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Species belonging to the genus Michelia are arboreous plants, growing in temperate zones of oriental India, southern China, Malaysia, and Indonesia. The species most utilized is Michelia champaca: its cortex and seeds are used as febrifuge and tonic-aromatic; the roots are employed as emmenagogue, the leaves as astringent, the gemmae in the treatment of hemorrhage, and the flowers and fruits are believed to possess curative properties in enteritis [1]. The less known species, M. figo, is used as ornamental plants and to obtain essences [1]. M. figo is an evergreen medium shrub, commonly called banana shrub, because of the heavy, sweet fragrant banana scent of its purple flowers. The plant is also known in Indian folk medicine as a remedy against hypertension [2]. To further understand the chemotaxonomy of the Michelia species [3,4,5,6,7], M. figo was chosen for phytochemical investigation. The chemical constituents of the leaves of this plant have not yet been reported. The compounds derived from the leaves include three alkaloids, (–)-nuciferine (1) [8], (–)-anonaine (2) [9], and N-methylcorydaldine (3) [10]; two steroids, β-sitostenone (4) [9] and stigmasta-4,22-dien-3-one (5) [9]; four benzenoids, p-hydroxybenzaldehyde (6) [10], p-hydroxybenzoic acid (7) [11], methylparaben (8) [11], and vanillin (9) [11]; six chlorophylls, pheophytin a (10) [12], pheophorbide a (11) [12], pheophytin b (12) [13], pheophorbide b (13) [13], aristophyll-C (14) [14], 132-hydroxy-(132-S)- pheophytin a (15) [15]; and one sesquiterpene lactone, 11,13-dehydrolanuginolide (16) [16]. All of these known compounds were obtained for the first time from the leaves of this plant and were identified by direct comparison with authentic samples (TLC, UV, IR, ESI-MS and NMR) and the literature [8,9,10,11,12,13,14,15,16].
The leaves of M. figo (Lour.) Spreng. were collected from Chiayi County, Taiwan, May 2011. Plant material was identified by Prof. Fu-Yuan Lu (Department of Forestry and Natural Resources, College of Agriculture, National Chiayi University). A voucher specimen (Michelia 5) was deposited in the School of Medicinal and Health Sciences, Fooyin University, Kaohsiung City, Taiwan. The air-dried leaves of M. figo (4.8 kg) were extracted with MeOH (6 L × 4) at room temperature, and a MeOH extract (121.6 g) was obtained upon concentration under reduced pressure. The MeOH extract, suspended in H2O (1 L), was partitioned with CH2Cl2 (3 L × 5) to give fractions soluble in CH2Cl2 (67.9 g) and H2O. The CH2Cl2-soluble fraction was chromatographed over silica gel (950 g, 70–230 mesh) using n-hexane–EtOAc–MeOH mixtures as eluents to give five fractions. Part of fraction 1 (8.24 g) was subjected to silica gel chromatography by eluting with n-hexane–EtOAc (60:1) and enriched gradually with EtOAc to furnish five fractions (1-1–1-5). Fraction 1-2 (3.11 g) was further purified on a silica gel column using n-hexane–EtOAc mixtures to obtain 4 (12 mg) and 5 (6 mg). Part of fraction 2 (11.78 g) was subjected to silica gel chromatography by eluting with n-hexane–EtOAc (60:1) and enriched gradually with EtOAc to furnish five fractions (2-1–2-5). Fraction 2-1 (2.78 g) was further purified on a silica gel column using n-hexane–EtOAc mixtures to obtain 10 (3 mg) and 11 (4 mg). Fraction 2-2 (2.17 g) was further purified on a silica gel column using n-hexane–EtOAc mixtures to obtain 12 (1 mg) and 13 (2 mg). Fraction 2-3 (2.86 g) was further purified on a silica gel column using n-hexane–EtOAc mixtures to obtain 14 (13 mg) and 15 (9 mg). Fraction 2-4 (1.55 g) was further purified on a silica gel column using n-hexane–EtOAc mixtures to obtain 16 (18 mg). Part of fraction 3 (16.97 g) was subjected to silica gel chromatography by eluting with n-hexane–EtOAc (40:1) and enriched with EtOAc to furnish six further fractions (3-1–3-6). Fraction 3-3 (4.24 g) was further purified on a silica gel column using CH2Cl2–MeOH mixtures to obtain 3 (7 mg). Fraction 3-4 (3.24 g) was further purified on a silica gel column using CH2Cl2–MeOH mixtures to obtain 2 (19 mg) and (–)-nuciferine (2 mg). Part of fraction 4 (21.23 g) was subjected to silica gel chromatography by eluting with CH2Cl2–MeOH (40:1) and enriched with MeOH to furnish four fractions (4-1–4-4). Fraction 4-2 (16.72 g) eluted with CH2Cl2–MeOH (40:1) was further separated using silica gel column chromatography and preparative TLC (CH2Cl2–MeOH (50:1)) to give 6 (17 mg),7 (22 mg), and 8 (13 mg). Part of fraction 5 (16.12 g) was subjected to silica gel chromatography by eluting with CH2Cl2–MeOH (40:1) and enriched with MeOH to furnish four fractions (5-1–5-4). Fraction 5-3 (5.31 g) eluted with CH2Cl2–MeOH (40:1) was further separated using silica gel column chromatography and preparative TLC (CH2Cl2–MeOH (45:1)) to give 9 (14 mg).
