Characterization of isolated compounds
1,6-Di-O-galloyl-β-d-glucopyranose (1): Brown amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 7.12 (2H, s, H-2,6I), 7.07 (2H, s, H-2,6VI), 5.68 (1H, d, J = 6.4 Hz, H-1), 4.54 (1H, br d, J = 12.0 Hz, H-6a), 4.39 (1 H, dd, J = 12.0, 4.9 Hz, H-6b), 3.71 (1H, m, H-5), 3.51 (3H, m, H-2, H-3, H-4); 13C NMR (100 MHz, CD3OD) δ: 168.34 (s, C-7VI), 167.03 (s, C-7I), 146.56 (s, C-3,5VI), 146.52 (s, C-3,5I), 140.51 (s, C-4I), 139.93 (s, C-4VI), 121.31 (s, C-1VI), 120.61 (s, C-1I), 110.61 (d, C-2,6I), 110.22 (d, C-2,6VI), 95.98 (d, C-1), 78.07 (d, C-3), 76.51 (d, C-5), 74.14 (d, C-2), 71.23 (d, C-4), 64.47 (t, C-6).
1,2,3-Tri-O-galloyl-β-d-glucopyranose (2): Brown amorphous solid; [α]
D
25
+33.3° (c = 0.04, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.03 (2H, s, H-2,6III), 7.02 (2H, s, H-2,6I), 6.91 (2H, s, H-2,6II), 6.05 (1H, d, J = 8.3 Hz, H-1), 5.53 (1H, t, J = 9.5 Hz, H-3), 5.41 (1H, dd, J = 9.9, 8.2 Hz, H-2), 3.92 (1H, br d, J = 12.9 Hz, H-6a), 3.88 (1H, t, J = 9.7 Hz, H-4), 3.80 (1H, dd, J = 12.2, 4.6 Hz, H-6b), 3.69 (1H, m, H-5); 13C NMR (100 MHz, CD3OD) δ: 167.83 (s, C-7III), 167.20 (s, C-7II), 166.42 (s, C-7I), 146.56 (s, C-4I), 146.39 (s, C-4III), 146.36 (s, C-4II), 140.68 (s, C-3,5I), 140.20 (s, C-3,5II), 139.99 (s, C-3,5III), 121.09 (s, C-1III), 120.51 (s, C-1II), 120.00 (s, C-1I), 110.56 (d, C-2,6I), 110.43 (d, C-2,6III), 110.39 (d, C-2,6II), 93.92 (d, C-1), 79.07 (d, C-5), 76.79 (d, C-3), 72.45 (d, C-2), 69.35 (d, C-4), 61.89 (t, C-6).
1,2,6-Tri-O-galloyl-β-d-glucopyranose (3): Brown amorphous solid; [α]
D
25
−80.7° (c = 0.09, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.11 (2H, s, H-2,6VI), 7.05 (2H, s, H-2,6II), 7.01 (2H, s, H-2,6I), 5.93 (1H, d, J = 8.4 Hz, H-1), 5.22 (1H, t, J = 9.0 Hz, H-2), 4.57 (1H, br d, J = 12.0 Hz, H-6a), 4.47 (1H, dd, J = 12.1, 4.6 Hz, H-6b), 3.84 (1H, m, H-5), 3.83 (1H, m, H-3), 3.67 (1H, t, J = 9.3 Hz, H-4); 13C NMR (100 MHz, CD3OD) δ: 168.30 (s, C-7VI), 167.62 (s, C-7II), 166.54 (s, C-7I), 146.54 (s, C-4VI), 146.51 (s, C-4I), 146.45 (s, C-4II), 140.63 (s, C-3,5I), 140.08 (s, C-3,5II), 139.95 (s, C-3,5VI), 121.30 (s, C-1VI), 121.08 (s, C-1II), 120.02 (s, C-1I), 110.60 (d, C-2,6I), 110.41 (d, C-2,6II), 110.24 (d, C-2,6VI), 94.15 (d, C-1), 76.65 (d, C-5), 76.00 (d, C-3), 74.31 (d, C-2), 71.40 (d, C-4), 64.26 (t, C-6).
