3.4. Spectroscopic Data Analysis
NMR spectra were obtained in acetone-
d6, CD
3OD, and CDCl
3. NMR data were acquired using a Bruker Ascend III 700 spectrometer (resonance frequency was 700.53 and 176.15 MHz for
1H and
13C, respectively). The
1H and
13C NMR spectra are shown in
Figure S1-S30 (Supplementary Material).
trans-3,3',5,5'-Tetrahydroxy-4-methoxystilbene (1): pale brown amorphous powder; UV (MeOH) λmax (log ε) 224 (3.55), 314 (3.75) nm; 1H-NMR (700 MHz, acetone-d6) δ 6.91 (1H, d, J = 16.1 Hz, H-8), 6.87 (1H, d, J = 16.1 Hz, H-7), 6.64 (2H, s, H-2′, 6′), 6.55 (2H, d, J = 2.1 Hz, H-2, 6), 6 .30 (1H, d, J = 2.1 Hz, H-4), 3.82 (3H, s, 4′-OCH3); 13C-NMR (175 MHz, acetone- d6) δ 159.6 (C-3, 5), 151.5 (C-3′, 5′), 140.6 (C-1), 136.3 (C-4′), 134.3 (C-1′), 129.3 (C-8), 128.8 (C-7), 106.8 (C-2′, 6′), 105.9 (C-2, 6), 103.0 (C-4), 60.8 (4′-OCH3); ESI-MS (positive ion mode) m/z 275 [M + H]+.
Resveratrol (2): pale brown amorphous powder; UV (MeOH) λmax (log ε) 216 (3.56), 305 (3.93) nm; 1H-NMR (700 MHz, CD3OD) δ 6.95 (1H, d, J = 16.1 Hz, H-8), 6.80 (1H, d, J = 16.1 Hz, H-7), 7.35 (2H, d, J = 8.4 Hz, H-2′, 6′), 6.76 (2H, d, J = 8.4 Hz, H-3′, 5′), 6.44 (2H, d, J = 2.1 Hz, H-2, 6), 6.16 (1H, t, J = 2.1 Hz, H-4); 13C-NMR (175 MHz, CD3OD) δ 159.8 (C-3, 5), 158.5 (C-4′), 141.5 (C-1), 130.6 (C-1′), 129.5 (C-8), 128.9 (C-2′, 6′), 127.2 (C-7), 116.2 (C-3′, 5′), 105.9 (C-2, 6), 102.8 (C-4); ESI-MS (positive ion mode) m/z 229 [M + H]+.
4-Hydroxybenzoic acid (3): white amorphous powder; UV (MeOH) λmax (log ε) 199 (3.95), 210 (sh), 255 (3.70) nm; 1H-NMR (700 MHz, CD3OD) δ 7.88 (2H, d, J = 8.4 Hz, H-2, 6), 6.82 (2H, d, J = 8.4 Hz, H-3, 5); 13C-NMR (175 MHz, CD3OD) δ 170.2 (C-7), 163.5 (C-4), 133.1 (C-2, 6), 122.8 (C-1), 116.2 (C-3, 5); ESI-MS (positive ion mode) m/z 139 [M + H]+.
2-O-Caffeoylglycerol (4): white amorphous powder; UV (MeOH) λmax (log ε) 217 (3.65), 240 (3.25), 295 (sh), 325 (3.95) nm; 1H-NMR (700 MHz, CD3OD) δ 7.60 (1H, d, J = 16.1 Hz, H-7), 7.05 (1H, d, J = 2.1 Hz, H-2), 6.95 (1H, dd, J = 8.4, 2.1 Hz, H-6), 6.78 (1H, d, J = 8.4 Hz, H-5), 6.31 (1H, d, J = 16.1 Hz, H-8), 4.98 (1H, p, J = 5.6 Hz, H-2′), 3.76 (2H, dd, J = 11.9, 4.9 Hz, Ha-1′, 3′), 3.73 (2H, dd, J = 11.9, 5.6 Hz, Hb-1′, 3′); 13C-NMR (175 MHz, CD3OD) δ 169.1 (C-9), 149.7 (C-4), 147.2 (C-7), 147.0 (C-3), 127.9 (C-1), 123.1 (C-6), 116.6 (C-5), 115.5 (C-8), 115.3 (C-2), 76.7 (C-2′), 61.9 (C-1′, 3′); ESI-MS (positive ion mode) m/z 255 [M + H]+.
