petrol extract of the aerial part of Sideritis distans Wild. Its structure and stereochemistry has been assigned by spectroscopic methods.

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