(–)-Nuciferine (1). C19H21NO2, brown powder (MeOH), mp 164–166°C. UV (λmax, nm): 230, 274, 312. IR (νmax, cm–1): 1250, 1375, 1425, 1500, 1605. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 2.71–3.15 (4H, m, H-4, 5), 3.65 (3H, s, 1-OCH3), 3.88 (3H, s, 2-OCH3), 6.62 (1H, s, H-3), 7.23–7.26 (3H, m, H-8, 9, 10), 8.35 (1H, d, J = 7.6, H-11). ESI-MS m/z 319 [M + Na + H]+ [8].
(–)-Anonaine (2). C17H15NO2, pale yellow powder (MeOH), mp 121–123°C. UV (λmax, nm): 230, 272, 310. IR (νmax, cm–1): 950, 1040. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 2.65 (1H, t, J = 13.4, H-7a), 2.85 (1H, dd, J = 13.4, 5.2, H-7b), 3.11–3.29 (3H, m, H-4a, 4b, 5a), 3.53 (1H, m, H-5b), 3.98 (1H, dd, J = 13.4, 5.2, H-6a), 5.92, 6.06 (each 1H, d, J = 1.6, OCH2O), 6.55 (1H, s, H-3), 7.21–7.30 (3H, m, H-8, 9, 10), 8.06 (1H, d, J = 7.6, H-11). ESI-MS m/z 289 [M + Na + H]+ [9].
N -Methylcorydaldine (3). C11H15NO3, colorless crystals (CHCl3), mp 112–113°C. UV (λmax, nm): 200, 219, 263, 303. IR (νmax, cm–1): 1612, 1656. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 2.93 (2H, t, J = 6.8, H-4), 3.12 (3H, s, N-CH3), 3.56 (2H, t, J = 6.8, H-3), 3.92 (3H, s, 6-OCH3), 3.93 (3H, s, 7-OCH3), 6.58 (1H, s, H-5), 7.41 (1H, s, H-8). ESI-MS m/z 245 [M + Na + H]+ [10].
β -Sitostenone (4). C29H48O, white needles (CHCl3), mp 85–86°C. IR (νmax, cm–1): 1375, 1385, 1460, 1620, 1675. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 0.68 (3H, s, H-18), 0.81 (3H, d, J = 6.7, H-26), 0.84 (3H, s, H-27), 0.86 (3H, t, J = 7.1, H-29), 0.92 (3H, d, J = 6.0, H-21), 1.02 (3H, s, H-19), 5.72 (1H, d, J = 1.4, H-3). EI-MS m/z 414 [M]+ [9].
Stigmasta-4,22-dien-3-one (5). C29H46O, white needles (CHCl3), mp 135–136°C. IR (νmax, cm–1): 1375, 1385, 1460, 1620, 1675. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 0.68 (3H, s, H-18), 0.81 (3H, d, J = 6.7, H-26), 0.84 (3H, s, H-27), 0.86 (3H, t, J = 7.1, H-29), 0.93 (3H, d, J = 6.0, H-21), 1.02 (3H, s, H-19), 5.02 (1H, dd, J = 16.1, 8.3, H-22), 5.12 (1H, dd, J = 16.1, 8.3, H-23), 5.72 (1H, d, J = 1.4, H-3). EI-MS m/z 412 [M]+ [9].
p -Hydroxybenzaldehyde (6). C7H6O2, brown powder (CHCl3). UV (λmax, nm): 223, 285, 290. IR (νmax, cm-1): 3200, 1660, 1600, 1155, 826. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 6.92 (2H, d, J = 8.4, H-3, 5), 7.80 (2H, d, J = 8.4, H-2, 6), 9.87 (1H, s, CHO). ESI-MS m/z 146 [M + Na + H]+ [10].
p -Hydroxybenzoic Acid (7). C7H6O3, brown powder (CHCl3). UV (λmax, nm): 250, 285, 290. IR (νmax, cm–1): 3500, 1660, 1590, 1165, 845. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 6.85 (2H, d, J = 8.6, H-3, 5), 7.96 (2H, d, J = 8.6, H-2, 6). ESI-MS m/z 162 [M + Na + H]+ [11].
