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170.7, 170.2, 170.1, 170.0 (C]O), 156, 136, 128.5, 128.3, 98.2 (C- 6), 4.14 (d, 1H, J ¼ 2.9 Hz H-4), 4.03 (dt, J1 ¼ 7.4 Hz, J2 ¼ 0.9 Hz,
1), 72.2, 71.5, 69.3, 68.9, 67.1, 63.5, 54.2, 52.8, 29.6 (2 ꢂ CH3 of 1H, H-5), 2.13 (s, 3H, COCH3), 2.10 (s, 3H, COCH3); 13C NMR:
COCH3), 25.8 (CH3 of C(CH3)3), 20.9 (2 ꢂ CH3 of COCH3), 18.2 (CDCl3): d (ppm) 170.7, 170.3 (C]O), 150.3, 141.4, 133.6, 125.1,
(CH3 of COCH3), ꢁ5.4 (CH3 of Si(CH3)2); IR: (neat) nmax 3361, 123.4, 118.9, 100.4 (C-1), 74.0, 71.1, 68.7, 66.7, 62.2, 20.7 (2 ꢂ
3034, 2927, 2855, 1748 (CO), 1530, 1462, 1438, 1371, 1248, 1141, CH3 of COCH3); IR: (neat) nmax 3445, 2924, 2854, 1743 (CO),
1048, 984, 836 cmꢁ1; ESI-HRMS: m/z calcd for C28H44NO12Si 1607, 1529, 1487, 1370, 1237, 1073, 748 cmꢁ1. ESI-HRMS: m/z
614.2633. Found: 614.2632 [M + H]+.
4.6.5 p-Nitrophenyl 3,4,6-tri-O-acetyl-b-D-galactopyrano-
calcd for C16H19NNaO10 408.0901. Found: 408.0900 [M + Na]+.
4.6.9 o-Nitrophenyl 4,6-di-O-acetyl-b-D-galactopyranoside
side (84). Viscous oil (0.8 g, 57%); [a]2D0 ꢁ15.2ꢀ (c ¼ 1, CH2Cl2); (92). 1H NMR (CDCl3): d (ppm) 7.88 (dd, J1 ¼ 8.1 Hz, J2 ¼ 1.4 Hz,
1H NMR (CDCl3): d (ppm) 8.22 (dd, J1 ¼ 9.2 Hz, J2 ¼ 3.7 Hz, 2H, 1H, H-30, ArNO2), 7.58–7.56 (m, 1H, H-40, ArNO2), 7.39–7.36 (m,
H-30, H-50, ArNO2), 7.16 (dd, J1 ¼ 9.2 Hz, J2 ¼ 3.2 Hz, 2H, H-20, H- 1H, H-50, ArNO2), 7.21–7.17 (m, 1H, H-60, ArNO2), 5.44 (d, J ¼
60, ArNO2), 5.46 (d, J ¼ 3.1 Hz, 1H, H-4), 5.14 (d, J ¼ 7.6 Hz, H-1), 2.8 Hz, 1H, H-4), 4.97 (d, J ¼ 7.4 Hz, 1H, H-1), 4.22–4.20 (m, 2H,
5.07 (dd, J1 ¼ 3.4 Hz, J2 ¼ 10.2 Hz, 1H, H-3), 4.23–4.11 (m, 4H, H- H-6), 4.09 (t, J ¼ 6.3 Hz, 1H, H-5), 4.02 (t, J ¼ 4.0 Hz, 1H, H-2),
2, H-5, H-6a & H-6b), 2.16 (s, 3H, COCH3), 2.04 (s, 6H, 2 ꢂ 3.96 (dd, J1 ¼ 9.7 Hz, J2 ¼ 3.3 Hz, 1H, H-3), 2.21 (s, 3H,
COCH3), 2.02 (s, 3H, COCH3); 13C NMR: (CDCl3): d (ppm) 170.4, COCH3), 2.12 (s, 3H, COCH3); 13C NMR: (CDCl3): d (ppm) 170.9,
170.3, 170.1 (C]O), 161, 143.0, 125.7, 116.6, 100.4 (C-1), 72.5, 170.5 (C]O), 150.3, 141.3, 134.4, 125.6, 123.3, 119.4, 102.8 (C-
71.3, 68.5, 66.9, 61.9, 20.7 (CH3 of COCH3), 20.5 (2 ꢂ CH3 of 1), 72.9, 71.8, 71.3, 68.7, 62.7, 20.8 (2 ꢂ CH3 of COCH3); IR:
COCH3); IR: (neat) nmax 3439, 2924, 2927, 1747 (CO), 1611, 1593, (Neat) nmax 3419, 2924, 1742 (CO), 1607, 1528, 1370, 1238, 1070,
1518, 1372, 1345, 1240, 1074, 862, 751 cmꢁ1; ESI-HRMS: m/z 749 cmꢁ1. ESI-HRMS: m/z calcd for C16H19NNaO10 408.0907.
calcd for C18H21NaNO11 450.1007. Found: 450.1003 [M + Na]+.
