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A New Halimane Diterpenoid from Croton crassifolius

  • Zhang, Zhan-Xin (School of Pharmacy, Lanzhou University) ;
  • Li, Hui-Hong (School of Pharmacy, Lanzhou University) ;
  • Qi, Feng-Ming (State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University) ;
  • Xiong, Hui-Yan (Agriculture and Animal Husbandry College, Qinghai University) ;
  • Dong, Le-Le (School of Pharmacy, Lanzhou University) ;
  • Fan, Gai-Xia (School of Pharmacy, Lanzhou University) ;
  • Fei, Dong-Qing (School of Pharmacy, Lanzhou University)
  • Received : 2013.12.09
  • Accepted : 2014.01.13
  • Published : 2014.05.20

Abstract

Keywords

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 GF254 (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% H2SO4 in C2H5OH (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 H2O 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 (CHCl3-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; –20° (c 0.1, CHCl3); UV (CH3OH) λmax (log ε) 216.2 (3.69) nm; IR (KBr) νmax 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 C21H25O5, 357.1697); 1H-NMR (600 MHz, CDCl3) and 13C-NMR (150 MHz, CDCl3) spectral data are listed in Table 1.

X-ray Crystallographic Analysis of Compound 1. C21H24O5, molecular weight (Mw) = 356.40, orthorhombic, space group P212121, a = 8.8900 (12) Å, b = 9.7794 (8) Å, c = 21.473 (3) Å, α = b = γ = 90°, V = 1866.9 (4) Å3, Z = 4, Dc = 1.268 mg/m3, 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-Ka 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 F2. The final R and RW factors were 0.060 and 0.128, respectively.

References

  1. Asare, G. A.; Sittie, A.; Bugyei, K.; Gyan, B. A.; Adjei, S.; Addo, P.; Wiredu, E. K.; Nyarko, A. K.; Out-Nyarko, L. S.; Adjei, D. N. J. Ethnopharmacol. 2011, 134, 938. https://doi.org/10.1016/j.jep.2011.02.004
  2. McChesney, J. D.; Silveira, E. R. Phytochemistry 1989, 28, 3411. https://doi.org/10.1016/0031-9422(89)80358-9
  3. Cai, Y.; Chen, Z. P. Phytochemistry 1993, 34, 265. https://doi.org/10.1016/S0031-9422(00)90816-1
  4. Block, S.; Baccelli, C.; Tinant, B.; Meervelt, L. C.l; Rozenberg, R.; Jiwan, H. J.; Llabres, G.; Pauw-Gillet, D. M.; Quetib-Leclercq, J. Phytochemistry 2004, 65, 1165. https://doi.org/10.1016/j.phytochem.2004.02.023
  5. Kuo, P. C.; Shen, Y. C.; Yang, M. L.; Wang, S. H.; Thang, T. D.; Dung, W. X.; Chiang, P. C.; Lee, K. H.; Lee, E. J.; Wu, T. S. J. Nat. Prod. 2007, 70, 1906. https://doi.org/10.1021/np070383f
  6. Pudhom, K.; Vilaivan, T.; Ngamrojanavanich, N.; Dechangvipart, S.; Sommit, D.; Petsom, A.; Roengsumran, S. J. Nat. Prod. 2007, 70, 659. https://doi.org/10.1021/np060520t
  7. Institute of Botany, Chinese Academy of Science Flora Republicae Popularis Sinicae; Science Press: Beijing, China, 1996, 44(2), 130.
  8. Jiangsu College of New Medicne A Dictionary of the Traditional Chinese Medicines; Shanghai Science and Technology Press: Shanghai, China, 1977; p 1210.
  9. Boonyarathanakornkit, L.; Che, C. T.; Fong, H. H. S.; Farnsworth, N. R. Planta Med. 1998, 54, 61.
  10. Boonyaratavej, S.; Roengsumran, S.; Bates, R. B.; Ortega, R. B.; Petsom, A. J. Nat. Prod. 1988, 51, 769. https://doi.org/10.1021/np50058a019
  11. Yang, X. H.; Chen, S. W.; Deng, S. M. Shizhen Guoyi Guoyao 2009, 20, 515.
  12. Wang, G. C.; Li, J. G.; Li, G. Q.; Xu, J. J.; Wu, X.; Ye, W. C.; Li, Y. L. J. Nat. Prod. 2012, 75, 2188. https://doi.org/10.1021/np300636k
  13. Hu, Y.; Zhang, L.; Wen, X. Q.; Zeng, X. J.; Rui, W.; Cen, Y. Z. J. Asian Nat. Prod. Res. 2012, 14, 785. https://doi.org/10.1080/10286020.2012.694872
  14. Fei, D. Q.; Zhang, Z. X. Chin. Chem. Lett. 2009, 20, 949. https://doi.org/10.1016/j.cclet.2009.04.009
  15. Zhang, Z. X.; Fei, D. Q. J. Asian Nat. Prod. Res. 2009, 11, 958. https://doi.org/10.1080/10286020903264093
  16. Marcos, I. S.; Hernandez, F. A.; Sexmero, M. J.; Diez, D.; Basabe, P.; Pedrero, A. B.; Garcia, N.; Urones, J. G. Tetrahedron 2003, 59, 685. https://doi.org/10.1016/S0040-0(02)01564-8
  17. Krebs, H. S.; Ramiarantsoa, H. Phytochemistry 1996, 41, 561. https://doi.org/10.1016/0031-9422(95)00624-9
  18. Peres, M. T. L. P.; Pizzolatti, M. G.; Yunes, R. A.; Monache, F. D. Phytochemistry 1998, 49, 171. https://doi.org/10.1016/S0031-9422(97)00873-X
  19. Kanlayavattanakul, M.; Ruangrungsi, N.; Watanabe, T.; Kawahata, M.; Therrien, B.; Yamaguchi, K.; Ishikawa, T. J. Nat. Prod. 2005, 68, 7. https://doi.org/10.1021/np049877s

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