1,2,3,6-Tetra-O-galloyl-β-d-glucopyranose (4): Brown amorphous solid; [α]
D
25
+37.4° (c = 0.18, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.13 (2H, s, H-2,6VI), 7.04 (2H, s, H-2,6III), 7.03 (2H, s, H-2,6I), 6.94 (2H, s, H-2,6II), 6.11 (1H, d, J = 8.3 Hz, H-1), 5.59 (1H, dd, J = 9.6, 9.0 Hz, H-3), 5.45 (1H, dd, J = 9.9, 8.3 Hz, H-2), 4.62 (1H, dd, J = 12.4, 1.9 Hz, H-6a), 4.53 (1H, dd, J = 12.1, 4.3 Hz, H-6b), 4.03 (1H, ddd, J = 10.0, 4.3, 1.9 Hz, H-5), 3.97 (1H, dd, J = 9.7, 8.8 Hz, H-4); 13C NMR (100 MHz, CD3OD) δ: 168.19 (s, C-7VI), 167.74 (s, C-7III), 167.20 (s, C-7II), 166.34 (s, C-7I), 146.54 (s, C-4VI), 146.54 (s, C-4I), 146.38 (s, C-4III), 146.35 (s, C-4II), 140.75 (s, C-3,5I), 140.24 (s, C-3,5II), 140.03 (s, C-3,5III), 140.00 (s, C-3,5VI), 121.23 (s, C-1VI), 120.98 (s, C-1III), 120.41 (s, C-1II), 119.84 (s, C-1I), 110.61 (d, C-2,6I), 110.43 (d, C-2,6III), 110.40 (d, C-2,6II), 110.24 (d, C-2,6VI), 93.93 (d, C-1), 76.65 (d, C-5), 76.49 (d, C-3), 72.39 (d, C-2), 69.66 (d, C-4), 64.00 (t, C-6).
1,2,3,4,6-Penta-O-galloyl-β-d-glucopyranose (5): Brown amorphous solid; [α]
D
25
+21.8° (c = 0.29, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.12 (2H, s, H-2VI), 7.06 (2H, s, H-2I), 6.98 (2H, s, H-2IV), 6.95 (2H, s, H-2II), 6.90 (2H, s, H-2III), 6.25 (1H, d, J = 8.3 Hz, H-1), 5.92 (1H, t, J = 9.7 Hz, H-3), 5.63 (1H, t, J = 9.7 Hz, H-4), 5.59 (1H, dd, J = 9.8, 8.4 Hz, H-2), 4.52 (1H, br d, J = 11.1 Hz, H-6a), 4.42 (1H, m, H-5), 4.39 (1H, m, H-6b); 13C NMR (100 MHz, CD3OD) δ: 167.94 (C-7VI), 167.31 (C-7III), 167.03 (C-7II), 166.93 (C-7IV), 166.23 (C-7I), 146.57 (C-3I), 146.49 (C-3VI), 146.46 (C-3IV), 146.39 (C-3II), 146.30 (C-3III), 140.78 (C-4I), 140.37 (C-4IV), 140.32 (C-4II), 140.14 (C-4III), 140.02 (C-4VI), 121.05 (C-1VI), 120.37 (C-1III), 120.25 (C-1II), 120.21 (C-1IV), 119.73 (C-1I), 110.62 (C-2I), 110.47 (C-2IV), 110.41 (C-2II), 110.38 (C-2III), 110.34 (C-2VI), 93.83 (C-1), 74.44 (C-5), 74.13 (C-3), 72.20 (C-2), 69.80 (C-4), 63.13 (C-6).
