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A New Halimane Diterpenoid from Croton crassifolius
A New Halimane Diterpenoid from Croton crassifolius
Bulletin of the Korean Chemical Society. 2014. May, 35(5): 1556-1558
Copyright © 2014, Korea Chemical Society
  • Received : December 09, 2013
  • Accepted : January 13, 2014
  • Published : May 20, 2014
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About the Authors
Zhan-Xin, Zhang
Hui-Hong, Li
Feng-Ming, Qi
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
Hui-Yan, Xiong
Agriculture and Animal Husbandry College, Qinghai University, Xining 810016, China
Le-Le, Dong
Gai-Xia, Fan
Dong-Qing, Fei

Abstract
Keywords
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Experimental Section
General Experimental Procedures. Melting points were determined on an X-4 digital display micromelting point apparatus, and are uncorrected. UV spectra were recorded on a Shimadzu UV-2550 UV-Vis spectrophotometer. Optical rotations were measured on a Perkin Elmer 341 polarimeter. IR spectra were taken on a Nicolet NEXUS 670 FT-IR spectrometer. NMR spectra were recorded on a Varian Mercury-600BB NMR spectrometers with TMS as internal standard. HR-ESI-MS data were recorded on a Thermo LTQ Orbitrap Elite mass spectrometer. Sephadex LH-20 were supplied by Amersham Pharmacia Biotech. Silica gel (200-300 mesh) used for column chromatography and silica gel GF 254 (10-40 μM) used for TLC were supplied by the Qingdao Marine Chemical Factory, Qingdao, China. Spots were detected on TLC under UV light or by heating after spraying with 5% H 2 SO 4 in C 2 H 5 OH (v/v).
Plant Material. The roots of C . crassifolius were pur-chased from Hebei Anguo Medicine Market, and were originally collected from Fujian province of China in September 2012. A voucher specimen (No. 201209CC) was deposited at the School of Pharmacy, Lanzhou University and was identified by Dr. Jian-Yin Li.
Extraction and Isolation. The air-dried and powdered roots of C . crassifolius (9.5 kg) were extracted four times with 95% aqueous EtOH at room temperature to give a residue (962 g) after evaporation. The residue was suspend-ed in H 2 O and extract with EtOAc and n -BuOH. The EtOAc partition (731 g) was applied to silica gel CC, eluting with petroleum ether-acetone (40:1–0:1 gradient system). Then six crude fractions (A-F) were obtained by TLC analysis. Fraction B was subjected to silica gel CC eluting with petro-leum ether-acetone (50:1 to 10:1) to give two subfractions (Fr.B1 and Fr.B2). The subfration Fr.B2 (6.5 g) was further applied to silica gel CC, and eluted with petroleum ether-EtOAc (20:1, 10:1, 5:1, 3:1) to give Fr.B2.1–Fr.B2.4. The Fr.B2.2 was subjected to CC on Sephadex LH-20 (CHCl 3 -MeOH, 1:1) and silica gel (petroleum ether-acetone, 15:1 to 2:1) to yield compound 1 (5 mg). Fraction D was subjected to silica gel CC eluting with petroleum ether-acetone (20:1 to 3:1) to give two subfractions (Fr.D1 and Fr.D2). The subfration Fr.D2 (55 g) was further applied to silica gel CC, and eluted with petroleum ether-acetone (10:1, 5:1, 3:1) to give compound 2 (10 g).
Crassifoliusin A (1): Yellow crystals (acetone); mp 126-129 °C;
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–20° ( c 0.1, CHCl 3 ); UV (CH 3 OH) λ max (log ε) 216.2 (3.69) nm; IR (KBr) ν max cm −1 : 3467, 2932, 2873, 1722, 1682, 1505, 1458, 1257, 1231, 1123, 870, 757; HR-ESI- MS m/z : 357.1688 [M + H] + (calcd for C 21 H 25 O 5 , 357.1697); 1 H-NMR (600 MHz, CDCl 3 ) and 13 C-NMR (150 MHz, CDCl 3 ) spectral data are listed in Table 1 .
X-ray Crystallographic Analysis of Compound 1. C 21 H 24 O 5 , molecular weight ( M w) = 356.40, orthorhombic, space group P 2 1 2 1 2 1 , a = 8.8900 (12) Å, b = 9.7794 (8) Å, c = 21.473 (3) Å, α = b = γ = 90°, V = 1866.9 (4) Å 3 , Z = 4, D c = 1.268 mg/m 3 , μ (Mo Kα) = 0.090 mm −1 , F (000) = 760, and T = 292 K, crystal dimensions 0.35 × 0.31 × 0.11 mm was selected for X-ray analysis. The reflection data were collected on an Agilent Technologies SuperNova, Dual source, EOS CCD with mirror optics, using graphite-monochromated Mo-K a radiation (λ = 0.7107 Å). A total of 3310 reflections were collected in the range 3.0° ≤ θ ≤ 25.7°, of which 2108 unique reflections with I > 2σ (I) were collected for the analysis. The structure was solved by direct methods using SHELXS97 and refined by full matrix least-squares on F 2 . The final R and R W factors were 0.060 and 0.128, respectively.
Acknowledgements
Supporting Information.The spectral data of compound1are available on request from the correspondence author.
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