Identifications of compounds 1–13
Lupeol (1): white crystal solid. 1 H NMR (CDCl3, 500 MHz): δ 4.59 (1 H, s, H-29a), 4.70 (1 H, s, H-29b), 3.23 (1 H, dd, J = 2.0, 5.8 Hz, H-3), 1.00 (3 H, s, H-23), 0.98 (3 H, s, H-24), 0.88 (3 H, s, H-25), 0.86 (3 H, s, H-26), 0.84 (3 H, s, H-27), 0.79 (3 H, s, H-28), 1.72 (3 H, s, H-30). 13 C NMR (CDCl3, 125 MHz): δ 14.6 (C-27), 16.1 (C-24), 16.1 (C-26), 16.2 (C-25), 18.1 (C-28), 18.4 (C-6), 19.4 (C-30), 21.1 (C-11), 27.7 (C-2), 25.3 (C-12), 27.6 (C-15), 28.1 (C-23), 29.9 (C-21), 34.5 (C-7), 35.7 (C-16), 37.4 (C-10), 38.1 (C-1), 38.9 (C-13), 39.0 (C-4), 40.1 (C-22), 41.0 (C-8), 42.9 (C-14), 43.1 (C-17), 47.9 (C-19), 48.4 (C-18), 50.6 (C-9), 55.4 (C-5), 79.2 (C-3), 109.4 (C-29), 151.0 (C-20).
4,5-Dihydroxy-3-methoxyxanthone (2): yellow oil. 1 H-NMR (acetone-d6, 500 MHz): δ 7.21 (1 H, t, J = 8.0 Hz, H-7), 7.30 (1 H, dd, J = 8.0, 1.8 Hz, H-6), 7.31 (1 H, d, J = 9.0 Hz, H-2), 7.41 (1 H, d, J = 9.0 Hz, H-1), 7.68 (1 H, dd, J = 8.0, 1.8 Hz, H-8), 3.93 (3 H, s, 3-OCH3). 13 C-NMR (acetone-d6, 125 MHz): δ 61.2 (3-OCH3), 113.5 (C-2), 116.1 (C-8), 116.1 (C-9a), 119.3 (C-6), 122.8 (C-8a), 123.1 (C-1), 123.3 (C-7), 144.7 (C-10a), 145.1 (C-3), 146.0 (C-5), 146.6 (C-4), 150.3 (C-4a), 175.4 (C-9).
4-Hydroxyxanthone (3): yellow crystal. 1 H-NMR (acetone-d6, 500 MHz): δ 7.26 (1 H, t, J = 8.0 Hz, H-2), 7.36 (1 H, dd, J = 8.0, 1.8 Hz, H-3), 7.45 (1 H, td, J = 7.6, 1.5 Hz, H-7), 7.62 (1 H, dd, J = 7.6, 1.5 Hz, H-5), 7.71 (1 H, dd, J = 8.0, 1.8 Hz, H-1), 7.84 (1 H, td, J = 7.6, 1.5 Hz, H-6), 8.24 (1 H, dd, J = 7.6, 1.5 Hz, H-8). 13 C-NMR (acetone-d6, 125 MHz): δ 115.9 (C-1), 118.1 (C-5), 120.1 (C-3), 121.5 (C-8a), 122.6 (C-9a), 123.8 (C-2), 124.0 (C-7), 126.1 (C-8), 134.9 (C-6), 145.4 (C-4a), 146.6 (C-4), 155.8 (C-10a), 176.2 (C-9).
1,7-Dihydroxyxanthone (4): yellow oil. 1 H-NMR (acetone-d6, 500 MHz): δ 6.77 (1 H, d, J = 8.3 Hz, H-2), 6.90 (1 H, d, J = 8.3 Hz, H-4), 7.34 (1 H, dd, J = 8.0, 2.6 Hz, H-6), 7.39 (1 H, d, J = 8.0 Hz, H-5), 7.54 (1 H, t, J = 8.3 Hz, H-3), 7.60 (1 H, d, J = 2.6 Hz, H-8), 12.66 (1 H, s, 1-OH). 13 C-NMR (acetone-d6, 125 MHz): δ 105.3 (C-8), 106.6 (C-4), 108.7 (C-9a), 110.0 (C-2), 119.0 (C-5), 120.8 (C-8a), 125.3 (C-6), 136.2 (C-3), 151.0 (C-10a), 156.0 (C-4a), 156.1 (C-7), 161.8 (C-1), 181.7 (C-9).
