8
Q. Liu et al.
Arch. Pharm. Chem. Life Sci. 2012, 000, 1–13
1.22 (d, 3H, J ¼ 6.0 Hz, H-600); 13C NMR (150 MHz, CDCl3):
d 198.5, 166.9, 166.1, 165.5, 165.3, 164.9, 164.3, 164.1, 163.7,
162.5, 136.3, 136.1, 135.7, 134.7, 133.6, 133.2, 131.6, 128.9,
128.7, 128.3, 128.1, 127.6, 127.3, 127.1, 125.9, 114.1, 110.9,
108.1, 102.5 (C-100), 98.1 (C-1000), 93.7, 89.1, 77.9, 76.1, 75.3,
73.5, 72.0, 71.3, 69.7, 69.5, 67.5, 67.3, 62.1, 26.3, 24.8;
HRESIMS: m/z calcd for C70H62O18Na [MþNa]þ, 1213.3827;
found, 1213.3855.
165.5, 164.9, 163.7, 161.8, 136.6, 135.9, 133.9, 133.5, 130.3,
128.9, 128.1, 126.7, 126.4, 126.2, 125.0, 114.3, 110.5, 104.6,
102.6 (C-100), 100.1 (C-1000), 93.1, 87.1, 78.3, 75.6, 71.3, 69.3,
67.3, 65.1, 61.0, 59.2, 25.3, 23.9, 21.6; HRESIMS: m/z calcd
for C63H58O16Na [MþNa]þ, 1093.3615; found, 1093.3633.
2-O-Benzyl-6-hydroxyl-40-O-benzyl benzophenone
4-O-[2,3,4,6-tetra-O-benzoyl-b-D-glucopyranosyl-
(1!4)-2,3-O-isopropylidene-a-L-rhamnoside (34)
40-O-Benzyl-6-hydroxyl-4-O-benzyl benzophenone
2-O-[2,3,4,6-tetra-O-benzoyl-a-D-mannopyranosyl-
(1!4)-2,3-O-isopropylidene-a-L-rhamnoside (29a)
27
Amorphous white solid; yield: 91%; ½aꢂD ꢃ45.3 (c 1.3, CHCl3);
1H NMR (600 MHz, CDCl3): d 11.50 (brs, OH), 7.33–8.01
(m, 32H), 7.10 (d, 2H, J ¼ 8.8 Hz), 6.51 (d, 1H, J ¼ 2.3 Hz),
6.33 (d, 1H, J ¼ 2.2 Hz), 5.89 (t, 1H, J ¼ 9.6 Hz, H-3000), 5.57
(t, 1H, J ¼ 9.7 Hz, H-4000), 5.43 (t, 1H, J ¼ 9.3 Hz, H-2000), 5.27
(s, 2H), 5.18 (s, 1H, H-100), 5.14 (dd, 1H, J ¼ 2.7, 1.3 Hz, H-200),
5.07 (s, 2H), 5.04 (d, 1H, J ¼ 8.3 Hz, H-1000), 4.43–4.59 (m, 2H,
H-300, H-400, H-500), 3.91 (dd, 1H, J ¼ 12.7, 5.3 Hz, H-6000-1), 3.85
(m, 1H, H-5000), 3.77 (dd, 1H, J ¼ 12.7, 4.5 Hz, H-6000-2), 1.53,
1.36 (s each, 3H each, O–(CH3)2C–O), 1.21 (d, 3H, J ¼ 6.0 Hz,
H-600); 13C NMR (150 MHz, CDCl3): d 197.9, 166.7, 165.5,
165.1, 164.8, 164.7, 164.3, 163.9, 163.5, 162.7, 136.3, 135.8,
134.3, 133.7, 133.1, 131.9, 128.9, 128.7, 128.6, 128.1, 127.9,
126.9, 125.7, 124.9, 114.7, 110.7, 107.1, 101.7 (C-100), 98.3
(C-1000), 94.7, 89.3, 79.1, 78.5, 76.2, 73.7, 72.3, 71.3, 70.9,
69.3, 66.9, 66.3, 62.7, 26.1, 24.7; HRESIMS: m/z calcd
for C70H62O18Na [MþNa]þ, 1213.3827; found, 1213.3861.
