A New Sulfated α-ionone Glycoside from Sonchus erzincanicus Matthews - PDF

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Molecules 0, 1, 9-99; doi:.90/molecules9 Article PEN ACCESS molecules ISSN A New Sulfated α-ionone Glycoside from Sonchus erzincanicus Matthews Ufuk zgen 1, *, Handan

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Molecules 0, 1, 9-99; doi:.90/molecules9 Article PEN ACCESS molecules ISSN A New Sulfated α-ionone Glycoside from Sonchus erzincanicus Matthews Ufuk zgen 1, *, Handan Sevindik 1, Cavit Kazaz, Demet Yigit, Ali Kandemir, Hasan Secen and Ihsan Calis, 1 Department of Pharmacognosy, Faculty of Pharmacy, Atatürk University, 0 Erzurum, Turkey; (H.S.) Department of Chemistry, Faculty of Sciences, Atatürk University, 0 Erzurum, Turkey; s: (C.K.); (H.S.) Department of Biology, Faculty of Education, Erzincan University, 00 Erzincan, Turkey; s: (D.Y.); (A.K.) Department of Pharmacognosy, Faculty of Pharmacy, Hacettepe University, 00 Sıhhıye, Ankara, Turkey; s: (I.C.) Present address: Department of Pharmacognosy and Pharmaceutical Botany, Faculty of Pharmacy, Near East University, Nicosia, North Cyprus, Turkey. * Author to whom correspondence should be addressed; Received: 1 March 0 / Accepted: March 0 / Published: 1 April 0 Abstract: Sonchus erzincanicus (Asteraceae) is an endemic species in Turkey, where six Sonchus species grow. In this study, a phytochemical study was performed on the aerial parts of the plant. The study describes the isolation and structure elucidation of five flavonoids and two α-ionone glycosides from S. erzincanicus. The compounds were isolated using several and repeated chromatographic techniques from ethyl acetate and aqueous phases that were partitioned from a methanol extract obtained from the plant.,7,,'-tetrahydroxy--methoxyflavone (1) and quercetin --β-d-glucoside () were isolated from the ethyl acetate phase, while corchoionoside C --sulfate (), corchoionoside C (), luteolin 7--glucuronide () and luteolin 7--β-Dglucoside (), apigenin 7--glucuronide (7) were isolated from the aqueous phase. Corchoionoside C --sulfate (), isolated for the first time from a natural source, was a new compound. The structures of the compounds were elucidated by means of 1 H-NMR, 1 C-NMR, D-NMR (CSY, HMQC, HMBC) and ESI-MS. Molecules 0, 1 9 Keywords: asteraceae; flavonoids; α-ionone glycoside; Sonchus erzincanicus 1. Introduction The Asteraceae family or Compositae is represented by about 900 genera and 1,000 species [1]. The genus Sonchus (Asteraceae) comprises 0 known species worldwide [1], and is represented by six species in the flora of Turkey, one of which, S. erzincanicus, is endemic, []. Sonchus species are variously known as sütlük, kuzu gevreği, and eşek marulu in Turkey []. It has been found that some Sonchus species contain sesquiterpene lactone glucosides, flavonoids, triterpenes and steroids [,]. No phytochemical study has so far been carried out on S. erzincanicus. This study describes the isolation and structure elucidation of five flavonoids and two α-ionone glycosides, one being a new compound, from S. erzincanicus.. Results and Discussion In our phytochemical studies on the aerial parts of Sonchus erzincanicus, we isolated flavonoids and α-ionone glycosides by using several chromatographic methods. The flavonoids were identified as,7,,'-tetrahydroxy--methoxyflavone (1) [], quercetin --β-d-glucoside () [7,], luteolin 7-glucuronide () [9], luteolin 7--β-glucoside () [] and apigenin 7--glucuronide (7) [11]. Compound was identified as a known α-ionone glycoside, corchoionoside C () [1]. Compound, corchoionoside C --sulfate, was identified as a new natural compound (Figure 1). Figure 1. Isolated compounds from Sonchus erzincanicus. H ' ' CH ' ' HC '' H H '' '' '' ' ' 7 9 ' ' ' ' (1),7,, -Tetrahydroxy--methoxy-flavone H ' ' ' ' ' H ' '' '' '' '' () Quercetin --β-d-glucoside H H '' '' '' () Luteolin 7--glucuronide '' ' ' ' ' () Luteolin 7--β-D-glucoside ' ' Molecules 0, 1 9 Figure 1. Cont H ' ' R ' ' () R= S H Corchoionoside C --sulfate () R= H Corchoionoside HC H H '' '' '' '' ' ' ' ' (7) Apigenin 7--glucuronide ' ' The NMR data of compound revealed the presence of a structure similar to that of compound. HRMS spectra of protonated (MH + ) was 7.1, which was in agreement with the calculated value: 7.1. The ESI-MS of compound showed the deprotonated molecule ion peak at m/z [M-H] - and a deprotonated positive ion peak with two added sodium atoms [M-H+Na] + at 11. The assignments of all proton and carbon resonances (Table 1) were based on D NMR (CSY, HETCR, HMBC) experiments. The anomeric proton signal at δ. (d, J = 7.7 Hz) together with other resonances assigned to the sugar unit having a β-glucose moiety. Remaining signals were attributed to the ionone skeleton. All 1 H-NMR and 1 C-NMR signals were in agreement with the data given for the structure of corchoionoside C () except for C-' and H -' due to esterification at this location [1]. While C-' of corchoionoside C () resonates at δ 1. ppm, the same carbon of its sulfate derivative resonates at δ 7.1 ppm due to inductive effect of sulfate ester group. Four diastereomeric reseosides, diastereomers of corchoinoside C, were recently synthesized by Yajima et al.: (S,9S), corchoinoside C; (S,9R); (R,9S), (R,9R). Comparing NMR spectral data of and with the ones of the four reseosides provided clear evidence that both corchoinoside C and corchoionoside C --sulfate are in agreement with the structure of (S,9S) reseoside [1]. Thus, the structure of was established as corchoionoside C --sulfate. It is the first time that this compound has been isolated from Nature. Table 1. NMR Spectroscopic data for compound ( 1 H-NMR: 00 MHz, 1 C-NMR: 0 MHz). C/H atom δc δh ppm, J (Hz) HMBC (H C) d (1.7) C-11, C-1.1 d (1.7) bs C-, C d (1.) C-9, C dd (1., 7.) C-, C quintet (.) C-, C d (.) C s C-, C s C-, C d (1.1) C-, C- Molecules 0, 1 9 Table 1. Cont. C/H atom δc δh ppm, J (Hz) HMBC (H C) Glucose 0.1. d (7.7) ' a ' 70. ' 7.9 ' dd, (.9, 1.).09 dd (.9,.) a Signal patterns are not clear due to overlapping.. Experimental.1. General 1 H-NMR and 1 C-NMR spectra were recorded with a Varian Mercury plus spectrometer at 00 and at 0 MHz, respectively. Mass spectra were recorded with Micromass ZQ Mass Spectrometer (Manchester, UK). Sephadex LH-0 (Sigma-Aldrich) and Silica gel (Kiesel gel 0, mm Merck 77 and mm Merck 9 and LiChroprep RP-1, -0 μm, Merck 90) were used for column chromatography, while silica gel 0 F (Merck, ) was used for TLC. TLC spots were detected with a UV lamp, spraying 1% Vanillin/H S and heated at C for 1- min... Plant material The aerial parts of S. erzincanicus were collected from Ekşisu (Erzincan Province, Turkey) in 00 and was identified by Dr. A. Kandemir. A voucher specimen was deposited in the Herbarium of Erzincan University, Faculty of Education (EEFH 779)... Extraction