Mixture of β-sitosterol and stigmasterol (2:1) (5): white powder.
β-sitosterol; 1 H NMR (CDCl3, 500 MHz): δ 5.35 (1 H, t, J = 6.5 Hz, H-5), 3.52 (1 H, tdd, J = 4.3, 4.0, 3.6 Hz, H-3), 1.00 (3 H, s, H-29), 0.92 (3 H, d, J = 6.3 Hz, H-19), 0.83 (3 H, t, J = 7.2 Hz, H-24), 0.82 (3 H, d, J = 6.3 Hz, H-26), 0.80 (3 H, d, J = 6.3 Hz, H-27), 0.67 (3 H, s, H-28). 13 C-NMR (CDCl3, 125 MHz): δ 12.0 (C-24), 12.4 (C-29), 19.1 (C-28), 19.4 (C-19), 19.7 (C-27), 20.3 (C-26), 21.5 (C-11), 23.5 (C-23), 26.5 (C-15), 26.5 (C-21), 28.6 (C-16), 29.6 (C-25), 32.1 (C-2), 32.2 (C-8), 32.3 (C-7), 34.3 (C-20), 36.5 (C-10), 36.8 (C-18), 37.4 (C-1), 40.1 (C-12), 42.6 (C-4), 42.8 (C-13), 46.4 (C-22), 50.4 (C-9), 56.5 (C-17), 57.1 (C-14), 72.1 (C-3), 121.9 (C-6), 141.1 (C-5).
Stigmasterol ; 1 H NMR (CDCl3, 500 MHz): δ 5.31 (1 H, t, J = 6.5 Hz, H-5), 3.51 (1 H, tdd, J = 4.3, 4.0, 3.6 Hz, H-3), 5.14 (1 H, m, H-21), 4.97(1 H, m, H-20), 1.02 (3 H, s, H-29), 0.91 (3 H, d, J = 6.3 Hz, H-19), 0.82 (3 H, t, J = 7.0 Hz, H-24), 0.81 (3 H, d, J = 6.5 Hz, H-26), 0.80 (3 H, d, J = 6.5 Hz, H-27), 0.70 (3 H, s, H-28). 13 C-NMR (CDCl3, 125 MHz): δ 12.2 (C-24), 12.4 (C-29), 19.0 (C-28), 19.8 (C-27), 20.4 (C-26), 21.7 (C-11), 21.9 (C-19), 24.6 (C-15), 25.5 (C-23), 29.4 (C-16), 29.7 (C-25), 31.9 (C-8), 32.1 (C-2), 32.3 (C-7), 36.7 (C-10), 37.6 (C-1), 40.0 (C-12), 40.7 (C-18), 42.3 (C-13), 42.6 (C-4), 50.2 (C-9), 56.4 (C-17), 56.9 (C-14), 72.3 (C-3), 121.7 (C-6), 129.8 (C-21), 138.9 (C-20), 141.3 (C-5).
Mammea A/AA cyclo D (6): yellow powder. 1 H-NMR (CDCl3, 500 MHz): δ 0.96 (1 H, d, J = 6.6 Hz, H-9ʹ), 0.96 (1 H, d, J = 6.6 Hz, H-10ʹ), 1.57 (1 H, s, H-4ʹ), 1.57 (1 H, s, H-5ʹ), 2.20 (1 H, m, H-8ʹ), 2.94 (1 H, d, J = 6.7 Hz, H-7ʹ), 5.61 (1 H, d, J = 10.0 Hz, H-2ʹ), 5.96 (1 H, s, H-3), 6.87 (1 H, d, J = 10.0 Hz, H-1ʹ), 7.27 (1 H, m, H-3ʹʹ), 7.30 (1 H, m, H-4ʹʹ), 7.30 (1 H, m, H-5ʹʹ), 7.38 (1 H, m, H-2ʹʹ), 7.41 (1 H, m, H-6ʹʹ), 14.77 (1 H, s, 5-OH). 13 C-NMR (CDCl3, 125 MHz): δ 22.4 (C-9ʹ), 22.4 (C-10ʹ), 24.9 (C-8ʹ), 28.1 (C-4ʹ), 28.1 (C-5ʹ), 53.3 (C-7ʹ), 79.6 (C-3ʹ), 101.3 (C-8), 102.0 (C-4a), 107.0 (C-6), 112.5 (C-3), 115.3 (C-1ʹ), 126.1 (C-2ʹ), 126.9 (C-4ʹʹ), 127.4 (C-2ʹʹ), 127.4 (C-6ʹʹ), 128.0 (C-5ʹʹ), 128.1 (C-3ʹʹ), 139.1 (C-1ʹʹ), 154.6 (C-8a), 156.1 (C-4), 157.9(C-7), 159.4 (C-2), 164.2 (C-5), 206.5 (C-6ʹ).
