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.

Four new resin glycosides, named calysolins XIV (1), XV (2), XVI (3), and XVII (4) were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae). Their structures were determined based on spectroscopic and chemical evidence, and consisted of two different types: those (1) with a macrolactone structure and those (2-4) with a non-macrolactone structure. Their sugar moieties were partially acylated by specific organic acids, including tiglic, 2S-methylbutyric, and 2S,3S-nilic acids. Additionally, evaluation of the antiviral activity of 1-4 revealed effects against the herpes simplex virus type 1.

Calysolins V-IX, Resin Glycosides from Calystegia soldanella and Their Antiviral Activity Toward Herpes. -(ONO*, M.; TAKIGAWA, A.; KANEMARU, Y.; KAWAKAMI, G.; KABATA, K.; OKAWA, M.; KINJO, J.; YOKOMIZO, K.; YOSHIMITSU, H.; NOHARA, T.; Chem. Pharm. Bull. 62 (2014) 1, 97-105, http://dx.doi.org/10.1248/cpb.c13-00610 ; Sch. Agric., Kyushu Tokai Univ., Aso, Kumamoto 869-14, Japan; Eng.) -H. Toeppel 23-210

Five new resin glycosides having macrolactone structures (jalapins), named calysolins V-IX (1-5), were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae). Their structures were determined on the basis of spectroscopic data as well as chemical evidence. The isolated compounds could be classified into two macrolactone types-one having a 22-membered ring (1-4) and the other with a 27-membered ring (5). The sugar moieties of 1-5 were found to exist in partially acylated forms comprising 2S-methylbutyric acid and tiglic acid. Compounds 4 and 5 are the first representatives of the calysolic acid C as the component glycosidic acid. Additionally, the antiviral activity of 1-5, together with calysolins I-IV and soldanelline B, which are previously isolated jalapins from this plant, toward herpes simplex virus type 1 was evaluated. All the compounds showed antiviral activity.Key words resin glycoside; jalapin; Calystegia soldanella; Convolvulaceae; calysolin; anti-herpes activityis widely distributed on the sandy beaches of seas and lakes in temperate regions of the world. The roots of this plant are used for the treatment of arthritis.1) In our previous investigations, we reported the isolation and structural elucidation of four new glycosidic acids, calysolic acids A-D, which were obtained along with the known glycosidic acid, soldanellic acid B, and three organic acids, 2S-methylbutyric, tiglic, and 2S,3S-nilic acids, upon alkaline hydrolysis of the crude resin glycoside fraction of the leaves, stems, and roots of C. soldanella.2) Further, we isolated four genuine resin glycosides named calysolins I-IV, all of which were found to possess characteristic macrolactone structures, as in already known jalapins, 3) along with one known jalapin, soldanelline B. 4) As part of an ongoing study of the resin glycosides from this plant, the present report deals with the isolation and structural elucidation of five new resin glycosides named calysolins V-IX. Additionally, the antiviral activity of calysolins I-IX and soldanelline B toward herpes simplex virus type 1 (HSV-1) 5) is described.The fresh leaves, stems, and roots of C. soldanella were extracted with methanol. The obtained extract was suspended in H 2 O and then extracted successively with ethyl acetate and n-butanol. The ethyl acetate-soluble fraction was subjected to silica gel column chromatography and HPLC on octadecyl silica (ODS) and naphthylethyl group bonded silica to yield five resin glycosides (1-5).Compound 1

Four new resin glycosides having macrolactone structures (jalapins), named calysolins X (1)-XIII (4), were isolated from the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae). Their structures were determined on the basis of spectroscopic data as well as chemical evidence. The sugar moieties of 1-4 were partially acylated by some organic acids, including tiglic acid, 2S-methylbutyric acid, and 2S,3S-nilic acid. Additionally, the antiviral activity of 1-4 toward herpes simplex virus type 1 was evaluated. All the compounds showed antiviral activity.Key words resin glycoside; jalapin; Calystegia soldanella; Convolvulaceae; calysolin; anti-herpes simplex virus activityis commonly found on the sandy beaches of seas and lakes located the temperate regions of the world. The roots of this plant are used in the treatment of arthritis.1) In our previous paper, we reported the isolation and structural elucidation of four new glycosidic acids, calysolic acids A-D, which were obtained along with the known glycosidic acid, soldanellic acid B, and three organic acids, 2S-methylbutyric, tiglic, and 2S,3S-nilic acids, upon alkaline hydrolysis of the crude resin glycoside fraction of the leaves, stems, and roots of C. soldanella.2) Further, we isolated nine genuine resin glycosides namely calysolins I-IX, all of which possessed characteristic macrolactone structures similar to those of the already known jalapins, 3) along with one known jalapin, soldanelline B, and their antiviral activities toward herpes simplex virus type 1 (HSV-1) were evaluated. 4,5) As a part of an ongoing study of the resin glycosides from this plant, the current study deals with the isolation and structural elucidation of four new resin glycosides named calysolins X (1)-XIII (4). Additionally, the antiviral activity of 1-4 toward HSV-1 is described herein.The fresh leaves, stems, and roots of C. soldanella were extracted using methanol (MeOH). This extract was suspended in H 2 O and then extracted successively using ethyl acetate (EtOAc) and n-butanol (BuOH). The EtOAc-soluble fraction was subjected to silica gel column chromatography and HPLC on octadecyl silica (ODS) and silica gel to yield 1-4.Calysolin X (1) was obtained as an amorphous powder. The negative-ion FAB-MS and positive-ion FAB-MS of 1 exhibited an [M-H] -ion peak at m/z 1051 and an [M+ Na] + ion peak at m/z 1075, respectively, indicating its molecular weight to be 1052. The molecular formula of 1 was found to be C 50 H 84 O 23 using high-resolution (HR)-positive-ion FAB-MS. Upon alkaline hydrolysis, 1 yielded a glycosidic acid and an organic acid fraction. The gas chromatography (GC) analysis of the organic acid fraction revealed the presence of tiglic and nilic acids. The glycosidic acid was identified as soldanelic acid B (5) by comparing with an authentic sample 2) using 1 H-NMR spectroscopy. The 1 H-NMR spectrum of 1 exhibited signals due to one H-2 of the niloyl residue, one H-3 of the tigloyl residue, and four anomeric protons. The 13 C-NMR spectrum...