1080
M.V. de Almeida et al. / European Journal of Medicinal Chemistry 42 (2007) 1076e1083
1
644 and 1071. Anal. Calcd. for C H N O : C, 72.12; H,
5
Anal. Calcd. for C H NO : C, 70.82; H, 10.98; N, 1.80.
46 85 8
1
96
2
7
1
1.39; N, 3.30. Found: C, 71.93; H, 11.07; N, 2.96.
Found: C, 70.43; H, 10.69; N, 2.12.
0
3
.3.5. 6-[(N,N -Dihexadecanoyl)-2-aminoethylamino]-6-
3.3.8. 6-[(N,O-Dioctadecanoyl)-2-hydroxyethylamino]-6-
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (9)
From compound 5 (1.06 g), solid (1.97 g, 72%), mp: 39.0e
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (12)
From compound 6 (1.06 g), oil (2.13 g, 67%). [a] : ꢁ9.0 (c
D
ꢀ
1
1
0.54, CH Cl ). H NMR (CDCl , 300 MHz): d 5.47 (2d, 1H,
4
3
4
1
2
1
1
2.0 C. [a] : þ34.2 (c 0.54, CH Cl ). H NMR (CDCl ,
D
2
2
3
2
2
3
00 MHz): d 6.63 (s, 1H, NH), 5.51 (d, 1H, J1,2 4.8, H ),
H , J 5.1), 4.55 (2dd, 1H, H , J 8.0), 4.24 (m, 4H, H2,
1 1,2 3 3,4
H , H ), 3.92 (m, 1H, H ), 3.67, 3.00 (m, 4H, H , H ),
4 8 5 6 7
0 0
2.39e2.26 (m, 4H, H , H ), 1.61 (m, 4H, H , H ), 1.47,
9 9 10 10
1
.59 (dd, 1H, J3,4 8.0, H ), 4.30 (m, 2H, H , H ), 4.18 (m,
3
2
4
H, H ), 3.90 (m, 1H, H or H
5
0
), 3.62 (m, 1H, H or H
6
0
),
),
6
6
6
9
.96e2.78 (m, 4H, H , H ), 2.12e2.04 (m, 4H, H , H
7
0
1.46, 1.44 (s, 9H, CH3i-Pr), 1.35e1.26 (m, 59H, CH3i-Pr,
1
8
9
3
.56 (m, 4H, H , H
0
0
), 1.46e1.44 (3 s, 6H, CH3i-Pr); 1.36e
.24 (m, 54H, CH3i-Pr, CH2aliph), 0.87 (t, 6H, J 6.7, CH3aliph);
CH2aliph), 0.87 (t, 6H, J 6.9); C NMR (CDCl , 75.0 MHz):
1
10
3
d 175.0e173.0 (CO), 109.7e108.8 (Ci-Pr), 96.5 (C-1), 72.0,
71.4 (C-4)*, 71.0, 70.7 (C-3)*, 70.6, 70.0 (C-2)*, 66.3 (C-
5), 62.3, 62.1 (C-8), 48.8, 48.3 (C-6), 48.0, 45.3 (C-7), 34.4
1
3
C NMR (CDCl , 75.0 MHz): d 174.6 and 174.0 (CO),
3
1
09.6e108.7 (Ci-Pr), 96.7 and 96.5 (C-1), 72.2 and 71.6
0
(
(
(
(
C-4)*, 71.0 (C-3)*, 70.7 and 70.5 (C-2)*, 66.6 (C-5), 49.5
C-6), 45.7 (C-7), 39.5 and 37.5 (C-8), 37.0 and 36.9
(C-9 )*, 34.3 (C-9)*, 32.1e22.9 (CH3i-Pr, CH2aliph), 14.3
ꢁ1
(CH3aliph). IR (n, cm , KRS-5): 2919, 2851, 1739, 1648
and 1071. Anal. Calcd. for C H NO : C, 71.81; H, 11.21;
N, 1.67. Found: C, 71.46; H, 10.93; N, 1.61.
0
C-9 )*, 33.5 (C-9)*, 32.1e22.9 (CH3i-Pr, CH2aliph), 14.3
ꢁ
50
93
8
1
CH3aliph). IR (n, cm , KBr): 3307, 2919, 2851, 1635 and
1
3
071. Anal. Calcd. for C H N O : C, 70.91; H, 11.12; N,
46 86 2 7
.60. Found: C, 70.56; H, 10.72; N, 3.73.
