Pumpkin, the fruits of Cucurbita moschata (Cucurbitaceae), has been used as a popular vegetable in cooking since antiquity and the pumpkin seeds are utilized in several countries as snacks after salting and roasting. The pumpkin seeds are also an important Traditional Chinese Medicine in the treatment of cestodiasis, ascariasis, and schistosomiasis.
1)Pharmacological studies on the seeds have demonstrated hepatoprotective 2) and antitumor activities.3) To our knowledge, most of the chemical studies on pumpkin seeds were carried out on lipids in the pumpkin seed oil, [4][5][6] and no report has been published concerning the water-soluble constituents. The nutritive value and potential medicinal importance prompted us to investigate its chemical constituents, which resulted in the isolation of five new phenolic glycosides, cucurbitosides A-E (1-5). This paper deals with the isolation and structural elucidation of the new constituents on the basis of spectroscopic analysis and chemical evidence.The seeds of C. moschata purchased in Harbin, China, were extracted with methanol. The methanolic extract was partitioned between ethyl acetate and water. The water layer was passed through a Diaion HP-20 column, and washed with methanol. The methanolic eluate was evaporated and applied to an ODS column chromatography (CC). Further purification by repeated reverse-phase HPLC gave five new phenolic glycosides, which were termed as cucurbitosides A-E (1-5).Cucurbitoside A (1) was isolated as an amorphous powder. The molecular formula was established as C 26 H 32 O 12 by high-resolution (HR)-FAB-MS. On acid hydrolysis, 1 afforded D-glucose and D-apiose as component sugars, which was identified by GLC analysis of its trimethylsilyl thiazolidine derivative.7) The 1 H-and 13 C-NMR spectra of 1 (Table 1) also revealed the presence of glucopyranose and apiofuranose moieties. The b-anomeric configuration for the glucopyranose was determined from a large 3 J H1,H2 coupling constant value (7.5 Hz). The b-anomeric configuration for the apiofuranose was suggested by the chemical shift of its anomeric carbon (d 110.5).8) Besides the signals due to sugars, the 1 H-NMR spectrum of 1 also showed a set of proton signals due to 1,4-disubstituted aromatic ring at d 6.95 (2H, dd, Jϭ8.9, 1.9 Hz) and 6.91 (2H, d, Jϭ8.9 Hz), as well as a benzylic methylene at d 2.65 (2H, td, Jϭ7.1, 1.9 Hz) and a hydroxymethyl at d 3.62 (2H, t, Jϭ7.1 Hz), indicating the presence of a 2-(4-hydroxyphenyl)ethanol moiety. Furthermore, the signals attributable to a monosubstituted aromatic ring were observed at d 7.94 (2H, dd, Jϭ8.3, 1.4 Hz), 7.41 (2H, t, Jϭ8.3 Hz) and 7.58 (1H, tt, Jϭ8.3, 1.4 Hz), in combination with the signal for a carbonyl carbon at d 167.8 in the 13 C-NMR spectrum, suggesting a benzoyl moiety in 1. The connection of the aforementioned structural units was determined by the 1 H-detected heteronuclear multiple bond connectivity (HMBC) data (Fig. 1). The b-D-glucopyranose was found to be connected to 4-OH of the 2-(4-hydroxy)phenylethanol moiety by ob...