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The characteristic components of the Ainsliaea (Compositae) genus are sesquiterpenes (especially eudesmanolide and guaianolide) [1–4]. Ainsliaea macrocephala Y.C. Tseng, a plant of Ainsliaea, is distributed mainly in the southwest of China. The whole plant of A. macrocephala has been used in Chinese folk medicine to treat rheumatism, lumbago, and gonitis [5]. Some chemical constituents of this plant have been reported previously [6–8]. In our continuing investigation of this plant, we now report 27 compounds isolated from the whole plant of A. macrocephala.
The whole plant of A. macrocephala were collected in Lijing, Yunnan province, China and authenticated as A. macrocephala by Prof. Li-Shang Xie of Kunming Institute of Botany, Chinese Academy of Sciences. A voucher specimen is deposited in the Herbarium of the School of Pharmacy, Second Military Medical University.
The whole air-dried plant of A. macrocephala (12 kg) was refluxed with alcohol for 3 × 2 h; then the alcohol extract was concentrated in vacuo to an aqueous residue, which was extracted successively with petroleum ether, EtOAc, and n-BuOH. Each fraction was purified by column chromatography with silica gel and Sephadex LH-20 or RP-18 to yield compounds 1–27.
The compounds were analyzed by spectroscopic methods, including NMR and mass spectrometry. All 27 compounds were determined as 4-hydroxybenzaldehyde (1) [9], linoleic acid (2) [10], gochnatiolide A (3) [11], betulin (4) [12], cholest-4-en-3-one (5) [13], (20Z)-cholest-5,20(22)-dien-3β-ol (6) [14], 4-hydroxyacetophenone (7) [15], vanillin (8) [16], protocatechualdehyde (9) [17], dihydrodehydrodiconiferyl alcohol (10) [18], secoisolariciresinol (11) [19], caffeic acid (12) [20], tianshic acid (13) [21], methyl 3-O-caffeoylquinate (14) [22], methyl 3,4-O-dicaffeoylquinate (15) [23], picein (16) [24], 2-isopropyl-5-methylphenol-O-β-D-glucopyranoside (17) [25], zataroside-A (18) [26], 4-allyl-2,6-dimethoxyphenol-β-Dglucoside (19) [27], phenylethyl-O-β-D-glucopyranoside (20) [28], 2-O-methyl-α-D-fructofuranoside (21) [29], 6-O-methyl-α-D-fructofuranoside (22) [30], ethyl-α-D-fructofuranoside (23) [30], methyl-β-D-fructopyranoside (24) [30], adenosine (25) [31], daucosterol (26) [32], and 4-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranosyl acetophenone (27) [33]. All these compounds were isolated from A. macrocephala for the first time.
Gochnatiolide A (3). White powder. ESI-MS m/z 526 [M + Na]+. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 6.26 (1H, d, J = 3.2, H-13a′), 6.17 (1H, br.s, H-15a), 6.16 (1H, d, J = 3.2, H-13a), 5.98 (1H, br.s, H-15b), 5.63 (1H, d, J = 2.8, H-13b′), 5.46 (1H, d, J = 3.2, H-13b), 5.07 (1H, br.s, H-14a′), 4.68 (1H, br.s, H-14b′), 4.24 (1H, t, J = 9.6, H-6′), 3.89 (1H, br.s, H-5), 3.87 (1H, br.s, H-7), 3.72 (1H, t, J = 10.0, H-6), 3.35 (1H, m, H-2a′), 3.32 (1H, m, H-5′), 3.24 (1H, m, H-1′), 3.05 (1H, m, H-7′), 2.63 (1H, m, H-2b′), 2.42 (1H, m, H-9a′), 2.21 (1H, m, H-15a′), 2.14 (1H, m, H-9b′), 2.04 (1H, m, H-8a′), 1.92 (1H, m, H-8a), 1.90 (1H, m, H-8b), 1.88 (1H, m, H-15b′), 1.85 (1H, m, H-9a), 1.62 (1H, m, H-9b), 1.54 (2H, m, H-14), 1.48 (1H, m, H-8b′). 13C NMR (100 MHz, CDCl3, δ, ppm): 170.0 (C-1), 143.1 (C-2), 194.2 (C-3), 142.1 (C-4), 49.1 (C-5), 83.7 (C-6), 39.4 (C-7), 23.0 (C-8), 43.5 (C-9), 70.9 (C-10), 140.4 (C-11), 170.9 (C-12), 119.6 (C-13), 35.3 (C-14), 122.7 (C-15), 39.8 (C-1′), 44.9 (C-2′), 220.4 (C-3′), 50.1 (C-4′), 51.1 (C-5′), 84.5 (C-6′), 43.4 (C-7′), 31.9 (C-8′), 38.2 (C-9′), 150.1 (C-10′), 138.1 (C-11′), 170.9 (C-12′), 121.6 (C-13′), 114.2 (C-14′), 28.3 (C-15′).
