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Isolation of a New Labdane-type Diterpene from Vitex rotundifolia
Isolation of a New Labdane-type Diterpene from Vitex rotundifolia
Bulletin of the Korean Chemical Society. 2013. Dec, 34(12): 3840-3842
Copyright © 2013, Korea Chemical Society
  • Received : August 28, 2013
  • Accepted : September 09, 2013
  • Published : December 20, 2013
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About the Authors
You Ah Kim
Da Seul Kim
Kwang-suk Oh
Department of Architecture and Ocean Space, College of Ocean Science and Technology, Korea Marine University, Busan 606-791, Korea
Youngwan Seo
Ocean Science & Technology School, Korea Marine University Busan 606-791, Korea.

Abstract
Keywords
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Experimental
General Experimental Procedures. Optical rotations were determined on a Perkin-Elmer polarimeter 341. NMR spectra were recorded in CD 3 OD and CDCl 3 on a Varian Mercury 300 instrument at 300 MHz for 1 H and 75 MHz for 13 C 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 CH 2 Cl 2 (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 CH 2 Cl 2 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 H 2 O. 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 C 18 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. CH 3 CN) to give 1 (2.5 mg) and 4 (15.0 mg), respectively. Subfraction 4-4 was separated by reversed-phase HPLC with 63% aq. CH 3 CN to afford 3 (18.0 mg). Similarly, subfraction 4-5 was applied on reversed-phase HPLC with 63% aq. CH 3 CN 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. CH 3 CN 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,
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+17.0 ( c = 0.42, MeOH). HR-ESI-MS (negative-ion mode) m/z : 393.2286 [M-H] - (calcd for C 22 H 33 O 6 : 393.2277); 1 H-NMR and 13 C-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,
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-7.2 (c, 0.21, MeOH). ESI-MS (negative-ion mode) m/z 407 (M-H) - , EI-MS m/z : 348 (M-CH 3 COOH ) + .
Vitexilactone (3): A pale yellow solid,
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-3.0 ( c = 0.37, MeOH). EI-MS m/z : 318 (M-CH 3 COOH)+. 1 H-NMR and 13 C-NMR, see Table 1 .
Vitetrifolin D (4): A colorless syrup,
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+104 ( c =1.28, MeOH). EI-MS m/z : 346 (M-CH 3 COOH) + , 286 (MCH 3 COOH×2) + .
Vitetrifolin E (5): A colorless solid,
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+60 ( c = 0.38, MeOH). EI-MS m/z : 304 (M-CH 3 COOH) + .
Vitetrifolin F (6): A colorless syrup,
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+83 ( c = 0.22, MeOH). EI-MS m/z : 304 (M-CH 3 COOH) + .
Acknowledgements
Mass spectral data were kindly provided by Korea Basic Science Institute. This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2012R1-A1A2002851) and is the outcome of a Manpower Development Program for Marine Energy by the Ministry of Land, Transport and Maritime Affairs (MLTM).
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