1-O-Caffeoylglycerol (5): white amorphous powder; UV (MeOH) λmax (log ε) 217 (3.68), 241 (3.29), 295 (sh), 325 (3.97) nm; 1H-NMR (700 MHz, CD3OD) δ 7.59 (1H, d, J = 15.4 Hz, H-7), 7.05 (1H, d, J = 2.1 Hz, H-2), 6.95 (1H, dd, J = 8.4, 2.1 Hz, H-6), 6.78 (1H, d, J = 2.1 Hz, H-5), 6.29 (1H, d, J = 15.4 Hz, H-8), 4.25 (1H, dd, J = 11.9, 4.2 Hz, Ha-1′), 4.16 (1H, dd, J = 11.9, 4.2 Hz, Hb-1′), 3.89 (1H, p, J = 6.3, 4.2 Hz, H-2′), 3.61 (1H, dd, J = 11.2, 4.9 Hz, Ha-3′), 3.59 (1H, dd, J = 11.2, 5.6 Hz, Hb-3′); 13C-NMR (175 MHz, CD3OD) δ 169.4 (C-9), 149.7 (C-4), 147.3 (C-7), 146.9 (C-3), 127.9 (C-1), 123.1 (C-6), 116.6 (C-5), 115.3 (C-2), 115.0 (C-8), 71.4 (C-2′), 66.7 (C-1′), 64.2 (C-3′); ESI-MS (positive ion mode) m/z 255 [M + H]+.
Juncusyl ester B (6): white amorphous powder; UV (MeOH) λmax (log ε) 210 (3.45), 226 (3.55), 297 (sh), 309 (4.05) nm; 1H-NMR (700 MHz, CD3OD) δ 7.67 (1H, d, J = 16.1 Hz, H-7), 7.46 (2H, d, J = 8.4 Hz, H-2, 6), 6.81 (2H, d, J = 8.4 Hz, H-3, 5), 6.37 (1H, d, J = 16.1 Hz, H-8), 4.99 (1H, p, J = 4.2 Hz, H-2′), 3.76 (1H, dd, J = 11.9, 4.9 Hz, Ha-1′, 3′), 3.73 (1H, dd, J = 11.9, 5.6 Hz, Hb-1′, 3′); 13C-NMR (175 MHz, CD3OD) δ 169.1 (C-9), 161.4 (C-4), 146.8 (C-7), 131.3 (C-2, 6), 127.4 (C-1), 117.0 (C-3, 5), 115.5 (C-8), 76.8 (C-2′), 61.9 (C-1′, 3′); ESI-MS (positive ion mode) m/z 239 [M + H]+.
Acertannin (7): white amorphous powder; UV (MeOH) λmax (log ε) 217 (4.15), 275 (3.53)
nm; 1H-NMR (700 MHz, CD3OD) δ 7.09 (2H, s, H-2′′, 6′′), 7.08 (2H, s, H-2′, 6′), 4.91 (1H, ddd, J = 10.5, 9.1, 5.6 Hz, H-2), 4.55 (1H, dd, J = 12.6, 2.1 Hz, Ha-6), 4.38 (1H, dd, J = 11.2, 4.9 Hz, Hb-6), 4.10 (1H, dd, J = 11.2, 5.6 Hz, Ha-1), 3.71 (1H, t, J = 9.1 Hz, H-3), 3.53 (1H, m, H-5), 3.52 (1H, m, H-4), 3.35 (1H, t-like, J = 10.5 Hz, Hb-1); 13C-NMR (175 MHz, CD3OD) δ 168.5 (C-7′′), 167.9 (C-7′), 146.7 (C-3′′, 5′′), 146.6 (C-3′, 5′), 140.1 (C-4′), 140.0 (C-4′′), 121.5 (C-1′′), 121.3 (C-1′), 110.4 (C-2′, 6′), 110.3 (C-2′′, 6′′), 80.3 (C-5), 77.1 (C-3), 73.3 (C-2), 72.1 (C-4), 68.1 (C-1), 65.0 (C-6); ESI-MS (positive ion mode) m/z 469 [M + H]+.
2-O-(E)-Feruloyl glyceride (8): white amorphous powder; UV (MeOH) λmax (log ε) 217 (3.60), 237 (2.50), 296 (sh), 325 (3.95) nm; 1H-NMR (700 MHz, CD3OD) δ 7.66 (1H, d, J = 16.1 Hz, H-7), 7.19 (1H, d, J = 2.1 Hz, H-2), 7.08 (1H, dd, J = 8.4, 2.1 Hz, H-6), 6.81 (1H, d, J = 8.4 Hz, H-5), 6.40 (1H, d, J = 16.1 Hz, H-8), 4.99 (1H, p, J = 4.9 Hz, H-2′), 3.89 (3H, s, 3-OCH3), 3.76 (1H, dd, J = 11.9, 4.2 Hz, Ha-1′, 3′), 3.73 (1H, dd, J = 11.9, 5.6 Hz, Hb-1′, 3′); 13C-NMR (175 MHz, CD3OD) δ 169.1 (C-9), 150.7 (C-4), 149.5 (C-3), 147.1 (C-7), 127.9 (C-1), 124.2 (C-6), 116.6 (C-5), 115.5 (C-8), 111.9 (C-2), 76.8 (C-2′), 61.9 (C-1′, 3′), 56.6 (3-OCH3); ESI-MS (positive ion mode) m/z 269 [M + H]+.