Found: 408.0903 [M + Na]+.
4.6.6 m-Nitrophenyl 2,3,6-tri-O-acetyl-b-D-galactopyrano-
4.6.10 o-Nitrophenyl 2,6-di-O-acetyl-b-D-galactopyranoside
side (87). Crystalline solid (1.0 g, 78%), mp 149–160 ꢀC; (93). 1H NMR (CDCl3): d (ppm) 7.79 (dd, J1 ¼ 8.1 Hz, J2 ¼ 1.4 Hz,
[a]2D0 ꢁ10.6ꢀ (c ¼ 0.5, CH2Cl2); 1H NMR (CDCl3): d (ppm) 7.97 (d, 1H, H-30, ArNO2), 7.56–7.52 (m, 1H, H-40, ArNO2), 7.39–7.37 (m,
J ¼ 8.0 Hz, 1H, H-40, ArNO2), 7.90 (d, J ¼ 2.0 Hz, 1H, H-20, 1H, H-50, ArNO2), 7.21–7.19 (m, 1H, H-60, ArNO2), 5.33 (t, J ¼
ArNO2), 7.49 (t, J ¼ 8.2 Hz, 1H, H-50, ArNO2), 7.72 (d, J ¼ 8.0 Hz, 9.0 Hz, 1H, H-2), 5.00 (d, J ¼ 7.9 Hz, 1H, H-1), 4.42–4.41 (m, 2H,
1H, H-60, ArNO2), 5.59 (dd, J1 ¼ 7.9 Hz, J2 ¼ 10.2 Hz, 1H, H-2), H-6), 4.03–4.00 (m, 1H, H-4), 3.90 (t, J ¼ 6.2 Hz, 1H, H-5), 3.80
5.14 (d, J ¼ 7.9 Hz, 1H, H-1), 5.09 (dd, J1 ¼ 10.3 Hz, J2
¼
(dd, J1 ¼ 9.5 Hz, J2 ¼ 3.1 Hz, 1H, H-3), 2.21 (s, 3H, COCH3), 2.11
3.12 Hz, 1H, H-3), 4.45 (dd, J1 ¼ 4.8 Hz, J2 ¼ 11.8 Hz, 1H, H-6a), (s, 3H, COCH3); 13C NMR: (CDCl3): d (ppm) 171.7, 170.9 (C]O),
4.37 (dd, J1 ¼ 7.4 Hz, J2 ¼ 11.8 Hz, 1H, H-6b), 4.19–4.16 and 149.5, 140.5, 133.6, 125.0, 123.2, 118.6, 100.4 (C-1), 72.2, 71.8,
4.04–4.00 (2m, 3H, H-4, H-5 & OH), 2.19 (s, 3H, COCH3), 2.09 (s, 71.5, 68.4, 61.9, 20.7 (2 ꢂ CH3 of COCH3); IR: (neat) nmax 3419,
6H, 2 ꢂ COCH3), 2.02 (s, 3H, COCH3); 13C NMR: (CDCl3): 2924, 1742 (CO), 1607, 1528, 1370, 1238, 1070, 749 cmꢁ1. ESI-
d (ppm) 170.5, 170.1, 169.9, 169.2 (C]O), 157.0, 149.1, 130.17, HRMS: m/z calcd for C16H19NNaO10 408.0901. Found:
123.7, 118.1, 111.3, 99.2 (C-1), 71.6, 70.6, 68.3, 66.9, 61.7, 20.6 408.0902 [M + Na]+.
(CH3 of COCH3), 20.5 (3 ꢂ CH3 of COCH3); IR: (neat) nmax 3459,
4.6.11 p-Nitrophenyl 3-O-acetyl-4,6-O-benzylidene-b-D-gal-
2933, 1746 (CO), 1634, 1532, 1352, 1230, 1080, 1141, 1048, 749 actopyranoside (95). Colourless solid (0.7 g, 60%), mp 201–
cmꢁ1; ESI-HRMS: m/z calcd for C21H26O11Na 477.1373. Found: 208 C; [a]D ꢁ18.3ꢀ (c ¼ 1, CHCl3); H NMR (CDCl3): d (ppm)
20
1
ꢀ
477.1370 [M + Na]+.
