Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Isolation of a New Labdane-type Diterpene from Vitex rotundifolia

  • Kim, You Ah (Division of Marine Environment and Bioscience, Korea Maritime University) ;
  • Kim, Da Seul (Division of Marine Environment and Bioscience, Korea Maritime University) ;
  • Oh, Kwang-Suk (Department of Architecture and Ocean Space, College of Ocean Science and Technology, Korea Marine University) ;
  • Seo, Youngwan (Ocean Science & Technology School, Korea Marine University)
  • Received : 2013.08.28
  • Accepted : 2013.09.09
  • Published : 2013.12.20
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Abstract

Keywords

Experimental

General Experimental Procedures. Optical rotations were determined on a Perkin-Elmer polarimeter 341. NMR spectra were recorded in CD3OD and CDCl3 on a Varian Mercury 300 instrument at 300 MHz for 1H and 75 MHz for 13C using standard pulse sequence programs. All chemical shifts were recorded with respect to TMS as an internal standard. Mass spectra were obtained at the Korean Basic Science Institute, Seoul, Korea. Column chromatography was carried out on RP 18 (YMC-Pack ODS-A, 12 nm, S-5 μm, 250 × 10 mmI.D., YMC, USA) and silica gel (YMCPack SIL, 12 nm, S-5 μm, 250 × 10 mmI.D., YMC, USA). High performance liquid chromatography (HPLC) was performed on a Dionex P580 HPLC system equipped with a Varian 350 RI detector. All solvents used were spectral grade or were distilled from glass prior to use.

Plant Material. The halophyte V. rotundifolia used for this study was collected from the Muan-gun, Jeollanamdo, Korea in July of 2008. The species was identified by Dr. Sung-Gi Moon by its morphological character. A voucher specimen (08H-6) is deposited at the Herbarium of the Division of Marine Environment and Bioscience, Korea Maritime University, Busan, Korea.

Extraction and Isolation. The air-dried sample of V. rotundifolia was chopped into small pieces and extracted successively for 48 h with CH2Cl2 (3 L × 2) and MeOH (3 L × 2), in turn. The combined crude extract (145.1 g) was evaporated under reduced pressure and then the residue was partitioned between CH2Cl2 and water. The organic layer was further partitioned between 85% aqueous MeOH and n-hexane, and the aqueous layer was fractionated with n- BuOH and H2O. The resulting four fractions were evaporated to dryness in vacuo, to yield n-hexane (33.6 g), 85% aqueous MeOH (21.0 g), n-BuOH (39.0 g), and water (47.8 g) fractions, respectively. The portion of the 85% aqueous MeOH (21.0 g) fraction was subjected to C18 reversed-phase vacuum flash chromatography and eluted with gradient system of MeOH-water of decreasing polarity (50, 60, 70, 80, 90, 100%; 800mL each) to provide 6 fractions. Fraction 4 was separated by reversed-phase HPLC (ODS-A, 78% aq. MeOH) to give 6 subfractions (4-1~6), in order of elution. Subfraction 4-2 and 4-3 were separately purified by reversed-phase HPLC with same solvent (ODS-A, 50% aq. CH3CN) to give 1 (2.5 mg) and 4 (15.0 mg), respectively. Subfraction 4-4 was separated by reversed-phase HPLC with 63% aq. CH3CN to afford 3 (18.0 mg). Similarly, subfraction 4-5 was applied on reversed-phase HPLC with 63% aq. CH3CN to give 5 (55.7 mg) and one mixture (4-5-1). Subfraction 4-5-1 was applied on normal-phase HPLC eluting with 25% EtOAc in hexane to give 2 (2.9 mg). Subfraction 4-6 was subjected reversed-phase HPLC with 60% aq. CH3CN to afford 6 (69.9 mg).

(5S*,6R*,8R*,9R*,10S*)-6-Acetoxy-9,16-dihydroxy-13(14)- labden-16,15-olide (1): A pale yellow solid, +17.0 (c= 0.42, MeOH). HR-ESI-MS (negative-ion mode) m/z: 393.2286 [M-H]- (calcd for C22H33O6: 393.2277); 1H-NMR and 13C-NMR, see Table 1.