Maplexin D (9): white amorphous powder; UV (MeOH) λmax (log ε) 216 (4.10), 276 (3.47) nm; 1H-NMR (700 MHz, CD3OD) δ 7.10 (2H, s, H-2′′, 6′′), 7.08 (2H, s, H-2′, 6′), 4.99 (1H, ddd, J = 10.5, 9.1, 5.6 Hz, H-2), 5.01 (1H, t, J = 9.1 Hz, H-4), 4.18 (1H, dd, J = 11.2, 5.6 Hz, Ha-1), 3.98 (1H, t, J = 9.1 Hz, H-3), 3.62 (1H, brd, J = 9.8 Hz, Ha-6), 3.52 (1H, m, Hb-6), 3.54 (1H, m, H-5), 3.40 (1H, t, J = 11.2 Hz, Hb-1); 13C-NMR (175 MHz, CD3OD) δ 167.78 (C-7′′), 167.82 (C-7′), 146.69 (C-3′, 5′), 146.65 (C-3′′, 5′′), 140.22 (C-4′′), 140.18 (C-4′), 121.23 (C-1′′), 121.2 (C-1′), 110.5 (C-2′′, 6′′), 110.4 (C-2′, 6′), 81.2 (C-5), 75.1 (C-3), 73.5 (C-2), 73.0 (C-4), 68.1 (C-1), 62.8 (C-6); ESI-MS (positive ion mode) m/z 469 [M + H]+.
trans-Caffeic acid (10): white amorphous powder; UV (MeOH) λmax (log ε) 217 (3.62), 239 (3.20), 297 (sh), 324 (3.92) nm; 1H-NMR (700 MHz, CD3OD) δ 7.53 (1H, d, J = 16.1 Hz, H-7), 7.03 (1H, d, J = 2.1 Hz, H-2), 6.93 (1H, dd, J = 8.4, 2.1 Hz, H-6), 6.77 (1H, d, J = 8.4 Hz, H-5), 6.21 (1H, d, J = 16.1 Hz, H-8); 13C-NMR (175 MHz, CD3OD) δ 171.2 (C-9), 149.6 (C-4), 147.2 (C-7), 147.0 (C-3), 127.9 (C-1), 123.0 (C-6), 116.6 (C-5), 115.2 (C-2), 115.7 (C-8); ESI-MS (positive ion mode) m/z 181 [M + H]+.
Syringic acid (11): white amorphous powder; UV (MeOH) λmax (log ε) 217 (4.15), 275 (3.42) nm; 1H-NMR (700 MHz, CD3OD) δ 7.33 (2H, s, H-2, 6), 3.88 (6H, s, 3, 5-OCH3); 13C-NMR (175 MHz, CD3OD) δ 170.1 (C-7), 149.0 (C-3, 5), 141.9 (C-4), 122.0 (C-1), 108.4 (C-2, 6), 56.9 (3, 5-OCH3); ESI-MS (positive ion mode) m/z 199 [M + H]+.
1-Syringoyl-1,2-dihydroxyethane (12): white amorphous powder; UV (MeOH) λmax (log ε) 205 (3.87), 230 (sh), 304 (3.35) nm; 1H-NMR (700 MHz, CD3OD) δ 7.34 (2H, s, H-2, 6), 5.14 (1H, dd, J = 5.6, 4.2 Hz, H-8), 3.91 (6H, s, 3, 5-OCH3), 3.89 (1H, dd, J = 11.2, 4.2 Hz, Ha-9), 3.75 (1H, dd, J = 11.2, 4.2 Hz, Hb-9); 13C-NMR (175 MHz, CD3OD) δ 199.9 (C-7), 149.3 (C-3, 5), 143.2 (C-4), 126.9 (C-1), 107.9 (C-2, 6), 75.7 (C-8), 66.4 (C-9), 57.1 (3, 5-OCH3); ESI-MS (positive ion mode) m/z 243 [M + H]+.
3,5-Dihydroxy-4-methoxybenzoic acid (13): white amorphous powder; UV (MeOH) λmax (log ε) 211 (3.97), 258 (3.39), 294 (3.15) nm; 1H-NMR (700 MHz, CD3OD) δ 7.03 (2H, s, H-2, 6), 3.89 (3H, s, 4-OCH3); 13C-NMR (175 MHz, CD3OD) δ 170.0 (C-7), 151.8 (C-3, 5), 141.2 (C-4), 127.3 (C-1), 110.5 (C-2, 6), 60.9 (4-OCH3); ESI-MS (positive ion mode) m/z 185 [M + H]+.
