F. Bouchikhi et al. / European Journal of Medicinal Chemistry 43 (2008) 755e762
761
3
H, CH ), 2.05 (s, 3H, CH ), 4.10e4.19 (m, 2H), 4.32e4.39
3
J ¼ 7.5 Hz, 1H), 7.49e7.57 (m, 1H), 8.02 (dd, J ¼ 8.5 Hz,
3
1
(
5
m, 1H), 5.28e5.39 (m, 1H), 5.58 (t, J ¼ 8.5 Hz, 1H), 5.54e
J ¼ 1.5 Hz, 1H), 9.11 (d, J ¼ 8.0 Hz, 1H), 9.64 (s, 1H),
2
1
3
.70 (m, 1H), 6.11e6.20 (m, 1H), 6.82 (d, J ¼ 8.5 Hz, 1H),
.11 (t, J ¼ 7.5 Hz, 1H), 7.47 (t, J ¼ 7.5 Hz, 1H), 7.49e7.58
11.36 (s, 1H, NH). C NMR (100 MHz, DMSO-d ): 13.7,
6
7
19.9, 20.3, 20.4, 20.5 (CH ), 17.5, 39.4, 61.9 (CH ), 67.4,
3
2
(
m, 2H), 9.13 (d, J ¼ 8.0 Hz, 1H), 9.17 (s, 1H), 11.11 (s,
67.8, 72.5, 73.0, 78.3 (CH), 109.6, 112.1, 122.4, 129.0,
129.6, 133.1, 133.4 (CH), 120.8, 121.3, 130.5, 131.9, 133.7,
141.2, 148.0 (C), 166.9, 168.8, 168.9, 169.4, 169.5, 170.0,
198.4 (C]O).
1
3
1
2
1
1
1
H, NH). C NMR (100 MHz, DMSO-d ): 19.9, 20.3, 20.4,
6
0.5 (CH ), 61.9 (CH ), 67.3, 67.8, 72.5, 73.1, 78.3 (CH),
3
2
11.6, 112.1, 122.5, 129.1, 131.3, 133.2, 135.1 (CH), 112.8,
20.7, 123.2, 132.2, 133.3, 141.3, 143.5 (C), 167.0, 168.2,
68.8, 169.4, 169.5, 170.0 (C]O).
0
4.1.10.9. 6-Nitro-5 -(1-oxobutyl)-1-(2,3,4,6-tetra-O-acetyl-b-
D-glucopyranosyl)isoindigo 25. Yield: 63%. Red solid
0
ꢀ
ꢂ1
4
.1.10.6. 5 -Chlorosulfonyl-1-(2,3,4,6-tetra-O-acetyl-b-D-glu-
(mp > 250 C). IR (KBr): n
ꢂ1
1618 cm ; nC]O 1690e
1780 cm ; nNH 3125e3670 cm . HRMS (ES) calcd for
C]C
ꢂ1
copyranosyl)isoindigo
22. Yield:
9%.
Red
1611 cm ; nC]O 1690e
solid
ꢀ
ꢂ1
þ
1
(
1
mp ¼ 235 C). IR (KBr): n
C H N NaO (M þ Na) 730.1860, found 730.1886. H
C]C
34 33
3
14
ꢂ1
ꢂ1
795 cm ; n
3200e3600 cm . HRMS (ES) calcd for
NMR (400 MHz, DMSO-d ): 0.95 (t, J ¼ 7.5 Hz, 3H, CH ),
2 3
NH
6
3
3
27
5
þ
C H ClN NaO S (M þ Na) 713.0820, found 713.0841.