Mammea A/AA cyclo F (7): yellow powder. 1 H-NMR (CDCl3, 500 MHz): δ 0.97 (1 H, s, H-9ʹ), 0.97 (1 H, s, H-10ʹ), 1.31 (1 H, s, H-5ʹ), 1.43 (1 H, s, H-4ʹ), 2.23 (1 H, m, H-8ʹ), 2.97 (2 H, dd, J = 15.3, 9.0 Hz, H-7ʹ), 3.32 (1 H, d, J = 9.0 Hz, H-1ʹ), 4.90 (1 H, t, J = 9.0 Hz, H-2ʹ), 5.94 (1 H, s, H-3), 7.32 (1 H, m, H-3ʹʹ), 7.32 (1 H, m, H-4ʹʹ), 7.32 (1 H, m, H-5ʹʹ), 7.42 (1 H, m, H-2ʹʹ), 7.42 (1 H, m, H-6ʹʹ). 13 C-NMR (CDCl3, 125 MHz): δ 22.6 (C-9ʹ), 22.6 (C-10ʹ), 24.8 (C-5ʹ), 25.0 (C-8ʹ), 26.1 (C-4ʹ), 26.7 (C-1ʹ), 51.8 (C-7ʹ), 71.5 (C-3ʹ), 92.7 (C-2ʹ), 102.4 (C-4a), 103.2 (C-6), 104.9 (C-8), 112.0 (C-3), 127.0 (C-6ʹʹ), 127.1 (C-2ʹʹ), 127.4 (C-5ʹʹ), 127.5 (C-3ʹʹ), 128.1 (C-4ʹʹ), 138.9 (C-1ʹʹ), 155.5 (C-8a), 156.4 (C-4), 159.5 (C-2), 164.0 (C-5), 164.3 (C-7), 204.9 (C-6ʹ).
1,6-Dihydroxyxanthone (8): yellow powder. 1 H-NMR (acetone-d6, 500 MHz): δ 6.77 (1 H, d, J = 8.0 Hz, H-2), 7.00 (1 H, d, J = 8.0 Hz, H-4), 7.43 (1 H, dd, J = 9.0, 3.0 Hz, H-7), 7.52 (1 H, d, J = 9.0 Hz, H-8), 7.61 (1 H, d, J = 3.0 Hz, H-5), 7.70 (1 H, t, J = 8.0 Hz, H-3). 13 C-NMR (acetone-d6, 125 MHz): δ 106.7 (C-4), 108.3 (C-5), 109.2 (C-9a), 109.3 (C-2), 119.2 (C-8), 120.8 (C-8a), 124.3 (C-7), 136.8 (C-3), 150.1 (C-6), 154.1 (C-10a), 156.4 (C-4a), 162.3 (C-1), 181.9 (C-9).
1-Hydroxy-5,6,7-trimethoxyxanthone (9): yellow powder. 1 H-NMR (acetone-d6, 500 MHz): δ 6.95 (1 H, d, J = 8.2 Hz, H-2), 7.13 (1 H, d, J = 8.2 Hz, H-4), 7.20 (1 H, s, H-8), 7.68 (1 H, t, J = 8.2 Hz, H-3), 12.70 (1 H, brs, 1-OH), 3.96 (3 H, s, 5-OCH3), 3.93 (3 H, s, 6-OCH3), 3.95 (3 H, s, 7-OCH3). 13 C-NMR (acetone-d6, 125 MHz): δ 54.3 (5-OCH3), 55.4 (7-OCH3), 60.1 (6-OCH3), 96.3 (C-8), 105.5 (C-4), 109.5 (C-2), 111.6 (C-9a), 118.4 (C-8a), 134.3 (C-3), 139.0 (C-5), 140.1 (C-10a), 141.3 (C-6), 150.0 (C-7), 157.8 (C-4a), 160.6 (C-1), 174.1 (C-9).
