Chemical Constituents of Callicarpa macrophylla
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CHEMICAL CONSTITUENTS OF Callicarpa macrophylla
Zhen-Hui Wang,1 Qiang Li,1 Mei Huang,1 Peng-Fei Xu,2 Lan-Ping Yang,1 Yang-Yang Zhai,1 Zhen-Zhen Zhang,1 Wen-Kui Zhang,1 Chao Niu,1* and Hui Wang3*
Callicarpa macrophylla Vahl belongs to the Callicarpa L. genus of the Verbenaceae family and is used as a folk medicine in Yunnan, including the roots, stems, and leaves. It is widely distributed in Guangdong, Guangxi, Guizhou, and Yunnan Provinces of China and grow at an altitude of 110–2000 m on hilly roads, sparse forests, or thickets [1]. Callicarpa macrophylla Vahl has a bitter taste, slightly acrid or flat, with clinical actions that eliminate stasis to promote blood circulation and stop bleeding, and it also has detumescence and analgesic actions [1]. Previous investigations on this genus have reported diterpenoids, triterpenoids, flavonoids, phenolic acids, volatile oils, and so on [2–5]. In our continuous effort to explore potentially active ingredients from this plant, 13 compounds, including five diterpenes (1–5) and eight flavonoids (6–13), were investigated. This is the first report of compounds 3, 10, and 12 from the genus Callicarpa, and compounds 1, 2, 4, 5, 7–9, and 11 from the family Verbenaceae. Extraction and Isolation. Dried whole herb of Callicarpa macrophylla Vahl (4.5 kg) was extracted with 50 L 95% EtOH (× 3) under reflux conditions for 3 h to give a crude extract, which was suspended in H2O and successively extracted with petroleum ether (PE), CHCl3, and EtOAc to yield a PE-soluble fraction (17.2 g), a CHCl3-soluble fraction (261.7 g), and an EtOAc-soluble fraction (55.3 g). A part of the CHCl3-soluble fraction (70 g) was subjected to column chromatography (CC, silica gel, gradient of PE–acetone, 100:1–0:100) to afford 46 fractions (Frs. 1–46). Fractions 25–29 (3.6 g) were separated by CC (ODS, MeCN–H2O, 45:55, MeCN–H2O, 60:40) to yield fraction ods50, which was further subjected to semipreparative reversed-phase HPLC (MeOH–H2O with 0.2% HCO2H (62:38) as mobile phase, flow rate 3.0 mL/min, wavelength 203 nm) to afford compounds 1–7. Fractions 40–44 (4.7 g) were separated by CC (ODS, MeCN–H2O, 30:70, MeCN–H2O, 40:60) to yield fraction ods35–45, which was further subjected to semipreparative reversed-phase HPLC (MeOH–H2O with 0.2% HCO2H (73:27) as mobile phase, flow rate 3.0 mL/min, wavelength 203 nm) to afford compounds 8–13. Compounds 1–13 were identified as 14α,18-dihydroxy-7,15-isopimaradiene (1), isopimaradiene-3β,18-diol (2), 14α-hydroxyisopimaric acid (3), 7α-hydroxysandaracopimaric acid (4), 8(14),15-sandaracopimaradiene-7α,18-diol (5), 5-hydroxy-3′,4′,3,7-tetramethoxyflavone (6), 3,5-dihydroxy-3′,4′,7-trimethoxyflavone (7), 5,7-dihydroxy-3′,4′,3trimethoxyflavone (8), 3′,4′,5-trihydroxy-3,7-dimethoxyflavone (9), 5,4′-dihydroxy-7-methoxyflavone (10), 3,5,7-trihydroxy4′-methoxyflavone (11), naringenin (12), and 5,4′-dihydroxy-7,3′-dimethoxyflavone (13). 14α,18-Dihydroxy-7,15-isopimaradiene (1). White flaky crystals. 1H NMR (600 MHz, CDCl3, δ, ppm, J/Hz): 0.88 (3H, s, CH3-20), 0.88 (3H, s, CH3
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