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2.3.3. Luteolin-7-O- glucoside (3)
2.3.9. 6-Methoxy-naringenin (9)
Yellow amorphous powder; [␣]25D = −19.8 (c 0.1, CH3OH);
ESI–MS: m/z 449 [M+H]+; 1H NMR (400 MHz, DMSO-d6) ␦H: 12.99
(1H, s, OH-5), 7.45 (1H, dd, J = 8.0, 2.0 Hz, H-6ꢀ), 7.42 (1H, d, J = 2.0 Hz,
H-2ꢀ), 6.90 (1H, d, J = 8.0 Hz, H-5ꢀ), 6.79 (1H, d, J = 2.0 Hz, H-8), 6.76
(1H, s, H-3), 6.44 (1H, dd, J = 2.0 Hz, H-6), 5.08 (1H, d, J = 7.2 Hz, H-1ꢀꢀ),
3.71 (1H, d, J = 11.2 Hz, H-6aꢀꢀ), 3.49 (1H, d, m, H-6bꢀꢀ), 3.44 (1H, m,
Yellow amorphous powder; [␣]25D = −11.4 (c 0.1, CH3OH);
ESI–MS: m/z 303 [M+H]+; 1H NMR (400 MHz, CD3OD) ␦H: 7.31 (1H,
d, J = 8.4 Hz, H-2ꢀ,6ꢀ), 6.81 (1H, d, J = 8.4 Hz, H-3ꢀ,5ꢀ), 5.97 (1H, s, H-8),
5.33 (1H, dd, J = 12.8, 1.6 Hz, H-2), 3.79 (3H, s, 6-OCH3), 3.12 (1H,
dd, J = 17.2, 13.2 Hz, H2-3␣) 2.70 (1H, dd, J = 17.2, 1.6 Hz, H2-3);
13C NMR (100 MHz, CD3OD) ␦C: 198.7 (C-4), 161.0 (C-7), 160.4 (C-
9), 159.2 (C-4ꢀ), 156.7 (C-5), 131.2 (C-6), 130.6 (C-1ꢀ), 129.2 (C-2ꢀ,6ꢀ),
116.5 (C-3ꢀ,5ꢀ), 103.6 (C-10), 96.4 (C-8), 80.8 (C-2), 61.1 (6-OCH3),
44.2 (C-3).
H-5ꢀꢀ), 3.34 (1H, m, H-3ꢀꢀ), 3.27 (1H, m, H-2ꢀꢀ), 3.19 (1H, m, H-4ꢀꢀ); 13
C
NMR (100 MHz, DMSO-d6) ␦C: 181.9 (C-4), 164.4 (C-2), 162.9 (C-7),
161.1 (C-5), 156.9 (C-9), 149.9 (C-4ꢀ), 145.8 (C-3ꢀ), 121.4 (C-1ꢀ), 119.2
(C-6ꢀ), 116.0 (C-5ꢀ), 113.6 (C-2ꢀ), 105.3 (C-10), 103.2 (C-3), 99.9 (C-
1ꢀꢀ), 99.5 (C-6), 94.7 (C-8), 77.2 (C-5ꢀꢀ), 76.4 (C-3ꢀꢀ), 73.1 (C-2ꢀꢀ), 69.5
(C-4ꢀꢀ), 60.6 (C-6ꢀꢀ).
2.3.10. Eriodictyol (10)
Light yellow amorphous powder; [␣]25D = −18.2 (c 0.1, CH3OH);
ESI–MS: m/z 289 [M+H]+; 1H NMR (400 MHz, acetone-d6) ␦H: 12.18
(1H, s, OH-5), 7.04 (1H, s, H-2ꢀ), 6.87 (2H, s, H-5ꢀ,6ꢀ), 5.96 (1H, s, H-
8), 5.94 (1H, s, H-6), 5.39 (1H, dd, J = 12.8, 3.2 Hz, H-2), 3.13 (1H,
dd, J = 17.2, 12.8, H-3␣), 2.72 (1H, dd, J = 17.2, 3.2 Hz, H-3); 13C
NMR (100 MHz, acetone-d6) ␦C: 197.3 (C-4), 167.5 (C-7), 165.4 (C-
5), 164.4 (C-9), 146.5 (C-4ꢀ), 146.1 (C-3ꢀ), 131.7 (C-1ꢀ), 119.3 (C-6ꢀ),
116.1 (C-5ꢀ), 114.8 (C-2ꢀ), 103.3 (C-10ꢀ), 96.9 (C-8ꢀ), 96.0 (C-6), 80.1
(C-2), 43.7 (C-3).