Tellimagrandin I (2,3-di-O-galloyl-4,6-hexahydroxydiphenoyl-β-d-glucopyranose, 6): Brown amorphous solid; [α]
D
25
+70.5° (c = 0.16, MeOH); 1H NMR (400 MHz, CD3OD) δ: α-anomer (60%): 7.01 (2H, s, H-2,6II), 6.92 (2H, s, H-2,6III), 6.60 (1H, s, H-2VI), 6.49 (1H, s, H-2IV), 5.83 (1H, t, J = 10.0 Hz, H-3), 5.49 (1H, d, J = 3.8 Hz, H-1), 5.32 (1H, dd, J = 12.7, 6.6 Hz, H-6), 5.12 (1H, t, J = 9.9 Hz, H-4), 5.09 (1H, dd, J = 9.4, 4.5 Hz, H-2), 4.64 (1H, dd, J = 10.1, 6.8 Hz, H-5), 3.82 (1H, d, J = 12.8 Hz, H-6); β-anomer (40%): 6.99 (2H, s, H-2,6II), 6.89 (2H, s, H-2,6III), 6.60 (1H, s, H-2VI), 6.45 (1H, s, H-2IV), 5.59 (1H, t, J = 9.7 Hz, H-3), 5.35 (1H, dd, J = 12.8, 6.6 Hz, H-6), 5.19 (1H, dd, J = 9.6, 8.1 Hz, H-2), 5.14 (1H, t, J = 9.9 Hz, H-4), 4.96 (1H, d, J = 8.1 Hz, H-1), 4.21 (1H, dd, J = 9.8, 6.4 Hz, H-5), 3.90 (1H, d, J = 13.0 Hz, H-6); 13C NMR (100 MHz, CD3OD) δ: α anomer: 169.78 (s, C-7VI), 169.32 (s, C-7IV), 167.94 (s, C-7III), 167.48 (s, C-7II), 146.41 (s, C-4II), 146.22 (s, C-4III), 145.94 (s, C-4IV), 145.87 (s, C-4VI), 144.82 (2×, s, C-5IV and C-5VI), 140.16 (s, C-3,5II), 139.93 (s, C-3,5III), 137.62 (2×, s, C-3IV and C-3VI), 126.36 (s, C-1IV), 125.96 (s, C-1VI), 120.79 (s, C-1III), 120.60 (s, C-1II), 116.71 (s, C-6VI), 116.42 (s, C-6IV), 110.46 (d, C-2,6III), 110.42 (d, C-2,6II), 108.66 (d, C-2VI), 108.26 (d, C-2IV), 91.80 (d, C-1), 73.61 (d, C-2), 72.00 (d, C-3), 71.99 (d, C-4), 67.61 (d, C-5), 64.29 (t, C-6); β anomer: 169.68 (s, C-7VI), 169.24 (s, C-7IV), 167.70 (s, C-7III), 167.12 (s, C-7II), 146.38 (s, C-4II), 146.19 (s, C-4III), 145.93 (s, C-4IV), 145.89 (s, C-4VI), 144.82 (2×, s, C-5IV and C-5VI), 140.01 (s, C-3,5II), 139.95 (s, C-3,5III), 137.62 (2×, s, C-3IV and C-3VI), 126.32 (s, C-1IV), 125.89 (s, C-1VI), 120.93 (s, C-1III), 120.59 (s, C-1II), 116.66 (s, C-6VI), 116.46 (s, C-6IV), 110.48 (d, C-2,6III), 110.37 (d, C-2,6II), 108.62 (d, C-2VI), 108.24 (d, C-2IV), 97.12 (d, C-1), 74.82 (d, C-2), 74.33 (d, C-3), 71.69 (d, C-4), 71.59 (d, C-5), 64.22 (t, C-6).
Tellimagrandin II (1,2,3-tri-O-galloyl-4,6-hexahydroxydiphenoyl-β-d-glucopyranose, 7): Brown amorphous solid; [α]
D
25
+32.1° (c = 0.08, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.05 (2H, s, H-2,6I), 6.95 (2H, s, H-2,6II), 6.91 (2H, s, H-2,6III), 6.61 (1H, s, H-2VI), 6.48 (1H, s, H-2IV), 6.11 (1H, d, J = 8.3 Hz, H-1), 5.76 (1H, t, J = 9.7 Hz, H-3), 5.54 (1H, dd, J = 9.3, 8.4 Hz, H-2), 5.39 (1H, dd, J = 13.3, 6.5 Hz, H-6a), 5.23 (1H, t, J = 9.9 Hz, H-4), 4.43 (1H, dd, J = 10.1, 6.4 Hz, H-5), 3.92 (1H, d, J = 13.3 Hz, H-6b); 13C NMR (100 MHz, CD3OD) δ: 169.59 (s, C-7VI), 169.24 (s, C-7IV), 167.57 (s, C-7III), 166.92 (s, C-7II), 166.19 (s, C-7I), 146.62 (s, C-4I), 146.43 (s, C-4II), 146.27 (s, C-4III), 145.86 (s, C-4IV), 145.82 (s, C-4VI), 145.17 (s, C-5IV), 145.15 (s, C-5VI), 140.82 (s, C-3,5I), 140.33 (s, C-3,5II), 140.11 (s, C-3,5III), 137.80 (s, C-3IV), 137.78 (s, C-3VI), 126.24 (s, C-1IV), 126.24 (s, C-1VI), 120.45 (s, C-1III), 120.32 (s, C-1II), 119.74 (s, C-1I), 116.87 (d, C-6VI), 116.69 (d, C-6IV), 110.61 (d, C-2,6I), 110.53 (d, C-2,6III), 110.41 (d, C-2,6II), 108.59 (d, C-2VI), 108.21 (d, C-2IV), 94.2 (d, C-1), 74.07 (d, C-3), 73.64 (d, C-5), 72.47 (d, C-2), 71.28 (d, C-4), 63.73 (t, C-6).