Methylparaben (8). C8H8O3, colorless needles (CHCl3), mp 130–131°C. UV (λmax, nm): 225, 256, 310. IR (νmax, cm–1): 3400, 2950, 1695, 1610. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 3.88 (3H, s, COOCH3), 5.46 (1H, br.s, OH), 6.87 (2H, d, J = 8.8, H-3, 5), 7.96 (2H, d, J = 8.8, H-2, 6). ESI-MS m/z 176 [M + Na + H]+ [11].
Vanillin (9). C8H8O3, yellow powder (CHCl3). UV (λmax, nm): 220, 280, 310. IR (νmax, cm–1): 3400, 1670, 1595, 1025. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 3.95 (3H, s, 3-OCH3), 6.20 (1H, br.s, OH), 7.09 (1H, d, J = 8.0, H-5), 7.31 (1H, d, J = 2.0, H-2), 7.42 (1H, dd, J = 8.0, 2.0, H-6), 9.77 (1H, s, CHO). ESI-MS m/z 176 [M + Na + H]+ [11].
Pheophytin a (10). C55H74N4O5, deep green needles (CHCl3), mp 113–114°C. UV (λmax, nm): 229, 274, 330, 372, 406, 508, 540, 610, 665. IR (νmax, cm–1): 3400, 1740, 1700, 1620. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –1.62 (1H, br.s, NH, D2O exchangeable), 0.81, 0.83 (each 3H, d, J = 6.6, H-38, 39), 0.87 (6H, d, J = 6.6, H-36, 37), 1.60 (3H, s, H-40), 1.01–1.10 (21H, m, H-24–35), 1.64 (3H, t, J = 7.6, H-82), 2.22 (1H, m), 2.32 (1H, m), 2.54 (1H, m), 2.65 (1H, m), 3.22, 3.42 (each 3H, s, H-71, 21), 3.54 (2H, q, J = 7.6, H-81), 3.72, 3.88 (each 3H, s, H-121, OCH3), 4.22 (1H, m, H-17), 4.48 (2H, m, H-18), 4.49 (1H, d, J = 7.2, H-21), 5.16 (1H, t, J = 7.4, H-22), 6.19 (1H, d, J = 11.6, H-32), 6.30 (1H, d, J = 17.8, H-32), 6.28 (1H, s, H-132), 8.00 (1H, dd, J = 17.8, 11.4, H-31), 8.57, 9.39, 9.52 (each 1H, s, H-20, 5, 10). FAB-MS m/z 871 [M + H]+ [12].
Pheophorbide a (11). C35H36N4O5, deep green needles (CHCl3), mp 115–116°C. UV (λmax, nm): 229, 274, 330, 372, 408, 506, 536, 608, 665. IR (νmax, cm–1): 3400, 1740, 1700, 1620. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –1.63 (1H, br.s, NH, D2O exchangeable), 1.64 (3H, t, J = 7.6, H-82), 2.22 (1H, m), 2.35 (1H, m), 2.50 (1H, m), 2.65 (1H, m), 3.22, 3.40 (each 3H, s, H-71, 21), 3.52 (2H, q, J = 7.6, H-81), 3.70, 3.88 (each 3H, s, H-121, OCH3), 4.22 (1H, m, H-17), 4.47 (2H, m, H-18), 6.17 (1H, d, J = 11.4, H-32), 6.28 (1H, s, H-132), 6.30 (1H, d, J = 17.8, H-32), 8.00 (1H, dd, J = 17.8, 11.4, H-31), 8.57, 9.39, 9.52 (each 1H, s, H-20, 5, 10). FAB-MS m/z 593 [M + H]+ [12].