3,4,5-Trihydroxyxanthone (10): yellow powder. 1 H-NMR (acetone-d6, 500 MHz): δ 7.22 (1 H, t, J = 8.1 Hz, H-7), 7.29 (1 H, dd, J = 8.1, 1.8 Hz, H-6), 7.30 (1 H, d, J = 9.0 Hz, H-2), 7.42 (1 H, d, J = 9.0 Hz, H-1), 7.69 (1 H, dd, J = 8.1, 1.8 Hz, H-8). 13 C-NMR (acetone-d6, 125 MHz): δ 113.7 (C-2), 116.0 (C-8), 116.2 (C-9a), 119.3 (C-6), 122.9 (C-8a), 123.0 (C-1), 123.3 (C-7), 144.7 (C-10a), 145.2 (C-3), 146.0 (C-5), 146.6 (C-4), 150.2 (C-4a), 175.4 (C-9).
5-Hydroxy-1-methoxyxanthone (11): yellow powder. 1 H-NMR (acetone-d6, 500 MHz): δ 6.94 (1 H, d, J = 8.3 Hz, H-2), 7.12 (1 H, d, J = 8.3 Hz, H-4), 7.19 (1 H, t, J = 7.9 Hz, H-7), 7.26 (1 H, dd, J = 7.9, 1.6 Hz, H-6), 7.62 (1 H, dd, J = 7.9, 1.6 Hz, H-8), 7.70 (1 H, t, J = 8.3 Hz, H-3), 3.94 (3 H, s, 1-OCH3), 9.24 (1 H, brs, 5-OH). 13 C-NMR (acetone-d6, 125 MHz): δ 55.5 (1-OCH3), 105.8 (C-4), 109.5 (C-2), 112.0 (C-9a), 115.8 (C-8), 119.1 (C-6), 123.3 (C-7), 123.9 (C-8a), 135.1 (C-3), 144.1 (C-10a), 145.7 (C-5), 157.5 (C-4a), 160.6 (C-1), 174.7 (C-9).
2-Hydroxyxanthone (12): yellow powder. 1 H-NMR (acetone-d6, 500 MHz): δ 7.36 (1 H, dd, J = 8.7, 2.8 Hz, H-3), 7.43 (1 H, td, J = 7.6, 1.3 Hz, H-7), 7.51 (1 H, d, J = 8.7 Hz, H-4), 7.54 (1 H, dd, J = 7.6, 1.3 Hz, H-5), 7.61 (1 H, d, J = 2.8 Hz, H-1), 7.81 (1 H, td, J = 7.6, 1.3 Hz, H-6), 8.23 (1 H, dd, J = 7.6, 1.3 Hz, H-8), 8.90 (1 H, s, 2-OH). 13 C-NMR (acetone-d6, 125 MHz): δ 114.2 (C-1), 123.2 (C-5), 124.5 (C-4), 126.2 (C-8a), 127.5 (C-9a), 128.8 (C-7), 129.3 (C-3), 131.3 (C-8), 139.9 (C-6), 155.2 (C-4a), 159.1 (C-2), 161.3 (C-10a), 181.1 (C-9).
1,5-Dihydroxy-6-methoxyxanthone (13): yellow powder, 1 H-NMR (acetone-d6, 500 MHz): δ 6.53 (1 H, d, J = 8.3 Hz, H-2), 6.79 (1 H, d, J = 8.8 Hz, H-7), 6.81 (1 H, d, J = 8.3 Hz, H-4), 7.45 (1 H, t, J = 8.3 Hz, H-3), 7.61 (1 H, d, J = 8.8 Hz, H-8), 12.62 (1 H, s, 1-OH), 3.79 (3 H, s, 6-OCH3). 13 C-NMR (acetone-d6, 125 MHz): δ 60.8 (6-OCH3), 106.6 (C-4), 107.8 (C-9a), 110.1 (C-2), 113.7 (C-7), 114.2 (C-8a), 121.1 (C-8), 134.5 (C-5), 136.3 (C-3), 150.9 (C-10a), 155.9 (C-4a), 156.7 (C-6), 161.8 (C-1), 181.1(C-9).