Ethyl gallate (8): Brown amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 7.05 (2H, s, H-2,6), 4.27 (2H, q, J = 7.1 Hz, H-1′), 1.35 (3 H, t, J = 7.1 Hz, H-2′); 13C NMR (100 MHz, CD3OD) δ: 168.58 (s, C-7), 146.50 (s, C-3,5), 139.71 (s, C-4), 121.77 (s, C-1), 110.00 (d, C-2,6), 61.71 (t, C-1′), 14.66 (q, C-2′).
Caffeic acid (9): White amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 7.59 (1H, d, J = 15.9 Hz, H-7), 7.05 (1H, d, J = 2.0 Hz, H-2), 6.95 (1H, dd, J = 8.3, 2.0 Hz, H-6), 6.77 (1H, d, J = 8.2 Hz, H-5), 6.30 (1H, d, J = 15.9 Hz, H-8); 13C NMR (100 MHz, CD3OD) δ: 169.05 (s, C-9), 149.65 (s, C-4), 147.26 (d, C-7), 146.84 (s, C-3), 127.76 (s, C-1), 123.04 (d, C-6), 116.52 (d, C-5), 115.20 (d, C-2), 114.88 (d, C-8).
Astragalin (kaempferol 3-O-β-d-glucopyranoside, 10): Yellow amorphous solid; [α]
D
25
−36.3° (c = 0.43, MeOH); 1H NMR (400 MHz, CD3OD) δ: 8.05 (2H, d, J = 8.7 Hz, H-2′,6′), 6.88 (2H, d, J = 8.8 Hz, H-3′,5′), 6.39 (1H, d, J = 2.0 Hz, H-8), 6.19 (1H, d, J = 2.0 Hz, H-6), 5.26 (1H, d, J = 7.2 Hz, H-1″), 3.69 (1H, dd, J = 11.9, 2.3 Hz, H-6″a), 3.53 (1H, dd, J = 12.0, 5.5 Hz, H-6″b), 3.43 (1H, m, H-2″), 3.42 (1H, m, H-3″), 3.30 (1H, m, H-4″), 3.20 (1H, ddd, J = 9.7, 5.5, 2.3 Hz, H-5″); 13C NMR (100 MHz, CD3OD) δ: 179.53 (s, C-4), 166.21 (s, C-7), 163.11 (s, C-5), 161.61 (s, C-4′), 159.07 (s, C-2), 158.55 (s, C-9), 135.47 (s, C-3), 132.31 (d, C-2′,6′), 122.82 (s, C-1′), 116.10 (d, C-3′,5′), 105.71 (s, C-10), 104.09 (d, C-1″), 99.96 (d, C-6), 94.81 (d, C-8), 78.46 (d, C-5″), 78.07 (d, C-3″), 75.77 (d, C-2″), 71.38 (d, C-4″), 62.65 (t, C-6″).