Dihydrodehydrodiconiferyl Alcohol (10). Colorless oil. ESI-MS m/z 383 [M + Na]+. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 6.94 (1H, d, J = 1.8, H-2), 6.88 (1H, dd, J = 1.8, 8.2, H-6), 6.80 (1H, d, J = 7.8, H-5), 6.68 (2H, br.s, H-2′, 6′), 5.54 (1H, d, J = 7.2, H-7), 3.84 (3H, s, 3′-OCH3), 3.82 (2H, m, H-9), 3.80 (3H, s, 3-OCH3), 3.70 (2H, t, J = 6.3, H-9′), 3.60 (1H, m, H-8), 2.70 (2H, m, H-7′), 1.91 (2H, m, H-8′). 13C NMR (100 MHz, CD3OD, δ, ppm): 133.1 (C-1), 108.8 (C-2), 146.7 (C-3), 146.4 (C-4), 114.3 (C-5), 116.0 (C-6), 87.8 (C-7), 53.8 (C-8), 63.9 (C-9), 135.4 (C-1′), 114.3 (C-2′), 127.8 (C-3′), 146.7 (C-4′), 143.8 (C-5′), 121.7 (C-6′), 32.0 (C-7′), 35.9 (C-8′), 62.3 (C-9′), 55.8 (3-OCH3), 56.0 (3′-OCH3).
Secoisolariciresinol (11). White powder. ESI-MS m/z 361 [M – H]–. 1H NMR (400 MHz, CDCl3, δ, ppm, J/Hz): 6.81 (2H, d, J = 7.8, H-5, 5′), 6.64 (2H, dd, J = 1.8, 7.8, H-6, 6′), 6.59 (2H, d, J = 1.5, H-2, 2′), 3.82 (6H, 2 × OCH3), 3.57 (4H, m, H-9, 9′), 2.68 (4H, m, H-7, 7′), 1.87 (2H, br.s, H-8, 8′). 13C NMR (100 MHz, CDCl3, δ, ppm): 132.4 (C-1, 1′), 111.4 (C-2, 2′), 146.5 (C-3, 3′), 143.8 (C-4, 4′), 114.1 (C-5, 5′), 121.7 (C-6, 6′), 35.9 (C-7, 7′), 43.8 (C-8, 8′), 61.0 (C-9, 9′), 55.8 (OCH3).
Methyl 3,4- O -Dicaffeoylquinate (15). Yellow powder. ESI-MS m/z 529 [M – H]–. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 7.61, 7.50 (1H each, d, J = 15.9, H-7′, 7″), 7.04, 7.00 (1H each, d, J = 1.8, H-2′, 2″), 6.91 (2H, m, H-6′, 6″), 6.75 (1H each, d, J = 8.4, H-5′, 5″), 6.28, 6.16 (1H each , d, J = 15.9, H-8′, 8″), 5.55 (1H, m, H-3), 5.11 (1H, dd, J = 3.0, 8.1, H-4), 4.33 (1H, m, H-5), 3.71 (3H, s, OCH3), 2.26 (4H, m, H-2, 6). 13C NMR (100 MHz, CD3OD, δ, ppm): 75.8 (C-1), 38.4 (C-2, 6), 69.1 (C-3), 74.9 (C-4), 68.6 (C-5), 175.2 (C-7), 127.6, 127.7 (C-1′, 1″), 115.2 (C-2′, 2″), 146.8 (C-3′, 3″), 149.7 (C-4′, 4″), 116.5 (C-5′, 5″), 123.1 (C-6′, 6″), 147.7 (C-7′, 7″), 114.6, 114.7 (C-8′, 8″), 167.9, 168.5 (C-9′, 9″), 53.1 (OCH3).