27
Amorphous white solid; yield: 83%; ½aꢂD ꢃ54.3 (c 1.2, CHCl3);
1H NMR (600 MHz, CDCl3): d 11.51 (brs, OH), 7.37–8.07
(m, 32H), 7.13 (d, 2H, J ¼ 8.7 Hz), 6.39 (d, 1H, J ¼ 2.3 Hz),
6.17 (d, 1H, J ¼ 2.3 Hz), 5.89 (dd, 1H, J ¼ 9.6, 3.2 Hz, H-3000),
5.67 (t, 1H, J ¼ 9.7 Hz, H-4000), 5.47 (dd, 1H, J ¼ 3.9, 2.8 Hz,
H-2000), 5.26 (s, 2H), 5.21 (s, 1H, H-100), 5.16 (d, 1H, J ¼ 3.5 Hz,
H-1000), 5.11 (brs, 1H, H-200), 5.06 (s, 2H), 4.61–4.79 (m, 3H,
H-400, H-5000, H-6000-1), 4.25–4.36 (m, 3H, H-300, H-500, H-6000-2),
1.59, 1.33 (s each, 3H each, O–(CH3)2C–O), 1.21 (d, 3H,
J ¼ 5.9 Hz, H-600); 13C NMR (150 MHz, CDCl3): d 197.9,
167.1, 166.3, 165.7, 165.3, 164.7, 164.5, 163.9, 163.5, 161.3,
136.5, 136.0, 135.7, 134.7, 133.9, 133.2, 131.7, 128.9, 128.4,
128.3, 127.9, 127.6, 127.1, 126.8, 125.9, 115.3, 110.2, 106.9,
103.1 (C-100), 99.3 (C-1000), 94.1, 85.3, 78.3, 75.6, 75.3, 72.9,
71.3, 68.5, 67.9, 66.6, 59.9, 26.9, 23.8; HRESIMS: m/z calcd
for C70H62O18Na [MþNa]þ, 1213.3829; found, 1213.3863.
2-O-Benzyl-6-hydroxyl-40-O-benzyl benzophenone
4-O-[2,3,4,6-tetra-O-benzoyl-b-D-galactopyranosyl-
(1!4)-2,3-O-isopropylidene-a-L-rhamnoside (35)
40-O-Benzyl-6-hydroxyl-4-O-benzyl benzophenone
2-O-[2,3,4-tri-O-benzoyl-b-D-xylopyranosyl-(1!4)-
2,3-O-isopropylidene-a-L-rhamnoside (30a)
27
Amorphous white solid; yield: 86%; ½aꢂD ꢃ19.3 (c 1.1, CHCl3);
1H NMR (600 MHz, CDCl3): d 11.53 (brs, OH), 7.35–8.07
(m, 32H), 7.13 (d, 2H, J ¼ 8.6 Hz), 6.37 (d, 1H, J ¼ 2.2 Hz),
6.26 (d, 1H, J ¼ 2.2 Hz), 5.83 (dd, 1H, J ¼ 9.7, 3.3 Hz, H-3000),
5.49 (t, 1H, J ¼ 3.2 Hz, H-4000), 5.33 (t, 1H, J ¼ 9.3 Hz, H-2000),
5.27 (s, 2H), 5.24 (d, 1H, J ¼ 7.9 Hz, H-1000), 5.21 (s, 1H, H-100),
5.11 (dd, 1H, J ¼ 2.3, 1.2 Hz, H-200), 5.07 (s, 2H), 4.68–4.87
(m, 2H, H-400, H-6000-1), 4.37–4.45 (m, 3H, H-300, H-500, H-5000),
3.99 (dd, 1H, J ¼ 12.7, 3.7 Hz, H-6000-2), 1.57, 1.31 (s each,
3H each, O–(CH3)2C–O), 1.22 (d, 3H, J ¼ 6.6 Hz, H-600);
13C NMR (150 MHz, CDCl3): d 198.1, 167.0, 166.6, 165.9,
165.3, 164.8, 164.3, 163.9, 163.7, 161.8, 136.3, 136.1, 135.9,
133.7, 133.3, 133.0, 131.6, 128.9, 128.2, 128.1, 127.9, 127.6,
126.9, 125.9, 115.0, 111.2, 107.8, 103.1 (C-100), 97.7 (C-1000), 94.1,
89.5, 78.1, 76.6, 75.4, 73.7, 72.1, 70.5, 69.7, 69.2, 67.3, 66.8, 62.2,
26.1, 24.5; HRESIMS: m/z calcd for C70H62O18Na [MþNa]þ,
1213.3827; found, 1213.3862.