1.68 (sext, J ¼ 7.5 Hz, 2H, CH ), 1.79 (s, 3H, CH ), 1.98 (s,
3 3 3
3
0
2
13
1
H NMR (400 MHz, DMSO-d ): 1.78 (s, 3H, CH ), 1.95 (s,
3
3H, CH ), 2.06 (s, 3H, CH ), 2.07 (s, 3H, CH ), 2.95 (t,
J ¼ 7.0 Hz, 2H, CH ), 4.14 (dd, J ¼ 12.5 Hz, J ¼ 2.0 Hz,
6
3
H, CH ), 2.03 (s, 3H, CH ), 2.04 (s, 3H, CH ), 4.12e4.18
3
3
3
2
1
2
(
(
(
1
(
m, 2H), 4.33e4.40 (m, 1H), 5.27e5.37 (m, 1H), 5.51e5.68
m, 2H), 6.11e6.22 (m, 1H), 6.79 (d, J ¼ 8.0 Hz, 1H), 7.09
t, J ¼ 7,0 Hz, 1H), 7.44 (t, J ¼ 7.0 Hz, 1H), 7.48e7.54 (m,
1H), 4.24 (dd, J ¼ 12.5 Hz, J ¼ 3.5 Hz, 1H), 4.42e4.48
1
2
(m, 1H), 5.26e5.37 (m, 1H), 5.49e5.68 (m, 1H), 5.68 (t,
J ¼ 9.0 Hz, 1H), 6.29 (d, J ¼ 9.0 Hz, 1H), 6.97 (d,
J ¼ 8.0 Hz, 1H), 8.00 (dd, J ¼ 9.0 Hz, J ¼ 2.0 Hz, 1H),
H), 7.63 (d, J ¼ 7.5 Hz, 1H), 9.10 (d, J ¼ 7.5 Hz, 1H), 9.28
1
2
1
s, 1H), 11.04 (s, 1H, NH). C NMR (100 MHz, DMSO-
3
8.07 (d, J ¼ 8.0 Hz, 1H), 8.15 (d, J ¼ 1.5 Hz, 1H), 9.32 (d,
1
3
d ): 20.0, 20.3, 20.4, 20.5 (CH ), 61.8 (CH ), 67.3, 67.8,
J ¼ 9.0 Hz, 1H), 9.62 (s, 1H) 11.47 (s, 1H, NH). C NMR
(100 MHz, DMSO-d ): 13.7, 19.9, 20.3 (2C), 20.4 (CH ),
17.4, 39.5, 61.1 (CH ), 67.2, 67.7, 72.0, 73.1, 78.8 (CH),
6
3
2
7
1
1
2.6, 73.1, 78.3 (CH), 108.6, 112.0, 122.3, 127.0, 128.7,
30.8, 132.6 (CH), 120.6, 120.9, 134.8, 141.1, 142.1 (2C),
44.5 (C), 166.7, 168.8, 168.9, 169.4 (2C), 170.1 (C]O).
6
3
2
105.9, 110.0, 117.6, 129.5, 130.4, 134.8 (CH), 121.0, 126.4,
129.2, 130.7, 137.8, 141.5, 149.0, 149.1 (C), 166.5, 168.5,
169.1, 169.3, 169.5, 170.0, 198.2 (C]O).
0
4
.1.10.7. 5 -N-Methylaminosulfonyl-1-(2,3,4,6-tetra-O-acetyl-
b-D-glucopyranosyl)isoindigo 23. Yield: 10%. Red solid
ꢀ
ꢂ1
0
(
1
mp ¼ 231 C). IR (KBr): n
1617 cm ; nC]O 1700e
3230e3610 cm . HRMS (ES) calcd for
4.1.10.10. 7 -Aza-1-(2,3,4,6-tetra-O-acetyl-b-D-glucopyranosyl)-
C]C
ꢂ1
ꢂ1
ꢀ
780 cm ; n
isoindigo 26. Yield: 10%. Red solid (mp ¼ 196 C). IR
NH
þ
1
ꢂ1
ꢂ1
C H N NaO S (M þ Na) 708.1475, found 708.1496. H
(KBr): n
1603 cm ; n
1690e1790 cm ; n
NH
3
1
31
3
13
C]C
C]O
ꢂ1
3240e3625 cm . HRMS (ES): calcd for C H N O
29 28 3 11
NMR (400 MHz, DMSO-d ): 1.78 (s, 3H, CH ), 1.96 (s, 3H,
6
3
þ
1
CH ), 2.03 (s, 3H, CH ), 2.05 (s, 3H, CH ), 2.44 (d,
3
(M þ H) 594.1724, found 594.1712. H NMR (500 MHz,
3
3
J ¼ 4.5 Hz, 3H), 4.10e4.19 (m, 2H), 4.35e4.42 (m, 1H),
DMSO-d ): 1.77 (s, 3H, CH ), 1.96 (s, 3H, CH ), 2.02 (s,
6
3
3
5
7