Isoquercetin (quercetin 3-O-β-d-glucopyranoside, 11): Yellow amorphous solid; [α]
D
25
−24.6° (c = 0.02, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.71 (1H, d, J = 2.2 Hz, H-2′), 7.59 (1H, dd, J = 8.4, 2.0 Hz, H-6′), 6.86 (1H, d, J = 8.5 Hz, H-5′), 6.36 (1H, br s, H-8), 6.18 (1H, d, J = 1.8 Hz, H-6), 5.23 (1H, d, J = 7.5 Hz, H-1″), 3.71 (1H, dd, J = 11.9, 2.3 Hz, H-6″a), 3.57 (1H, dd, J = 11.9, 5.2 Hz, H-6″b), 3.47 (1H, t, J = 8.2 Hz, H-2″), 3.42 (1H, t, J = 8.6 Hz, H-3″), 3.34 (1H, m, H-4″), 3.21 (1H, m, H-5″);
Trifolin (kaempferol 3-O-β-d-galactopyranoside, 12): Yellow amorphous solid; [α]
D
25
−32.4° (c = 0.11, MeOH); 1H NMR (400 MHz, CD3OD) δ: 8.09 (2H, d, J = 8.7 Hz, H-2′,6′), 6.88 (2H, d, J = 8.7 Hz, H-3′,5′), 6.40 (1H, d, J = 1.5 Hz, H-8), 6.20 (1H, d, J = 1.9 Hz, H-6), 5.14 (1H, d, J = 7.8 Hz, H-1″), 3.81 (1H, d, J = 3.5 Hz, H-4″), 3.78 (1H, dd, J = 9.6, 7.9 Hz, H-2″), 3.62 (1H, dd, J = 11.1, 6.1 Hz, H-6″a), 3.52 (1H, m, H-3″), 3.51 (1H, m, H-6″b), 3.43 (1H, t, J = 6.1 Hz, H-5″); 13C NMR (100 MHz, CD3OD) δ: 166.40 (s, C-7), 163.10 (s, C-5), 161.65 (s, C-4′), 159.04 (s, C-2), 158.57 (s, C-9), 135.59 (s, C-3), 132.40 (d, C-2′,6′), 122.73 (s, C-1′), 116.14 (d, C-3′,5′), 105.61 (s, C-10), 105.00 (d, C-1″), 100.02 (d, C-6), 94.85 (d, C-8), 77.17 (d, C-5″), 75.07 (d, C-3″), 73.05 (d, C-2″), 70.05 (d, C-4″), 62.01 (t, C-6″).
Kaempferol 3-O-β-d-xylopyranoside (13): Yellow amorphous solid; [α]
D
25
−63.8° (c = 0.18, MeOH); 1H NMR (400 MHz, CD3OD) δ: 8.03 (2H, d, J = 8.8 Hz, H-2′,6′), 6.88 (2H, d, J = 8.8 Hz, H-3′,5′), 6.40 (1H, d, J = 2.1 Hz, H-8), 6.20 (1H, d, J = 2.0 Hz, H-6), 5.19 (1H, d, J = 7.2 Hz, H-1″), 3.77 (1H, dd, J = 11.5, 5.1 Hz, H-5″a), 3.48 (1H, m, H-2″), 3.48 (1H, m, H-4″), 3.40 (1H, t, J = 8.6 Hz, H-3″), 3.11 (1H, dd, J = 11.6, 9.6 Hz, H-5″b); 13C NMR (100 MHz, CD3OD) δ: 179.4 (s, C-4), 166.1 (s, C-7), 163.0 (s, C-5), 161.6 (s, C-4′), 158.9 (s, C-2), 158.4 (s, C-9), 135.3 (s, C-3), 132.2 (d, C-2′,6′), 122.6 (s, C-1′), 116.1 (d, C-3′,5′), 105.6 (s, C-10), 104.6 (d, C-1″), 99.9 (d, C-6), 94.8 (d, C-8), 77.5 (d, C-3″), 75.3 (d, C-2″), 71.0 (d, C-4″), 67.2 (t, C-5″).
