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Labdane-type Diterpenoids from the Fruits of Vitex rotundifolia
Labdane-type Diterpenoids from the Fruits of Vitex rotundifolia
Bulletin of the Korean Chemical Society. 2014. Feb, 35(2): 672-674
Copyright © 2014, Korea Chemical Society
  • Received : July 02, 2013
  • Accepted : September 09, 2013
  • Published : February 20, 2014
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About the Authors
Xiao-Qiang Wang
Teng Zhang
Department of Pharmacy, School of Ocean, Shandong University at Weihai, Weihai 264209, P.R. China
Bin Zheng
Wei-Dong Xie
Department of Pharmacy, School of Ocean, Shandong University at Weihai, Weihai 264209, P.R. China
Tong Shen

Abstract
Keywords
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Experimental Section
General Procedures . Melting points were determined on Kofler melting point apparatus and uncorrected. Optical rotations were measured on a Perkin-Elmer 341 polarimeter. IR spectra were obtained from Nicolet NEXUS 670 FT-IR spectrometer. 1 H-, 13 C-NMR (DEPT) and 2D NMR were recorded on Bruker AVANCE 500 spectrometer. HR-ESI-MS spectrum was obtained on Bruker APEX spectrometer. Silica gel used for column chromatography (CC) and silica GF 254 for thin layer chromatography (TLC) were purchased from Qingdao Marine Chemical Factory in China. Silica gel C-18 used for low pressure CC was purchased from Merck . Spots were detected on TLC under UV light at 254 nm or by heating after spraying with 5% H 2 SO 4 in EtOH.
Plant Material . The fruits of V. rotundifolia were collect-ed from Wendeng, Weihai, Shandong Province, P. R. China, in September 2010, and identified by Associate Prof. Hong Zhao (Shandong University at Weihai). A voucher specimen (No. KY201001) is deposited at the herbarium in the Labo-ratory of Botany, Marine College, Shandong University at Weihai.
Extraction and Isolation . The powered fruits (35 kg) of V. rotundifolia were extracted with MeOH at room temper-ature (7 days × 3). The extract was partitioned with petro-leum ether (60-90 °C), CHCl 3 and H 2 O. The CHCl 3 soluble fraction (1204g) was separated by silica gel CC eluting with hexane-acetone gradient (20:1 to 2:1) to give four fractions (Fr1-Fr4). Fr2 (hexane-acetone, 10:1, 155 g) was isolated by silica gel CC with hexane-EtOAc gradient (20:1 to 2:1) to afford subfractions f 1 - f 4 . Compound 3 (72 mg) was purified from f 1 (hexane-EtOAc, 20:1). Fr3 (hexane-acetone, 5:1, 232 g) was isolated by silica gel CC with hexane-EtOAc gradient (20:1 to 2:1) to afford subfractions f 5 - f 8 . Subfraction f 5 (hexane-EtOAc, 15:1) was subject to a silica gel CC puri-fication with hexane-acetone(10:1) elution, and further purified by C-18 CC (H 2 O-MeOH 1:1) to give 2 (68 mg). Compounds 1 (45 mg) was obtained by repeated silica gel CC (hexane-acetone, 10:1) and C-18 CC (H 2 O-MeOH, 1:1) from f 6 (hexane-EtOAc, 5:1). The R f values of compounds 1 and 2 were 0.16 and 0.27 respectively when they were checked by TLC in silica gel developed with hexane-acetone (10:1).
Vitrifolin B (1) . Colorless crystal; mp 171-173 °C;
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= +32 ( c 0.625, CH 3 OH); IR (KBr): v max 3414, 2964, 2928, 1739, 1686, 1463, 1384, 1261, 1098, 1051, 1020, 801, 637, 615 cm −1 ; HR-ESI-MS m/z : 403.2451 ([M + Na] + , Calcd for C 22 H 36 O 5 Na + : 403.2455). 1 H-NMR (500 MHz, CDCl 3 ) and 13 C-NMR (DEPT) (125 MHz, CDCl 3 ): see Table 1 .
Vitexlactam A (2) . Colorless needle crystal; mp 205-207 °C; 1 H-NMR (500 MHz, CDCl 3 ) δ 6.70 (1H, brs, H-14), 5.32 (1H, brs, H-6), 3.90 (2H, brs, H 2 -15), 1.97 (3H, s, H 3 - 2'), 1.14 (3H, s, H 3 -20), 0.92 (3H, s, H 3 -19), 0.89 (3H, s, H 3 - 18), 0.85 (3H, d, J = 6.7 Hz, H 3 -17); 13 C-NMR (125 MHz, CDCl 3 ) δ 32.7 (C-1), 17.8 (C-2), 42.7 (C-3), 32.9 (C-4), 46.5 (C-5), 69.6 (C-6), 35.2 (C-7), 32.6 (C-8), 76.2 (C-9), 42.9 (C-10), 31.3 (C-11), 20.8 (C-12), 139.6 (C-13), 136.2 (C-14), 45.5 (C-15), 173.8 (C-16), 15.5 (C-17), 31.2 (C-18), 22.7 (C-19), 17.9 (C-20), 169.5 (C-1'), 20.9 (C-2').
Vitexilactone (3) . Colorless needle crystal; mp 143 - 145 ° C; 1 H-NMR (500 MHz, CDCl 3 ) δ 5.77 (1H, m, H-14), 5.32 (1H, m, H-6), 4.68 (2H, brs, H 2 -16), 1.98 (3H, s, H 3 -2'), 1.18 (3H, s, H 3 -20), 0.94 (3H, s, H 3 -19), 0.89 (3H, s, H 3 -18), 0.83 (3H, d, J = 6.8 Hz, H 3 -17); 13 C-NMR (125 MHz, CDCl 3 ) δ 31.0 (C-1), 17.5 (C-2), 42.5 (C-3), 32.9 (C-4), 46.6 (C-5), 68.7 (C-6), 34.9 (C-7), 32.5 (C-8), 75.4 (C-9), 42.7 (C-10), 30.5 (C-11), 24.3 (C-12), 170.1 (C-13), 113.9 (C-14), 173.0 (C-15), 72.1 (C-16), 15.0 (C-17), 31.0 (C-18), 22.6 (C-19), 17.9 (C-20), 169.4 (C-1'), 20.8 (C-2').
Acknowledgements
This work was financially supported by the Independent Innovation Foundation of Shandong University, China (No. 2010ZRYB005). And the publication cost of this paper was supported by the Korean Chemical Society.
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