27
Amorphous white solid; yield: 88%; ½aꢂD ꢃ18.6 (c 0.9, CHCl3);
1H NMR (600 MHz, CDCl3): d 11.37 (brs, OH), 7.31–8.02
(m, 27H), 7.07 (d, 2H, J ¼ 8.6 Hz), 6.31 (d, 1H, J ¼ 2.1 Hz),
6.17 (d, 1H, J ¼ 2.1 Hz), 5.79 (t, 1H, J ¼ 9.1 Hz, H-3000), 5.43–
5.53 (m, 2H, H-2000, H-4000), 5.29 (s, 2H), 5.17 (s, 1H, H-100), 5.03
(d, 1H, J ¼ 7.0 Hz, H-1000), 5.07–5.10 (m, 3H), 4.53–4.65 (m, 2H,
H-400, H-5000-1), 4.21–4.33 (m, 3H, H-300, H-500, H-5000-2), 1.59,
1.27 (s each, 3H each, O–CH3)2C–O), 1.19 (d, 3H, J ¼ 6.0 Hz,
H-600); 13C NMR (150 MHz, CDCl3): d 197.6, 166.7, 166.3,
165.3, 164.6, 163.9, 163.6, 162.1, 136.5, 135.7, 134.7, 133.5,
131.7, 128.9, 128.0, 127.9, 127.3, 127.1, 126.4, 125.1, 114.7,
110.3, 105.3, 102.7 (C-100), 96.7 (C-1000), 93.8, 78.9, 75.6, 72.7,
69.9, 68.1, 67.3, 61.6, 58.7, 25.1, 24.3; HRESIMS: m/z calcd
for C62H56O16Na [MþNa]þ, 1079.3461; found, 1079.3493.
40-O-Benzyl-6-hydroxyl-4-O-benzyl benzophenone
2-O-[2,3,4-tri-O-benzoyl-a-L-rhamnosyl-(1!4)-
2,3-O-isopropylidene-a-L-rhamnoside (31a)
2-O-Benzyl-6-hydroxyl-40-O-benzyl benzophenone
4-O-[2,3,4,6-tetra-O-benzoyl-a-D-mannopyranosyl-
(1!4)-2,3-O-isopropylidene-a-L-rhamnoside (36)
1H NMR (600 MHz, CDCl3): d 11.53 (brs, OH), 7.31–8.05
(m, 32H), 7.09 (d, 2H, J ¼ 8.7 Hz), 6.27 (d, 1H, J ¼ 2.6 Hz),
6.11 (d, 1H, J ¼ 2.5 Hz), 5.76 (dd, 1H, J ¼ 9.7, 3.6 Hz, H-3000),
5.46–5.57 (m, 2H, H-2000, H-4000), 5.29 (s, 2H), 5.21 (m, 3H, H-100,
H-200, H-1000), 5.06 (s, 2H), 4.53–4.67 (m, 3H, H-400, H-5000,
H-6000-1), 4.27–4.41 (m, 3H, H-300, H-500, H-6000-2), 1.63, 1.27
(s each, 3H each, O–(CH3)2C–O), 1.23 (d, 3H, J ¼ 6.0 Hz,
H-600); 13C NMR (150 MHz, CDCl3): d 197.3, 166.8, 166.1,
27
Amorphous white solid; yield: 81%; ½aꢂD ꢃ23.1 (c 1.0, CHCl3);
27
1H NMR (600 MHz, CDCl3): d 11.32 (brs, OH), 7.35–7.98
(m, 27H), 7.03 (d, 2H, J ¼ 8.7 Hz), 6.33 (d, 1H, J ¼ 2.3 Hz),
6.09 (d, 1H, J ¼ 2.3 Hz), 5.91 (dd, J ¼ 9.9, 3.5 Hz, 1 H, H-3000),
5.82 (dd, J ¼ 3.3, 1.7 Hz, 1 H, H-2000), 5.77 (brs, 1 H, H-1000),
5.69 (t, J ¼ 9.3 Hz, 1 H, H-4000), 5.31 (s, 2H), 5.11 (s, 1H, H-100),
5.05–5.11 (m, 3H), 4.41–4.55 (m, 2H, H-400, H-5000), 4.26–4.35
(m, 2H, H-300, H-50), 1.59, 1.23 (s each, 3H each,
O–(CH3)2C–O), 1.23 (d, 3H, J ¼ 6.0 Hz, H-6000), 1.20 (d, 3H,
J ¼ 5.9 Hz, H-600); 13C NMR (150 MHz, CDCl3): d 197.3, 165.8,
Amorphous white solid; yield: 85%; ½aꢂD ꢃ37.7 (c 1.0, CHCl3);
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.archpharm.com