2.3.4. Isorhamnetin (4)
Yellow amorphous powder; [␣]25D = −17.6 (c 0.1, CH3OH);
ESI–MS: m/z 317 [M+H]+; 1H NMR (400 MHz, DMSO-d6) ␦H: 12.70
(1H, s, OH-5), 7.54 (1H, d, J = 2.0 Hz, H-2ꢀ), 7.44 (1H, dd, J = 8.4, 2.0 Hz,
H-6ꢀ), 6.89 (1H, d, J = 8.4 Hz, H-5ꢀ), 6.39 (1H, s, H-8), 6.17 (1H, s, H-
6), 3.77 (3H, s, 3ꢀ-OCH3); 13C NMR (100 MHz, DMSO-d6) ␦C: 177.7
(C-4), 164.6 (C-7), 161.2 (C-5), 156.3 (C-9), 155.5 (C-4ꢀ), 148.8 (C-
3ꢀ), 145.3 (C-2), 137.5 (C-3), 120.6 (C-1ꢀ), 120.5 (C-6ꢀ), 115.7 (C-5ꢀ),
115.3 (C-2ꢀ), 103.9 (C-10), 98.6 (C-6), 93.6 (C-8), 59.6 (3ꢀ-OCH3).
2.3.11. Filifolin (11)
Light yellow amorphous powder; [␣]25D = −10.2 (c 0.1, CH3OH);
ESI–MS: m/z 319 [M+H]+; 1H NMR (400 MHz, acetone-d6) ␦H: 12.31
(1H, s, OH-5), 7.03 (1H, s, H-2ꢀ), 6.86 (2H, s, H-5ꢀ,6ꢀ), 6.00 (1H, s,
H-8), 5.37 (1H, dd, J = 12.8, 2.8 Hz, H-2), 3.77 (6-OCH3), 3.13 (1H,
dd, J = 17.2, 12.8, H-3␣), 2.73 (1H, dd, J = 17.2, 2.8 Hz, H-3); 13C
NMR (100 MHz, acetone-d6) ␦C: 198.1 (C-4), 160.0 (C-7), 159.7 (C-
9), 156.4 (C-5), 146.4 (C-4ꢀ), 146.1 (C-3ꢀ), 131.7 (C-1ꢀ), 130.0 (C-6),
119.3 (C-5ꢀ), 116.1 (C-6ꢀ), 114.8 (C-2ꢀ), 103.4 (C-10), 95.8 (C-8), 80.1
(C-2), 60.8 (6-OCH3), 43.8 (C-3).
2.3.5. Hispidulin (5)
Yellow amorphous powder; [␣]25D = −18.6 (c 0.1, CH3OH);
ESI–MS: m/z 301 [M+H]+; 1H NMR (600 MHz, acetone-d6) ␦H: 7.92
(2H, d, J = 8.4 Hz, H-2ꢀ,6ꢀ), 7.00 (2H, d, J = 8.4 Hz, H-3ꢀ,5ꢀ), 6.62 (1H,
s, H-3), 6.60 (1H, s, H-8), 3.87 (3H, s, 6-OCH3); 13C NMR (125 MHz,
acetone-d6) ␦C: 183.6 (C-4), 165.2 (C-2), 162.1 (C-4ꢀ), 158.0 (C-7),
154.0 (C-5), 132.3 (C-6), 129.3 (C-2ꢀ,6ꢀ), 123.3 (C-1ꢀ), 117.0 (C-3ꢀ,5ꢀ),
105.7 (C-10), 103.5 (C-3), 94.9 (C-8), 60.7 (6-OCH3).