8.22 (dt, J1 ¼ 9.2 Hz, J2 ¼ 3.3 Hz, 2H, H-30, ArNO2), 7.51–7.49 (m,
4.6.7 o-Nitrophenyl
2,4,6-tri-O-acetyl-b-D-galactopyrano- 2H, ArH), 7.39–7.35 (m, 3H, ArH), 7.16 (dt, J1 ¼ 9.2 Hz, J2 ¼
1
side (90). H NMR (CDCl3): d (ppm) 7.88 (dd, J1 ¼ 8.1 Hz, J2 ¼ 3.3 Hz, 2H, H-20, ArNO2), 5.54 (s, 1H, CH of PhCH), 5.14 (d, J ¼
1.6 Hz, 1H, H-30, ArNO2), 7.58–7.56 (m, 1H, H-40, ArNO2), 7.42– 7.7 Hz, 1H, H-1), 4.99 (dd, J1 ¼ 10.2 Hz, J2 ¼ 3.5 Hz, 1H, H-3),
7.40 (m, 1H, H-50, ArNO2), 7.23–7.19 (m, 1H, H-60, ArNO2), 5.43– 4.49 (d, J ¼ 2.9 Hz, 1H, H-4), 4.38–4.34 (m, 1H, H-2), 4.35 (dd,
5.42 (m, 1H, H-4), 5.33 (dd, J1 ¼ 10.0 Hz, J2 ¼ 7.8 Hz, 1H, H-2), J1 ¼ 12.6 Hz, J2 ¼ 1.5 Hz, 1H, H-6a, CH2), 4.15 (dd, J1 ¼ 12.6 Hz,
5.07 (d, J ¼ 7.9 Hz, 1H, H-1), 4.41 (d, J ¼ 6.4 Hz, 2H, H-6), 3.97 J2 ¼ 1.5 Hz, 1H, H-6b, CH2), 3.73 (s, 1H, H-5), 2.18 (s, 3H,
(dd, J1 ¼ 9.7 Hz, J2 ¼ 3.2 Hz, 1H, H-3), 3.96 (t, 1H, J ¼ 6.4 Hz, H- COCH3); 13C NMR: (CDCl3): d (ppm) 171.0 (C]O), 161.6, 142.9,
5), 2.23 (s, 3H, COCH3), 2.22 (s, 3H, COCH3), 2.11 (s, 3H, 137.3, 129.1, 128.2, 126.1, 125.7, 116.7, 101.0, 100.5, 73.4, 73.0,
COCH3); 13C NMR: (CDCl3): d (ppm) 171.3, 170.7, 170.3 (C]O), 68.7, 68.0, 66.8, 21.0 (CH3 of COCH3); IR: (neat) nmax 3482, 2992,
149.4, 141.4, 134.5, 125.6, 123.5, 119.4, 103.6 (C-1), 74.0, 72.8, 2936, 2864, 1755 (C]O), 1593, 1519, 1347, 1230, 1089, 994, 910,
71.5, 69.2, 66.7, 61.9, 20.7 (3 ꢂ CH3 of COCH3); IR: (Neat) nmax 850, 750 cmꢁ1; anal. calcd for C21H21NO9: C, 58.47; H, 4.91; N,
3445, 2924, 2854, 1743 (CO), 1607, 1529, 1487, 1370, 1237, 1073, 3.25. Found: C, 58.12; H, 5.02; N, 2.87. ESI-MS: m/z calcd for
748 cmꢁ1. ESI-HRMS: m/z calcd for C18H21NNaO11 450.1007.
C
21H21NO9 431.12. Found: 431.21 [M]+.
4.6.12 3-Methoxy-4-(2,3,6-tri-O-acetyl-b-D-glucopyr-
Found: 450.1006 [M + Na]+.
4.6.8 o-Nitrophenyl 3,6-di-O-acetyl-b-D-galactopyranoside anosyloxy)acetophenone (98). Viscous oil (1.05 g, 77%);
1
(91). 1H NMR (CDCl3): d (ppm) 7.82 (dd, J1 ¼ 8.0 Hz, J2 ¼ 1.6 Hz, [a]2D0 ꢁ39.5ꢀ (c ¼ 1.5, CH2Cl2); H NMR (CDCl3): d (ppm) 7.52
1H, H-30, ArNO2), 7.58–7.55 (m, 1H, H-40, ArNO2), 7.38–7.28 (m, (dd, J ¼ 2 Hz, 1H, H-2, ArNO2), 7.51 (dd, J1 ¼ 8.2 Hz, J2 ¼ 1.9 Hz,
1H, H-50, ArNO2), 7.24–7.20 (m, 1H, H-60, ArNO2), 5.01 (dd, J1 ¼ 1H, H-6, ArNO2), 7.14 (d, J ¼ 8.2 Hz, 1H, H-5, Ar NO2), 5.28 (dd,
10.2 Hz, J2 ¼ 3.2 Hz, 1H, H-3), 4.97 (d, J ¼ 7.6 Hz, 1H, H-1), 4.23 J1 ¼ 7.7 Hz, J2 ¼ 9.5 Hz, 1H, H-20), 5.14 (dd, J1 ¼ 8.8 Hz, J2 ¼
(dd, 1H, J1 ¼ 7.8 Hz, J2 ¼ 10.2 Hz, H-2), 4.22 (d, J ¼ 6.3 Hz, 2H, H- 9.4 Hz, 1H, H-30), 5.06 (d, J ¼ 7.7 Hz, 1H, H-10), 4.49 (dd, J1 ¼
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RSC Adv., 2017, 7, 13653–13667 | 13665