and isolation Dried aerial parts (0 g) of the plant material were extracted by refluxing with methanol ( L x ) on a mantle. The methanol extract was concentrated and dried under reduced pressure to give a residue (. g). Methanol extract (.0 g) was dissolved in H -Me (9:1) and partitioned with chloroform and then ethyl acetate, which were separately concentrated and dried under reduced pressure to give 9. g and 0.9 g residues, respectively. The remaining aqueous phase was g. There were too few compounds to isolate and identify in chloroform phase. The ethyl acetate phase (0.9 g) was subjected to silica gel column chromatography using CHCl - Me-H (0:0:, 70:0:, 0:0:) solvent systems. Fifty nine fractions were collected. Fraction (.7 mg) gave compound 1 (9 mg) while fractions 1- (7 mg) gave compound (1 mg). The remaining aqueous phase ( g) was subjected to reversed phase silica gel column chromatography using 0-0% aqueous Me as solvent systems. Fractions were monitored by TLC on silica gel plates and similar fractions were combined to give fraction A (Fr. 1-,. g), fraction B (Fr. 0-0, mg) and fraction C (Fr. -, 70 mg). Molecules 0, 1 97 Fraction A was subjected to silica gel column chromatography with CHCl :Me:H (70:0:, ::) solvent system. Fr. -7 gave compound (1 mg). Fraction B was subjected to a gel chromatography (Sephadex LH-0) eluting with Me and 1 fractions were collected. The fractions - (B1, 17 mg) were further purified by successive column chromatography on silica gel and Sephadex LH-0, respectively, yielding pure (1 mg). The fractions - (B, mg) gave compound. Fraction C was subjected to a silica gel column chromatography with CHCl -Me-H (70:0:) and 0 fractions were collected. The fractions -1 (C1, 0 mg) were subjected to gel chromatography (Sephadex LH-0) with Me to give compound (1 mg). The fractions 1-0 (C, 1 mg) were subjected to a gel chromatography (Sephadex LH-0) with Me to give compound 7 ( mg). Compound 1: Yellow powder; 1 H-NMR (CD D): δ 7.0 (1H, bs, H-'), 7. (1H, d, H-', J =. Hz),.9 (1H, d, H-', J =. Hz),.7 (1H, bs, H-),.1 (1H, bs, H-),.77 (s, CH ); 1 C-NMR (CD D): δ 17. (C-), 1.9 (C-7), 11. (C-), 17. (C-9), 1. (C-), 1.7 (C-'), 1. (C-), 1. (C-), 11.7 (C-), 11.1 (C-'), 11. (C-'), 11. (C-'),. (C-), 9. (C- ), 9. (C-), 9. (CH ). 1 H-NMR and 1 C-NMR agree with data given in the literature for,7,,'-tetrahydroxy--methoxyflavone []. Compound : Yellow powder; 1 H-NMR (CD D): δ 7.70 (1H, d, H-', J = 1.9 Hz), 7. (1H, dd, H- ', J =. Hz, 1.9 Hz),. (1H, d, H-', J =. Hz),. (1H, d, H-, J =. Hz),.17 (1H, d, H-, J =. Hz),. (1H, d, H-', J = 7. Hz),.-.0 (H, sugar protons); 1 C-NMR (CD D): δ 17.1 (C-), 1. (C-7), 11. (C-), 17. (C-), 17. (C-9), 1.7 (C-'), 1.7 (C-), 1. (C- ), 1.0 (C-), 11.9 (C-'), 11. (C-'), 11. (C-'),.1 (C-),. (C-'), 99. (C-), 9. (C-), 77. (C-''), 7.9 (C-'), 7. (C-''), 70.0 (C-''), 1. (C-''). 1 H-NMR and 1 C-NMR agree with data given in the literature for quercetin --β-d-glucoside [7,]. Compound : Amorphous colourless solid; [α] D = + (c=1, Me), ESI-MS (C 19 H 0 11 S), m/e: [M-H] and 11 [M-H+Na] +. HRMS: calculated for C 19 H 1 11 S + : 7.1; found: 7.1. For 1 H-NMR (CD D) and 1 C-NMR (CD D). See (Table 1). Compound : Amorphous colourless solid, ESI-MS (C 19 H 0 ), m/e: 09 [M+Na] + and [M-H] -, 1 H-NMR (CD D): δ.97 (1H, d, H-7, J = 1. Hz),. (1H, s, H-),.7 (1H, dd, H-, J = 1. Hz, J = 7.0 Hz),. (1H, quintet, H-9, J =. Hz),. (1H, d, H-, J = 7.7 Hz),. (1H, dd, H- a ', J = 11.9 Hz, J =. Hz),. (1H, dd, H- b ', J = 11.9 Hz, J =.0 Hz),.