Zataroside-A (18). White powder. ESI-MS m/z 351 [M + Na]+. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 6.91 (1H, s, H-6), 6.62 (1H, s, H-3), 4.71 (1H, d, J = 7.8, H-1′), 3.87 (1H, m, H-6a′), 3.73 (1H, m, H-6b′), 3.30–3.47 (5H, m, H-7 and H-2′, 3′, 4′, 5′), 2.17 (3H, s, H-10), 1.18 (6H, br.s, H-8, 9). 13C NMR (100 MHz, CD3OD, δ, ppm): 138.2 (C-1), 151.7 (C-2), 120.3 (C-3), 123.2 (C-4), 149.1 (C-5), 113.1 (C-6), 27.0 (C-7), 23.6, 23.7 (C-8, 9), 16.1 (C-10), 104.3 (C-1′), 75.1 (C-2′), 77.9 (C-3′), 71.5 (C-4′), 78.2 (C-5′), 62.6 (C-6′).
4-Allyl-2,6-dimethoxyphenol-β-D-glucopyranoside (19). White powder. ESI-MS m/z 379 [M + Na]+. 1H NMR (400 MHz, DMSO-d6, δ, ppm, J/Hz): 6.48 (2H, s, H-3, 5), 5.98 (1H, m, H-8), 5.13 (2H, br.s, H-9), 4.88 (1H, d, J = 7.5, H-1′), 3.72 (6H, s, 2 × OCH3), 2.98–3.70 (8H, m, H-7 and H-2′, 3′, 4′, 5′, 6′). 13C NMR (100 MHz, DMSO-d6, δ, ppm): 135.4 (C-1), 152.4 (C-2, 6), 106.5 (C-3, 5), 132.8 (C-4), 40.4 (C-7), 137.5 (C-8), 115.9 (C-9), 56.2 (2 × OCH3), 102.7 (C-1′), 74.1 (C-2′), 76.5 (C-3′), 69.9 (C-4′), 77.1 (C-5′), 60.9 (C-6′).
Phenylethyl- O -β-D-glucopyranoside (20). White powder. ESI-MS m/z 307 [M + Na]+. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 7.25 (4H, br.s, H-2, 3, 5, 6), 7.16 (1H, m, H-4), 4.30 (1H, d, J = 7.8, H-1′), 3.72 (2H, m, H-7), 3.18 (2H, m, H-8). 13C NMR (100 MHz, CD3OD, δ, ppm): 140.4 (C-1), 130.0 (C-2, 6), 129.3 (C-3, 5), 127.2 (C-4), 37.2 (C-7), 71.7 (C-8), 104.4 (C-1′), 75.1 (C-2′), 78.1 (C-3′), 71.6 (C-4′), 77.9 (C-5′), 62.8 (C-6′).
4- O -α-L-Rhamnopyranosyl-(1→6)-β-D-glucopyranosyl Acetophenone (27). White powder. ESI-MS m/z 467 [M + Na]+. 1H NMR (400 MHz, CD3OD, δ, ppm, J/Hz): 1.17 (3H, d, J = 6.6, H-6″), 2.55 (3H, s, H-8), 3.29 (1H, m, H-4′), 3.34 (1H, m, H-2″), 3.48 (1H, m, H-5′), 3.59–3.64 (4H, m, H-3′, 3″, 4″, 6′), 3.68 (1H, m, H-2′), 3.82 (1H, m, H-5″), 4.03 (1H, d, J = 9.0, H-6′), 4.68 (1H, d, J = 1.2, H-1″), 4.99 (1H, d, J = 7.2, H-1′), 7.14 (2H, d, J = 9.0, H-3, 5), 7.98 (2H, d, J = 9.0, H-2, 6). 13C NMR (100 MHz, CD3OD, δ, ppm): 132.7 (C-1), 131.7 (C-2, 6), 117.3 (C-3, 5), 163.0 (C-4), 199.6 (C-7), 26.5 (C-8), 102.2 (C-1′), 74.0 (C-2′), 77.1 (C-3′), 71.5 (C-4′), 78.0 (C-5′), 67.8 (C-6′), 101.5 (C-1″), 72.2 (C-2″), 72.4 (C-3″), 74.8 (C-4″), 69.9 (C-5″), 18.0 (C-6″).
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Acknowledgment
This research work was supported by the program for Changjiang Scholars and Innovative Research Team in University (PCSIRT), NCET Foundation, NSFC (C03050201), and National 863 Program (2006AA02Z338).
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Published in Khimiya Prirodnykh Soedinenii, No. 1, January–February, 2013, pp. 148–149.
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Wu, ZJ., Shen, YH. & Zhang, WD. Chemical constituents of Ainsliaea macrocephala . Chem Nat Compd 49, 167–169 (2013). https://doi.org/10.1007/s10600-013-0546-8
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DOI: https://doi.org/10.1007/s10600-013-0546-8