2.3.12. Protocatechuic acid (12)
2.3.6. Homoplantaginin (6)
Brown amorphous powder; [␣]25D = −31.6 (c 0.1, CH3OH);
Yellow amorphous powder; [␣]25D = −95.8 (c 0.1, CH3OH);
ESI–MS: m/z 463 [M+H]+; 1H NMR (400 MHz, DMSO-d6) ␦H: 7.88
(2H, d, J = 8.8 Hz, H-2ꢀ,6ꢀ), 6.96 (1H, s, H-8), 6.92 (1H, d, J = 8.8 Hz,
H-3ꢀ,5ꢀ), 6.65 (1H, s, H-3), 5.13 (1H, d, J = 7.2 Hz, H-1ꢀꢀ), 3.96 (1H, dd,
J = 12.0, 1.6 Hz, H-6aꢀꢀ), 3.89 (3H, s, 6-OCH3), 3.72 (1H, dd, J = 12.0,
6.0 Hz, H-6bꢀꢀ), 3.58 (1H, m, H-5ꢀꢀ), 3.57 (1H, m, H-2ꢀꢀ), 3.52 (1H, t,
J = 9.2 Hz, H-3ꢀꢀ), 3.42 (1H, t, J = 9.2, H-4); 13C NMR (100 MHz, DMSO-
d6) ␦C: 184.5 (C-4), 167.1 (C-2), 163.4 (C-4ꢀ), 158.0 (C-7), 154.4 (C-9),
154.2 (C-5), 134.4 (C-6), 129.8 (C-2ꢀ,6ꢀ), 123.0 (C-1), 117.3 (C-3ꢀ,5ꢀ),
107.7 (C-10), 103.8 (C-3ꢀ), 102.2 (C-1ꢀꢀ), 96.0 (C-8), 78.7 (C-3ꢀꢀ),78.2
(C-5ꢀꢀ), 74.9 (C-2ꢀꢀ), 71.5 (C-4ꢀꢀ), 62.7 (C-6ꢀꢀ), 61.6 (6-OCH3).
ESI–MS: m/z 155 [M+H]+; 1H NMR (400 MHz, CD3OD) ␦H: 7.44 (1H,
s, H-2), 7.43 (1H, d, J = 8.0 Hz, H-6), 6.80 (1H, d, J = 8.0, Hz, H-5); 13
C
NMR (100 MHz, CD3OD) ␦C: 170.4 (C-7), 151.6 (C-4), 146.2 (C-3),
124.0 (C-6), 123.4 (C-1), 117.9 (C-2), 115.9 (C-5).
2.3.13. Caffeic acid (13)
Yellow amorphous powder; [␣]25D = −3.6 (c 0.1, CH3OH);
ESI–MS: m/z 179 [M−H]−; 1H NMR (400 MHz, CD3OD) ␦H: 7.41 (1H,
d, J = 16.0 Hz, H-7), 7.02 (1H, d, J = 2.0 Hz, H-2), 6.96 (1H, dd, J = 8.0,
2.0 Hz, H-6), 6.75 (1H, d, J = 8.0 Hz, H-5), 6.17 (1H, d, J = 16.0 Hz, H-
8); 13C NMR (100 MHz, CD3OD) ␦C: 171.2 (C-9), 149.6 (C-4), 147.1
(C-7), 146.9 (C-3), 128.0 (C-1), 123.0 (C-5), 116.6 (C-2), 115.8 (C-6),
115.2 (C-8).