-. (sugar protons, overlapped, H, H-', H-, H-', H-'),.1 (1H, d, H-a, J = 17. Hz),.1 (1H, d, H-b, J = 17. Hz), 1.9 (H, bs, H-1), 1.0 (H, d, H-, J =. Hz), 0.91 (H, s, H-11), 0. (H, s, H- 1); 1 C-NMR (CD D): δ 00.0 (C-), 1.0 (C-), 1. (C-7), 1. (C-), 1.9 (C-), 0.1 (C- ), 77.1 (C-), 77.0(C-'), 7. (C-), 7. (C-'), 70.7 (C-9), 70. (C-'), 1. (C-'), 9. (C-), 1. (C-1),. (C-1),. (C-11),. (C-), 1. (C-1). 1 H-NMR and 1 C-NMR agree with data given in the literature for corchoionoside C [1]. Molecules 0, 1 9 Compound : Yellow powder; 1 H-NMR (DMS-d ): δ 7.0 (1H, d, H-', J =.0 Hz), 7. (1H, dd, H- ', J =. Hz, J =.0 Hz),. (1H, d, H-', J =. Hz),.7 (1H, d, H-, J = 1.9 Hz),.9 (1H, s, H-),.9 (1H, d, H-, J = 1.9 Hz),.0 (1H, d, H-', J = 7. Hz),.0 (1H, d, H-'', J = 9.9 Hz),.9-.1 (m, H, sugar protons, overlapped with DMS-d signals); 1 C-NMR (DMS-d ): δ 1. (C-), 17. (C-''), 1.1 (C-), 1. (C-7), 11.7 (C-), 17. (C-9),. (C-'), 1. (C-), 11.7 (C-), (C-'), 11.7 (C-'), 11.1 (C-'),.9 (C-),. (C-), 0. (C-'), 0. (C-), 9. (C-), 77.1 (C-'), 7. (C-''), 7. (C-''), 7. (C-''). 1 H-NMR and 1 C-NMR agree with data given in the literature for luteolin 7--glucuronide [9]. Compound : Yellow powder; 1 H-NMR (DMS-d ): δ 7. (1H, bd, H-', J =. Hz), 7.0 (1H, bs, H-'),.7 (1H, d, H-', J =. Hz),.77 (1H, d, H-, J = 1. Hz),.7 (1H, s, H-),. (1H, d, H-, J = 1. Hz),.0 (1H, d, H-', J = 7. Hz), (H, sugar protons); 1 C-NMR (DMSd ): δ 1. (C-), 1. (C-), 1. (C-7), 11. (C-), 17. (C-9), 11.1 (C-'), 1. (C-), 11.7 (C-), (C-'), 11. (C-'), 11.1 (C-'),.0 (C-),.7 (C-), 0. (C-'), 0. (C-), 9. (C-), 77. (C-''), 77.1 (C-'), 7. (C-''), 70. (C-''), 1. (C-''). 1 H-NMR and 1 C-NMR agree with data given in the literature for luteolin 7--β-D-glucoside []. Compound 7: Yellow powder; 1 H-NMR (DMS-d ): δ 7. (H, quasi d, H-'/', J =. Hz),. (H, quasi d, H-/', J =. Hz),. (1H, d, H-, J =.0 Hz),. (1H, s, H-),.9 (1H, d, H-, J =.0 Hz),. (1H, d, H-', J =. Hz),.90-. (sugar protons, H, H-'', H-', H-'', H-''); 1 C- NMR (DMS-d ): δ 1.0 (C-), 17.1 (C-''), 1.9 (C-), 1.7 (C-7), 11. (C, C-' and C-), 17. (C-9), 1. (C, C-'/'), 11.1 (C-), 11. (C, C-/'),.0 (C-),. (C-), 0. (C- '), 0. (C-), 9.9 (C-), 7. (C-''), 7. (C-'), 7. (C-''), 7. (C-''). 1 H-NMR [11] and 1 C- NMR [1] agree with data given in the literature for apigenin 7--glucuronide. Acknowledgements The authors are grateful to Erhan Palaska (Hacettepe University, Faculty of Pharmacy, Ankara, Turkey) for ESI mass spectra. We thank Arata Yajima for providing graphical NMR spectra of the four reseosides by which we could establish the structures of and. References 1. Evans, W.C. Trease and Evans Pharmacognosy, 1th ed.; Balliére Tindall: London, UK, 199; pp. 7.. Matthews, V.A. Sonchus L. In Flora of Turkey and the East Aegean Islands; Davis, P.H., Ed.; University Press: Edinburgh, UK, 197; Volume, pp Akartürk, R. Şifalı Bitkiler, Flora ve Sağlığımız; rman Genel Müdürlüğü Mensupları Yardımlaşma Vakfı (in Turkish): Ankara, Turkey, Helal, A.M.; Nakamura, N.; El-Askary, H.; Haatori, M. Sesquiterpene lactone glucosides from Sonchus asper. Phytochemistry 000,, 7 77. Molecules 0, Devkota, K.P. Cholinesterase inhibiting and antiplasmodial steroidal alkaloids from Sarcococca hookeriana. Ph.D. Thesis. 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This article is an open-access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/.0/).
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