(5S*,6R*,8R*,9R*,10S*)-6-Acetoxy-9-hydroxy-15-methoxy- 13(14)-labden-16,15-olide (2): An amorphous white solid, -7.2 (c, 0.21, MeOH). ESI-MS (negative-ion mode) m/z 407 (M-H)-, EI-MS m/z: 348 (M-CH3COOH )+.

Vitexilactone (3): A pale yellow solid, -3.0 (c = 0.37, MeOH). EI-MS m/z: 318 (M-CH3COOH)+. 1H-NMR and 13C-NMR, see Table 1.

Vitetrifolin D (4): A colorless syrup, +104 (c =1.28, MeOH). EI-MS m/z: 346 (M-CH3COOH)+, 286 (MCH3COOH×2)+.

Vitetrifolin E (5): A colorless solid, +60 (c = 0.38, MeOH). EI-MS m/z: 304 (M-CH3COOH)+.

Vitetrifolin F (6): A colorless syrup, +83 (c = 0.22, MeOH). EI-MS m/z: 304 (M-CH3COOH)+.

References

  1. Lee, Y. N. Flora of Korea; Kyo-Hak Publishing Co. Ltd.: 2002; p 241.
  2. Ono, M.; Yamamoto, M.; Yanaka, T.; Ito, Y.; Nohara, T. Chem. Pharm. Bull. 2001, 49, 82. https://doi.org/10.1248/cpb.49.82
  3. Kondo, Y.; Sugiyama, K.; Nozoe, S. Chem. Pharm. Bull. 1986, 33, 4829.
  4. Hoberg, E.; Orjala, J.; Meier, B.; Sticher, O. Phytochemistry 1999, 52, 1555. https://doi.org/10.1016/S0031-9422(99)00181-8
  5. Ono, M.; Ito, Y.; Nohara, T. Chem. Pharm. Bull. 2001, 49, 1220. https://doi.org/10.1248/cpb.49.1220
  6. Ono, M.; Ito, Y.; Kubo, S.; Nohara, T. Chem. Pharm. Bull. 1997, 45, 1094. https://doi.org/10.1248/cpb.45.1094
  7. You, K. M.; Son, K. H.; Chang, H. W.; Kang, S. S.; Kim, H. P. Planta Med. 1998, 64, 546. https://doi.org/10.1055/s-2006-957511
  8. Ono, M.; Ito, Y.; Nohara, T. A. Phytochemistry 1998, 48, 207. https://doi.org/10.1016/S0031-9422(97)00863-7
  9. Kawazoe, K.; Yutani, A.; Takaishi, Y. Phytochemistry 1999, 52, 1657. https://doi.org/10.1016/S0031-9422(99)00405-7
  10. Ono, M.; Yamamoto, M.; Masuoka, C.; Ito, Y.; Yamashita, M.; Nohara, T. J. Nat. Prod. 1999, 62, 1532. https://doi.org/10.1021/np990204x
  11. Ono, M.; Sawamura, H.; Ito, Y.; Mizuki, K.; Nohara, T. Phytochemistry 2000, 55, 873. https://doi.org/10.1016/S0031-9422(00)00214-4
  12. Shin, T. Y.; Kim, S. H.; Lim, J. P.; Suh, E. S.; Jeong, H. J.; Kim, B. D.; Park, E. J.; Hwang, W. J.; Rye, D. G.; Baek, S. H.; An, N. H.; Kim, H. M. J. Ethnopharmacol. 2000, 72, 443. https://doi.org/10.1016/S0378-8741(00)00258-0
  13. Ko, W. G.; Kang, T. H.; Lee, S. J.; Kim, N. Y.; Kim, Y. C.; Sohn, D. H.; Lee, B. H. Food Chem. Toxicol. 2000, 38, 861. https://doi.org/10.1016/S0278-6915(00)00079-X
  14. Ko, W. G.; Kang, T. H.; Lee, S. J.; Kim, Y. C.; Lee, B. H. Phytother. Res. 2001, 15, 535. https://doi.org/10.1002/ptr.743
  15. Wang, H. Y.; Cai, B.; Cui, C. B.; Zhang, D. Y.; Yang, B. F. Yao Xue Xue Bao. 2005, 40, 27.
  16. Kim, Y. A.; Lee, J. I.; Hong, J. W.; Jung, M. E.; Seo, Y. Ocean and Polar Research 2011, 33, 255. https://doi.org/10.4217/OPR.2011.33.3.255

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