NoteCalystegia soldanella ROEM. et SCHULT. (Convolvulaceae) is widely distributed on temperate sandy beaches of seas and lakes. The root of this plant is used for the treatment of arthritis.1) The isolation and structural elucidation were reported for two genuine resin glycosides, soldanellines A and B, as chemical constituents of the root.2,3) Prior to reinvestigation of the genuine resin glycosides of this plant, we examined the chemical components of the crude resin glycoside fraction of the leaves, stems, and roots of C. soldanella. This paper deals with the isolation and structural elucidation of four new glycosidic acids along with one known glycosidic acid and three known organic acids.The flesh leaves, stems, and roots of C. soldanella were extracted with methanol (MeOH). This extract was partitioned between ethyl acetate (EtOAc) and H 2 O. The EtOAcsoluble fraction was subjected to Sephadex LH-20 column chromatography to afford a crude resin glycoside fraction. The alkaline hydrolysis product of part of the fraction was fractionated into organic acid and glycosidic acid fractions.The organic acid fraction was acylated with p-bromophenacyl bromide followed by chromatographic separation to give p-bromophenacyl 2-methylbutyrate (1), p-bromophenacyl tiglate (2), and p-bromophenacyl nilate (3) (Fig. 1).4) The absolute configurations of 1 and 3 were defined as S and 2S,3S, respectively, by comparison of the specific rotations and 1 H-NMR spectral data for (ϩ)-a-methoxy-a-trifluoromethylphenylacetic acid (MTPA) ester (3a) of 3 with those of authentic samples (Fig. 1). 4)Acidic hydrolysis of the glycosidic acid fraction gave aglycone and monosaccharide fractions. Methylation of the former with trimethylsilyldiazomethane-hexane yielded methyl 11S-jalapinolate (4), which was identified by 13 C-NMR spectral data of 4 and 1 H-NMR spectral data of (ϩ)-MTPA ester (4a) of 4 (Fig. 1). 5,6) HPLC analysis with optical rotation chiral detection of the monosaccharide fraction indicated the presence of D-glucose, D-quinovose, and L-rhamnose.The glycosidic acid fraction was treated with trimethylsilyldiazomethane-hexane and then chromatographed over HPLC on the octadecyl silica (ODS) and silica gel column to yield five methyl esters (5-9) of glycosidic acids. Upon alkaline hydrolysis, 5-9 gave the free glycosidic acids 5a-9a, respectively. Compound 5a was identified as soldanellic acid B based on the physical and spectral data (Fig. 1). 3)Compound 6a, named calysolic acid A, was obtained as an amorphous powder and showed an [MϪH] Ϫ ion peak at m/z 1049 along with fragment ion peaks at m/z 887 [1049Ϫ162 (hexosyl unit)] Ϫ in the negative-ion FAB-MS (Fig. 2). The molecular formula of 6a was analyzed as C 46 H 82 O 26 by high-resolution (HR)-negative-ion FAB-MS. The 1 H-NMR spectrum of 6, which was similar to that of 5 except for the appearance of signals due to one more glucosyl unit, showed signals due to five Human and Environmental Studies, Kyoto University; Japan: c Faculty of Pharmaceutical Sciences, Fukuoka Universit...

Treatment of the crude ether-insoluble resin glycoside (convolvulin) from seeds of Pharbitis nil (Pharbitis Semen), called pharbitin, with indium(III) chloride in methanol provided seven oligoglycosides of hydroxy fatty acid methyl esters partially acylated by 2-methyl-3-hydroxybutyric (nilic) and 2S-methylbutyric acids. Their structures were elucidated on the basis of NMR and MS data and chemical conversions.

Four new resin glycosides having intramolecular cyclic ester structures (jalapins), named calysolins I-IV (1-4), were isolated from the methanol extract of leaves, stems, and roots of Calystegia soldanella , along with one known jalapin (5) derivative. The structures of 1-4 were determined on the basis of spectroscopic data and chemical evidence. They fall into two types, one having a 22-membered ring (1 and 4) and the other with a 27-membered ring (2 and 3). The sugar moieties of 1-4 were partially acylated by some organic acids. Compound 4 is the first example of a hexaglycoside of jalapin.