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Diterpenoids from Leonurus japonicus

  • Wu, Hankui (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Wang, Sensheng (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Liu, Haijuan (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Yan, E. (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Wang, Jinjin (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Wang, Xiangbei (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Wei, Wenchao (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Xu, Zhiyong (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Sun, Shanshan (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Li, Yan (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Liu, Ruijin (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Li, Gang (College of Chemistry and Chemical Engineering, Anyang Normal University) ;
  • Shi, Yunfeng (College of Chemistry and Chemical Engineering, Anyang Normal University)
  • 투고 : 2014.12.11
  • 심사 : 2015.01.21
  • 발행 : 2015.04.20

초록

키워드

EXPERIMENTAL

Reagents and Instruments

NMR spectra were recorded on a Bruker Avance III spectrometer operating at 400 MHz for 1H and 100 MHz for 13C. HRESIMS were measured with Waters UPLC-LCT Premier XE and was controlled by MassLynx 4.1 software. Optical rotations were acquired with a WZZ-2ss automatic polarimeter (Shanghai Shenguang High Strength Bolts Co., Ltd, China). Column chromatography was performed with silica gel (200-300 mesh, Yantai Institute of Chemical Technology, Yantai, China), Sephadex LH-20 (GE Healthcare). HPLC separation was performed on an instrument (LC-3000, Beijing Chuangxintongheng Science & Technology Co., Ltd, Beijing China) consisting of two pumps and a UV/Vis detector with an YMC-ODS-A (25×1 cm) semi-preparative column packed with C18 (5 μm). All organic solutions used were of analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Methanol used for HPLC was of HPLC-grade and purchased from Fisher Scientific Company (Fair Lawn, NJ, USA).

Plant Material

The herb of L. japonicus was purchased from Zhangye, Gansu Province of China in March, 2014. It was identified by one of the authors (Dr. H. Wu). A voucher specimen (Code: hkwu-aynu-20140301) was deposited at the Pharmaceutical Research Lab, Anyang Normal University.

Extraction and Isolation

The dried and powdered herb of L. japonicus (85 kg) was extracted with 95% EtOH (3 × 400 L) by percolation at room temperature. The solvent was evaporated under reduced pressure at 45 ℃ to yield 7.2 kg viscous syrup, which was dissolved in water and extracted with EtOAc to get 3 kg extract. The EtOAc fraction was suspended in 30% EtOH and allowed to pass through a column (30 cm × 100 cm) packed with AB-8 macroporous resin (10 kg), then eluted with 50%, 70%, 90%, and 95% EtOH to obtain fractions A-D. Fraction C (693 g) was separated by silica gel CC over petroleum ether-EtOAc (10:1) to get subfraction C1. The further separation of C1 with Sephadex LH-20 (MeOH) to yield a mixture rich in diterpenes (total diterpenoids). The total diterpenoids sample was purified by preparative HPLC. The mobile phase was a linear gradient of methanol (A) and H2O (B) as follows: methanol-water (methanol: 0−20 min, 85−98%; 20−22 min, 95−85%; 22−27 min, 85%). The flowrate was 4.0 ml min−1, the injection volume was 200 mL for each run and the effluent was monitored at 215 nm by a UV detector. Peaks were collected manually, and the retention times for the isolates were 7.4 min (1, 15 mg), 9.3 min (3, 46 mg), 10.4 min (4, 35 mg), 12.7 min (5, 27 mg), and 15.1 min (2, 18 mg) respectively. Identification of the HPLC peak fractions was performed by HRESIMS, 1H and 13C NMR, HMBC and HMQC technologies. The typical HPLC graph was shown in Fig. 4.

Figure 4.HPLC separation of compounds 1−5.

Supporting Information. The 1H and 13C NMR, DEPT, HMQC, and HMBC spectra measured in CDCl3 of new compounds 1−2 are provided.

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피인용 문헌

  1. Structurally Diverse Labdane Diterpenoids from Leonurus japonicus and Their Anti-inflammatory Properties in LPS-Induced RAW264.7 Cells vol.83, pp.9, 2015, https://doi.org/10.1021/acs.jnatprod.9b00597