1-(3,4,5-Trimethoxyphenyl)-1,2,3-propanetriol (14): white amorphous powder; UV (MeOH) λmax (log ε) 204 (3.85), 227 (sh), 269 (2.55) nm; 1H-NMR (700 MHz, CD3OD) δ 6.72 (2H, s, H-2, 6), 4.59 (1H, d, J = 5.6 Hz, H-7), 3.84 (6H, s, 3, 5-OCH3), 3.74 (3H, s, 4-OCH3), 3.67 (1H, m, H-8), 3.54 (1H, dd, J = 11.2, 4.2 Hz, Ha-9), 3.40 (1H, dd, J = 11.2, 5.6 Hz, Hb-9); 13C-NMR (175 MHz, CD3OD) δ 154.5 (C-3, 5), 139.9 (C-1), 138.4 (C-4), 105.2 (C-2, 6), 77.5 (C-8), 75.4 (C-7), 64.4 (C-9), 61.2 (4-OCH3), 56.7 (3, 5-OCH3); ESI-MS (positive ion mode) m/z 259 [M + H]+.
1-O-trans-ρ-Coumaroylglycerol (15): white amorphous powder; UV (MeOH) λmax (log ε) 210 (3.35), 226 (3.45), 296 (sh), 310 (3.90) nm; 1H-NMR (700 MHz, CD3OD) δ 7.65 (1H, d, J = 16.1 Hz, H-7), 7.46 (1H, d, J = 9.1 Hz, H-2, 6), 6.80 (1H, d, J = 9.1 Hz, H-3, 5), 6.36 (1H, d, J = 16.1 Hz, H-8), 4.26 (1H, dd, J = 11.2, 4.2 Hz, Ha-1′), 4.16 (1H, dd, J = 11.2, 6.3 Hz, Hb-1′), 3.89 (1H, m, H-2′), 3.61 (1H, dd, J = 11.2, 5.6 Hz, Ha-3′), 3.59 (1H, dd, J = 11.2, 5.6 Hz, Hb-3′); 13C-NMR (175 MHz, CD3OD) δ 169.3 (C-9), 161.5 (C-4), 146.9 (C-7), 131.3 (C-2, 6), 127.3 (C-1), 117.0 (C-3, 5), 115.1 (C-8), 71.4 (C-2′), 66.7 (C-1′), 64.2 (C-3′); ESI-MS (positive ion mode) m/z 239 [M + H]+.
Sieboldic acid (
16): white amorphous powder; ‒4.8° (
c = 0.14, MeOH);
1H-NMR (700 MHz, CD
3OD) and
13C-NMR (175 MHz, CD
3OD) (
Table 1); HRESI-MS (positive ion mode)
m/z 199.0575 [M + Na]
+ (calcd. for C
7H
12O
5Na, 199.0577).
Smilaxsiebolane A (
17): white amorphous powder; +46.4° (
c = 0.11, CH
2Cl
2); IR (KBr) ν
max 3382, 3043, 2920, 2856, 1706, 1634, 1462, 1371, 1044, 979, 890 cm
-1;
1H-NMR (700 MHz, CDC1
3) and
13C-NMR (175 MHz, CDC1
3) (
Table 2); HRESI-MS (positive ion mode)
m/z 455.4275 [M + H]
+ (calcd. for C
32H
55O, 455.4247).
Smilaxsiebolane B (
18): white amorphous powder; +26.4° (
c = 0.36, CH
2Cl
2); IR (KBr) ν
max 2959, 2870, 1706, 1635, 1461, 1368, 1114, 986, 890 cm
-1;
1H-NMR (700 MHz, CDC1
3) and
13C-NMR (175 MHz, CDC1
3) (
Table 2); HRESI-MS (positive ion mode)
m/z 453.4071 [M + H]
+ (calcd. for C
32H
53O, 453.4091).
trans-ρ-Ethyl coumarate (19): white amorphous powder; UV (MeOH) λmax (log ε) 217 (3.44), 236 (3.53), 294 (sh), 325 (4.13) nm; 1H-NMR (700 MHz, CD3OD) δ 7.60 (1H, d, J = 16.1 Hz, H-7), 7.45 (1H, d, J = 8.4 Hz, H-2, 6), 6.80 (1H, d, J = 8.4 Hz, H-3, 5), 6.31 (1H, d, J = 16.1 Hz, H-8), 4.21 (2H, q, J = 7.0 Hz, H-1′), 1.31 (1H, t, J = 7.0 Hz, H-2′); 13C-NMR (175 MHz, CD3OD) δ 169.5 (C-9), 161.4 (C-4), 146.5 (C-7), 131.3 (C-2, 6), 127.3 (C-1), 117.0 (C-3, 5), 115.5 (C-8), 61.6 (C-1′), 14.8 (C-2′); ESI-MS (positive ion mode) m/z 193 [M + H]+.