2.3.7. Nepetin (7)
Yellow amorphous powder; [␣]25D = −8.8 (c 0.1, CH3OH);
ESI–MS: m/z 317 [M+H]+;1H NMR (400 MHz, DMSO-d6) ␦H: 13.08
(1H, s, OH-5), 7.42 (1H, dd, J = 8.0, 2.0, H-6ꢀ), 7.39 (1H, br s, H-2ꢀ),
6.88 (1H, d, J = 8.0 Hz, H-5ꢀ), 6.66 (1H, s, H-3), 6.54 (1H, s, H-8), 3.74
(6-OCH3); 13C NMR (100 MHz, DMSO-d6) ␦C: 182.2 (C-4), 164.1 (C-
2), 154.5 (C-7), 149.8 (C-5), 149.7 (C-9), 146.4 (C-4ꢀ), 145.9 (C-3ꢀ),
130.0 (C-6), 121.8 (C-1ꢀ), 119.0 (C-6ꢀ), 116.1 (C-5ꢀ), 113.5 (C-2ꢀ),
105.1 (C-10), 102.6 (C-3), 91.1 (C-8), 56.3 (6-OCH3).
2.3.14. Ethyl caffeate (14)
Yellow amorphous powder; [␣]25D = −4.4 (c 0.1, CH3OH);
ESI–MS: m/z 209 [M+H]+; 1H NMR (400 MHz, CD3OD) ␦H: 7.53
(1H, d, J = 16.0 Hz, H-7), 7.03 (1H, d, J = 1.2 Hz, H-2), 6.94 (1H, d,
J = 8.0 Hz, H-6), 6.77 (1H, d, J = 8.0 Hz, H-5), 6.24 (1H, d, J = 16.0 Hz,
H-8), 4.22 (2H, q, J = 7.2 Hz, H2-1ꢀ) 1.30 (3H, t, J = 7.2 Hz, H3-2ꢀ); 13
C
NMR (100 MHz, CD3OD) ␦C: 169.5 (C-9), 149.7 (C-4), 147.0 (C-7),
146.9 (C-3), 127.9 (C-1), 123.0 (C-5), 116.6 (C-2), 115.4 (C-6), 115.3
(C-8), 61.5 (C-1ꢀ), 14.8 (C-2ꢀ).
2.3.8. Cirsimaritin (8)
Yellow amorphous powder; [␣]25D = −8.0 (c 0.1, CH3OH);
ESI–MS: m/z 315 [M+H]+; 1H NMR (400 MHz, DMSO-d6) ␦H: 13.01
(1H, s, 5-OH), 7.92 (1H, d, J = 8.8 Hz, H-2ꢀ,6ꢀ), 6.92 (1H, s, H-8), 6.85
(1H, d, J = 8.8 Hz, H-3ꢀ,5ꢀ), 6.79 (1H, s, H-3), 3.92 (3H, s, 7-OCH3),
3.73 (3H, s, 6-OCH3); 13C NMR (100 MHz, DMSO-d6) ␦C: 182.0 (C-4),
164.4 (C-2), 163.6 (C-4ꢀ), 158.4 (C-7), 152.5 (C-5), 152.1 (C-9), 131.8
(C-6), 128.5 (C-2ꢀ,6ꢀ), 119.2 (C-1ꢀ), 116.5 (C-3ꢀ,5ꢀ), 105.0 (C-10), 101.8
(C-3), 91.5 (C-8), 60.0 (6-OCH3), 56.4 (7-OCH3).
2.3.15. Rosmarinic acid (15)
Yellow amorphous powder; [␣]25D = +80.0 (c 0.1, CH3OH);
ESI–MS: m/z 361 [M+H]+; 1H NMR (400 MHz, CD3OD) ␦H: 7.55 (1H,
d, J = 16.0 Hz, H-7ꢀ), 7.04 (1H, d, J = 2.0 Hz, H-2ꢀ), 6.95 (1H, dd, J = 8.0
2.0 Hz, H-6ꢀ), 6.78 (1H, d, J = 8.0 Hz, H-5ꢀ), 6.75 (1H, d, J = 2.0 Hz, H-
2), 6.70 (1H, d, J = 8.0 Hz, H-5), 6.61 (1H, dd, J = 8.0, 2.0 Hz, H-6), 6.27
(1H, d, J = 16.0 Hz, H-8ꢀ), 5.18 (1H, d, J = 8.4, 4.4 Hz, H-8), 3.10 (1H, dd,
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