Pheophytin b (12). C55H72N4O6, deep green needles (CHCl3), mp 118–119°C. UV (λmax, nm): 233, 280, 330, 411, 435, 536, 608, 665. IR (νmax, cm–1): 3500, 1730, 1700, 1665, 1616. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –1.49 (1H, br.s, NH, D2O exchangeable), 0.77 (3H, d, J = 6.4, H-38), 0.78 (3H, d, J = 6.4, H-39), 0.83 (6H, d, J = 6.6, H-36, 37), 1.58 (3H, s, H-40), 1.00–1.90 (21H, m, H-24–35), 1.63 (3H, t, J = 7.6, H-82), 2.21 (1H, m), 2.35 (1H, m), 2.50 (1H, m), 2.64 (1H, m), 3.38 (3H, s, H-21), 3.69 (3H, s, H-71), 3.88 (2H, q, J = 7.6, H-81), 3.90 (3H, s, OCH3), 4.07 (1H, m, H-17), 4.45 (2H, m, H-18), 4.53 (2H, m, H-21), 5.14 (1H, t, J = 7.2, H-22), 6.21 (1H, d, J = 11.6, H-32), 6.23 (1H, s, H-132), 6.37 (1H, d, J = 17.8, H-32), 8.01 (1H, dd, J = 17.8, 11.6, H-31), 8.54, 9.66, 10.38 (each 1H, s, H-20, 5, 10), 11.01 (1H, s, CHO). FAB-MS m/z 885 [M + H]+ [13].
Pheophorbide b (13). C35H34N4O6, deep green needles (CHCl3), mp 118–119°C. UV (λmax, nm): 233, 280, 330, 411, 435, 536, 608, 665. IR (νmax, cm–1): 3500, 1730, 1700, 1665, 1616. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –1.49 (1H, br.s, NH, D2O exchangeable), 1.63 (3H, t, J = 7.6, H-82), 2.21 (1H, m), 2.35 (1H, m), 2.50 (1H, m), 2.64 (1H, m), 3.38 (3H, s, H-21), 3.69 (3H, s, H-71), 3.88 (2H, q, J = 7.6, H-81), 3.90 (3H, s, OCH3), 4.07 (1H, m, H-17), 4.45 (2H, m, H-18), 6.21 (1H, d, J = 11.6, H-32), 6.23 (1H, s, H-132), 6.37 (1H, d, J = 17.8, H-32), 8.01 (1H, dd, J = 17.8, 11.6, H-31), 8.54, 9.66, 10.38 (each 1H, s, H-20, 5, 10), 11.01 (1H, s, CHO). FAB-MS m/z 607 [M + H]+ [13].
Aristophyll-C (14). C53H70N4O5, deep green needles (CHCl3), mp 247–248°C. UV (λmax, nm): 282, 360, 412, 480, 512, 550, 642, 702. IR (νmax, cm–1): 1740, 1725. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –0.18, 0.12 (each 1H, br.s, NH, D2O exchangeable), 0.78, 0.80 (each 3H, d, J = 7.0, H-38, 39), 0.83 (6H, d, J = 6.8, H-36, 37), 1.01–1.62 (21H, m), 1.62 (3H, s, H-40), 1.66 (3H, t, J = 7.6, H-82), 1.75 (3H, d, J = 7.0, H-181), 2.04 (1H, m, H-171), 2.45 (2H, m, H-171, 172), 2.73 (1H, m, H-172), 3.15 (3H, s, CH3-7), 3.37 (3H, s, CH3-2), 3.62 (2H, q, J = 7.6, H-81), 3.75 (3H, s, CH3-12), 4.36 (1H, q, J = 7.0, H-18), 4.52 (2H, m, H-21), 5.22 (2H, m, H-17, 22), 6.22 (1H, d, J = 11.4, H-32), 6.30 (1H, d, J = 18.0, H-32), 7.89 (1H, dd, J = 18.0, 11.5, H-31), 8.56, 9.40, 9.56 (each 1H, s, H-20, 5, 10). FAB-MS m/z 843 [M + H]+ [14].