.29e5.39 (m, 1H), 5.53e5.68 (m, 2H), 6.13e6.22 (m, 1H),
.05 (d, J ¼ 8.0 Hz, 1H), 7.12 (t, J ¼ 7.5 Hz, 1H), 7.29e7.35
3H, CH ), 2.05 (s, 3H, CH ), 4.10e4.18 (m, 2H), 4.33e4.40
3 3
(m, 1H), 5.27e5.41 (m, 1H), 5.52e5.68 (m, 2H), 6.04e6.16
(m, 1H), 7.06 (dd, J ¼ 7.5 Hz, J ¼ 5.5 Hz, 1H), 7.13 (t,
(
m, 1H, NH), 7.48 (t, J ¼ 7.5 Hz, 1H), 7.52e7.57 (m, 1H),
1
2
7
1
1
7
1
1
.78 (d, J ¼ 8.0 Hz, 1H), 9.13 (d, J ¼ 8.0 Hz, 1H), 9.46 (s,
J ¼ 7.5 Hz, 1H), 7.48 (t, J ¼ 7.5 Hz, 1H), 7.51e7.59 (m,
1H), 8.20 (d, J ¼ 5.0 Hz, 1H), 9.14 (d, J ¼ 8.0 Hz, 1H), 9.17
1
3
H), 11.40 (s, 1H, NH). C NMR (100 MHz, DMSO-d ):
9.9, 20.3, 20.4, 20.5, 28.7 (CH ), 61.9 (CH ), 67.4, 67.8,
3
2.5, 73.1, 78.3 (CH), 110.1, 112.3, 122.5, 128.1, 129.1,
31.6, 133.4 (CH), 120.7, 121.2, 132.0, 132.5, 133.1, 141.4,
47.3 (C), 166.9, 168.7, 168.9, 169.4, 169.5, 170.1 (C]O).
6
1
3
(d, J ¼ 8.0 Hz, 1H), 11.59 (s, 1H, NH).
C NMR
(125 MHz, DMSO-d ): 20.0, 20.3, 20.4, 20.5 (CH ), 61.9
6 3
2
(CH ), 67.3, 67.8, 72.5, 73.1, 78.3 (CH), 111.6, 117.7,
2
122.6, 129.1, 133.2, 136.4, 150.5 (CH), 116.1, 120.6, 132.1,
132.5, 141.3, 157.9 (C), 167.0, 168.2, 168.8, 169.4, 169.5,
170.0 (C]O).
0
4
.1.10.8. 5 -(1-Oxobutyl)-1-(2,3,4,6-tetra-O-acetyl-b-D-gluco-
ꢀ
pyranosyl)isoindigo 24. Yield: 12%. Red solid (mp ¼ 210 C).
ꢂ1
ꢂ1
0
0
IR (KBr): n
3
1612 cm ; n
1675e1785 cm ; n
4.1.10.11. 7 -Aza-5 -bromo-1-(2,3,4,6-tetra-O-acetyl-b-D-glu-
C]C
ꢂ1
C]O
NH
175e3520 cm . HRMS (ES) calcd for C H N NaO
12
copyranosyl)isoindigo
ꢀ
27. Yield:
(mp ¼ 228e230 C). IR (KBr): n
55%.
Red
solid
1617 cm ; nC]O
3
4
34
2
þ
1
ꢂ1
(
M þ Na) 685.2009, found 685.1990. H NMR (400 MHz,
DMSO-d ): 0.95 (t, J ¼ 7.5 Hz, 3H, CH ), 1.67 (sext,
C]C
ꢂ1
ꢂ1
1715e1800 cm ; n 3300e3600 cm . HRMS (ES): calcd
NH
6
3
7
9
þ
J ¼ 7.5 Hz, 2H, CH ), 1.78 (s, 3H, CH ), 1.96 (s, 3H, CH )
for C H BrN O (M þ H) 672.0829, found 672.0833.
2
3
3
29 27
3 11
1
2
2
5
.03 (s, 3H, CH ), 2.05 (s, 3H, CH ), 2.95 (t, J ¼ 7.0 Hz,
H NMR (500 MHz, DMSO-d ): 1.78 (s, 3H, CH ), 1.96 (s,
6 3
3
3
H, CH ), 4.12e4.19 (m, 2H), 4.36e4.43 (m, 1H), 5.28e
2
3H, CH ), 2.03 (s, 3H, CH ), 2.05 (s, 3H, CH ), 4.10e4.18
3 3 3
.41 (m, 1H), 5.55e5.70 (m, 2H), 6.13e6.24 (m, 1H), 6.95
(m, 2H), 4.32e4.38 (m, 1H), 5.29e5.40 (m, 1H), 5.52e5.68
(m, 1H), 5.58 (t, J ¼ 9.0 Hz, 1H), 6.10e6.20 (m, 1H), 7.15
(
d, J ¼ 8.0 Hz, 1H), 7.12 (t, J ¼ 7.0 Hz, 1H), 7.47 (t,