Reinutrin (quercetin 3-O-β-xylopyranoside, 14): Brown amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 7.60 (1H, m, H-2′), 7.59 (1H, m, H-6′), 6.85 (1H, d, J = 8.4 Hz, H-5′), 6.39 (1H, br s, H-8), 6.20 (1H, br s, H-6), 5.18 (1H, d, J = 7.2 Hz, H-1″), 3.78 (1H, dd, J = 11.6, 5.2 Hz, H-5″a), 3.51 (1H, m, H-2″), 3.50 (1H, m, H-4″), 3.39 (1H, t, J = 8.6 Hz, H-5″b), 3.09 (1H, dd, J = 11.7, 9.6 Hz, H-5″b). 13C NMR (100 MHz, CD3OD) δ: 166.6 (C-7), 163.1 (C-5), 159.8 (C-2), 158.5 (C-9), 149.9 (C-4′), 146.1 (C-3′), 135.4 (C-3), 123.3 (C-6′), 123.1 (C-1′), 117.2 (C-2′), 116.0 (C-5′), 106.3 (C-10), 105.5 (C-1″), 100.1 (C-6), 94.8 (C-8), 77.6 (C-3″), 75.3 (C-2″), 71.0 (C-4″), 67.3 (C-5″).
Juglanin (kaempferol 3-O-α-l-arabinofuranoside, 15): Yellow amorphous solid; [α
D
25
] −112.9° (c = 0.16, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.96 (2H, d, J = 8.5 Hz, H-2′,6′), 6.93 (2H, d, J = 8.5 Hz, H-3′,5′), 6.41 (1H, d, J = 2.1 Hz, H-8), 6.21 (1H, d, J = 2.1 Hz, H-6), 5.49 (1H, s, H-1″), 4.33 (1H, d, J = 3.0 Hz, H-2″), 3.91 (1H, dd, J = 5.2, 3.1 Hz, H-3″), 3.80 (1H, dd, J = 9.3, 4.7 Hz, H-4″), 3.49 (2H, d, J = 4.2 Hz, H-5″); 13C NMR (100 MHz, CD3OD) δ: 179.95 (s, C-4), 166.04 (s, C-7), 163.12 (s, C-5), 161.60 (s, C-4′), 159.42 (s, C-2), 158.59 (s, C-9), 134.96 (s, C-3), 132.02 (d, C-2′,6′), 122.80 (s, C-1′), 116.54 (d, C-3′,5′), 109.65 (d, C-1″), 105.69 (s, C-10), 99.90 (d, C-6), 94.82 (d, C-8), 88.03 (d, C-4″), 83.39 (d, C-2″), 78.66 (d, C-3″), 62.55 (t, C-5″).
Avicularin (quercetin 3-O-α-arabinofuranoside, 16): Orange amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 7.53 (1H, d, J = 2.1 Hz, H-2′), 7.50 (1H, dd, J = 8.3, 2.1 Hz, H-6′), 6.91 (1H, d, J = 8.3 Hz, H-5′), 6.40 (1H, d, J = 2.1 Hz, H-8), 6.22 (1H, d, J = 1.9 Hz, H-6), 5.47 (1H, s, H-1″), 4.33 (1H, s, H-2″), 3.92 (1H, dd, J = 5.2, 2.9 Hz, H-3″), 3.86 (1H, m, H-4″), 3.50 (2H, m, H-5″); 13C NMR (100 MHz, CD3OD) δ: 180.02 (s, C-4), 166.20 (s, C-7), 163.12 (s, C-5), 159.38 (s, C-2), 158.62 (s, C-9), 149.90 (s, C-4′), 146.41 (s, C-3′), 134.94 (s, C-3), 123.13 (s, C-1′), 122.99 (d, C-6′), 116.86 (d, C-2′), 116.47 (d, C-5′), 109.55 (d, C-1″), 105.62 (s, C-10), 99.95 (d, C-6), 94.83 (d, C-8), 88.05 (d, C-4″), 83.35 (d, C-2″), 78.73 (d, C-3″), 62.57 (t, C-5″).