13 2 -Hydroxy-(13 2 - S )-pheophytin a (15). C55H74N4O6, deep green needles (CHCl3), mp 205–206°C. UV (λmax, nm): 225, 410, 505, 611, 665. IR (νmax, cm–1): 3400, 1740, 1700, 1620. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): –1.82 (1H, br.s, NH, D2O exchangeable), 0.77, 0.78 (each 3H, d, J = 6.4, H-38, 39), 0.83 (3H, d, J = 6.4, H-36), 0.86 (3H, d, J = 6.4, H-37), 1.60 (3H, s, H-40), 1.62 (3H, d, J = 7.4, H-181), 2.21–2.34 (2H, m), 2.56 (1H, m), 2.93 (1H, m), 3.27, 3.43 (each 3H, s, H-71, 21), 3.61 (3H, s, H-121, OCH3), 3.75 (3H, s, H-134, OCH3), 4.16 (1H, m, H-17), 4.52 (2H, m, H-18), 4.57 (1H, d, J = 7.2, H-21), 5.20 (1H, t, J = 7.2, H-22), 6.20 (1H, d, J = 11.6, H-32), 6.30 (1H, d, J = 17.8, H-32), 8.03 (1H, dd, J = 17.8, 11.6, H-31), 8.64, 9.50, 9.63 (each 1H, s, H-20, 5, 10). FAB-MS m/z 887 [M + H]+ [15].
11,13-Dehydrolanuginolide (16). C17H22O5, colorless needles (MeOH), mp 168–170°C. UV (λmax, nm): 210. IR (νmax, cm–1): 1770, 1655. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 1.29 (3H, s, H-15), 1.84 (3H, s, H-14), 3.30 (1H, dd, J = 7.2, 3.6, H-7), 4.32 (1H, dd, J = 9.2, 6.8, H-6), 4.60 (1H, m, H-8), 5.33 (1H, m, H-1), 5.80, 6.43 (each 1H, d, J = 3.4, H-13). ESI-MS m/z 330 [M + Na + H]+ [16].
References
C. T. Huang, S. J. Chen, H. M. Wu, Y. F. Kang, H. L. Chen, W. J. Li, H. T. Li, and C. Y. Chen, Chem. Nat. Compd., 50, 1047 (2014).
S. Chericoni, L. Testai, E. Campeol, V. Calderone, I. Morelli, and E. Martinotti, J. Ethnopharmacol., 91, 263 (2004).
W. L. Lo, L. Y. Huang, H. M. Wang, and C. Y. Chen, Chem. Nat. Compd., 46, 664 (2010).
H. M. Wang, W. L. Yang, S. C. Yang, and C. Y. Chen, Chem. Nat. Compd., 46, 327 (2010).
M. J. Cheng, W. L. Lo, J. C. Huang, Y. T. Yeh, Z. L. Hong, Y. C. Lu, M. S. Chang, and C. Y. Chen, Nat. Prod. Res., 24, 682 (2010).
W. L. Lo, J. C. Huang, L. Y. Huang, and C. Y. Chen, Nat. Prod. Res., 24, 326 (2010).
C. Y. Chen, L. Y. Huang, L. J. Chen, W. L. Lo, S. Y. Kuo, Y. D. Wang, S. H. Kuo, and T. J. Hsieh, Chem. Nat. Compd., 44, 137 (2008).
H. Guinaudeau, A. Cave, and R. R. Paris, Phytochemistry, 10, 1963 (1971).
C. Y. Chen, F. R. Chang, and Y. C. Wu, J. Chin. Chem. Soc., 44, 313 (1997).
A. K. Sinha, S. C. Verma, and U. K. Sharma, J. Sep. Sci., 30, 15 (2007).
C. Y. Chen, F. R. Chang, C. M. Teng, and Y. C. Wu, J. Chin. Chem. Soc., 46, 77 (1999).
J. S. Walkera, A. H. Squiera, D. A. Hodgsonb, and B. J. Keelya, Org. Geochem., 33, 1667 (2002).
Y. Nakatani, G. Ourisson, and J. P. Beck, Chem. Pharm. Bull., 29, 2261 (1981).
Y. Y. Chan, Y. L. Leu, and T. S. Wu, Chem. Pharm. Bull., 47, 887 (1999).
L. Ma and D. Dolphin, J. Org. Chem., 61, 2501 (1996).
S. K. Talapatra, A. Patra, and B. Talapatra, Phytochemistry, 12, 1827 (1973).
Acknowledgment
This investigation was supported by a grant from the Ministry of Science and Technology of the Republic of China (MOST-104-2320-B-0242- 001-MY3) awarded to C. Y. Chen.
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Published in Khimiya Prirodnykh Soedinenii, No. 2, March–April, 2018, pp. 343–345.
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Chen, H.C., Kao, C.L., Chen, C.T. et al. Chemical Constituents of the Leaves of Michelia figo. Chem Nat Compd 54, 407–410 (2018). https://doi.org/10.1007/s10600-018-2364-5
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DOI: https://doi.org/10.1007/s10600-018-2364-5