Juglalin (kaempferol 3-O-α-arabinopyranoside, 17): Yellow amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 8.06 (2H, d, J = 8.6 Hz, H-2′,6′), 6.89 (2H, d, J = 8.5 Hz, H-3′,5′), 6.40 (1H, d, J = 2.0 Hz, H-8), 6.20 (1H, d, J = 1.9 Hz, H-6), 5.14 (1H, d, J = 6.4 Hz, H-1″), 3.89 (1H, dd, J = 8.2, 6.3 Hz, H-2″), 3.78 (1H, m, H-4″), 3.77 (1H, m, H-5″a), 3.63 (1H, m, H-3″), 3.40 (1H, dd, J = 13.5, 3.1 Hz, H-5″b); 13C NMR (100 MHz, CD3OD) δ: 179.58 (s, C-4), 166.42 (s, C-7), 163.11 (s, C-5), 161.68 (s, C-4′), 158.84 (s, C-2), 158.53 (s, C-9), 135.58 (s, C-3), 132.30 (d, C-2′,6′), 122.66 (s, C-1′), 116.29 (d, C-3′,5′), 105.60 (s, C-10), 104.41 (d, C-1″), 100.04 (d, C-6), 94.86 (d, C-8), 74.04 (d, C-3″), 72.80 (d, C-2″), 68.97 (d, C-4″), 66.78 (t, C-5″).
Benzyl 2-O-β-glucopyranosyl-2,6-hydroxybenzoate (18): Yellowish oil; [α
D
25
] −14.8° (c = 0.047, MeOH); 1H NMR (400 MHz, CD3OD) δ: 7.50 (2H, d, J = 7.4 Hz, H-2′,6′), 7.38 (2H, t, J = 7.4 Hz, H-3′,5′), 7.32 (1H, t, J = 7.1 Hz, H-4′), 7.27 (1H, t, J = 8.3 Hz, H-4), 6.75 (1H, d, J = 8.4 Hz, H-3), 6.59 (1H, d, J = 8.4 Hz, H-5), 5.38 (2H, s, H-7′), 4.94 (1H, d, J = 6.4 Hz, H-1″), 3.86 (1H, br d, J = 12.2 Hz, H-6″a), 3.66 (1H, dd, J = 12.2, 5.7 Hz, H-6″b), 3.43 (1H, m, H-5″), 3.39 (1H, m, H-2″), 3.39 (1H, m, H-3″), 3.34 (1 H, m, H-4″); 13C NMR (100 MHz, CD3OD) δ: 170.00 (s, C-7), 159.80 (s, C-6), 158.25 (s, C-2), 137.40 (s, C-1′), 134.04 (d, C-4), 129.55 (d, C-3′,5′), 129.22 (2×, d, C-2′,6′, C-4′), 111.57 (d, C-5), 110.87 (s, C-1), 107.79 (d, C-3), 102.75 (d, C-1″), 78.34 (d, C-3″), 77.99 (d, C-5″), 74.93 (d, C-2″), 71.25 (d, C-4″), 68.19 (t, C-7′), 62.54 (t, C-6″).
Byzantionoside B (19): Orange amorphous solid; 1H NMR (400 MHz, CD3OD) δ: 5.81 (1H, s, H-4), 4.33 (1H, d, J = 8.0 Hz, H-1′), 3.87 (1H, m, H-9), 3.86 (1H, m, H-6′a), 3.65 (1H, m, H-6′b), 3.35 (1H, m, H-3′), 3.26 (1H, m, H-4′), 3.26 (1H, m, H-5′), 3.14 (1H, dd, J = 9.1, 7.8 Hz, H-2′), 2.47 (1H, d, J = 17.4 Hz, H-2), 2.05 (3H, d, J = 1.3 Hz, H-13), 1.98 (1H, m, H-6), 1.97 (1H, m, H-2), 1.95 (1H, m, H-7), 1.63 (2H, m, H-8), 1.51 (1H, m, H-7), 1.19 (3H, d, J = 6.2 Hz, H-10), 1.10 (3H, s, H-12), 1.01 (3H, s, H-11); 13C NMR (100 MHz, CD3OD) δ: 202.48 (s, C-3), 170.17 (s, C-5), 125.41 (d, C-4), 102.15 (d, C-1′), 78.20 (d, C-3′), 77.93 (d, C-5′), 75.54 (d, C-9), 75.20 (d, C-2′), 71.88 (d, C-4′), 62.95 (t, C-6′), 52.43 (d, C-6), 48.12 (t, C-2), 37.84 (t, C-8), 37.36 (s, C-1), 29.10 (q, C-11), 27.56 (q, C-12), 26.87 (t, C-7), 25.01 (q, C-13), 19.91 (q, C-10).