3.3.9. 6-[(3-N-Octadecanoyl)-3-aminopropylamino]-6-
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (13)
0
3
.3.6. 6-[(N,N -Dioctadecanoyl)-2-aminoethylamino]-6-
From compound 4 (0.5 g), oil (0.46 g, 50%). [a] : ꢁ30.5 (c
D
1
0.59, CH Cl ). H NMR (CDCl , 300 MHz): d 6.83 (s, 1H,
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (10)
2
2
3
From compound 5 (1.06 g), oil (1.96 g, 67%). [a] : þ32.1
NH), 5.53 (d, 1H, J1,2 5.1, H ), 4.60 (dd, 1H, J 8.0, J3,2
1 3,4
2.6, H ), 4.32 (dd, 1H, J 5.1, J2,3 2.6, H ), 4.17 (dd, 1H,
3 2,1 2
D
1
(
c 0.80, CH Cl ). H NMR (CDCl , 300 MHz): d 6.68 (s, 1H,
2
2
3
NH), 5.48 (d,1H, J1,2 4.8, H ), 4.57 (dd, 1H, J 8.0, H ), 4.30
J4,3 8.0, J4,5 2.0, H ), 3.96 (m, 1H, H ), 3.33 (t, 2H, J or
4 5 7,8
1
3,4
3
(
m, 1H, H ), 4.17 (dd, 1H, J4,3 8.0, H ), 4.00 (m, 1H, H ),
J9,8 6.2, H or H ), 2.95e2.75 (m, 5H, H or H , H , NH),
7 9 7 9 6
2
4
5
3
.90e3.30 (m, 4H, H , H ), 3.62 (m, 1H, H or H
7
0
), 2.85
), 1.57 (m,
2.14 (t, 2H, J10,11 6.9, H ), 1.72 (m, 2H, H ), 1.60 (m, 2H,
10 8
8
6
6
(
m, 1H, H or H6
6
0
), 2.31e2.04 (m, 4H, H , H
9
0
H ), 1.53, 1.44 (s, 6H, CH ), 1.32e1.24 (m, 34H, CH3i-Pr,
11 3i-Pr
9
1
3
4
H, H , H ), 1.45e1.43 (4 s, 6H, CH3i-Pr), 1.36e1.24 (m,
0
62H, CH3i-Pr and CH2aliph), 0.85 (t, 6H, CH3aliph, J 7.1);
NMR (CDCl , 75.0 MHz): 178.0, 174.0 (CO), 109.6e108.7
CH2aliph), 0.87 (t, 3H, J 6.9, CH3aliph); C NMR (CDCl3,
75.0 MHz): d 173.4 (CO), 109.3, 108.6 (Ci-Pr), 96.3 (C-1),
71.8 (C-4)*, 70.8 (C-3)*, 70.5 (C-2)*, 66.2 (C-5), 49.2 (C-
6), 47.6 (C-7), 38.3 (C-9), 36.8 (C-10), 31.8e22.6 (CH3i-Pr,
1
0
10
1
3
C
3
(
7
4
Ci-Pr), 96.7, 96.5 (C-1), 72.1, 71.5 (C-4)*, 71.0 (C-3)*,
ꢁ1
0.7, 70.4 (C-2)*, 66.6, 66.1 (C-5), 49.4, 49.1 (C-6), 48.4,
0
CH2aliph), 29.7 (C-8), 14.1 (CH3i-Pr). IR (n, cm , KRS-5):
3229, 2918, 2850, 1642 and 1070. Anal. Calcd. for
C H N O : C, 68.00; H, 10.72; N, 4.81. Found: C, 67.68;
5.4 (C-7), 39.3, 37.5 (C-8), 36.9, 36.8 (C-9 )*, 34.2, 33.5
(
C-9)*, 32.1e22.9 (CH3i-Pr, CH2aliph), 14.3 (CH3aliph). IR (n,
ꢁ
33
62 2 6
1
cm , KRS-5): 3316, 2918, 2851, 1629 and 1071. Anal.
Calcd. for C H N O : C, 71.90; H, 11.34; N, 3.35. Found:
C, 71.55; H, 10.96; N, 3.15.
H, 10.38; N, 4.44.
5
0 94 2 7
3.3.10. 6-[(2-N-Octadecanoyl)-2-aminoethylamino]-6-
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (14)
From compound 5 (0.5 g), oil (0.47 g, yield 50%). [a] :
3
.3.7. 6-[(N,O-Dihexadecanoyl)-2-hydroxyethylamino]-6-
D
1
deoxy-1,2:3,4-di-O-isopropylidene-a-D-galactopyranose (11)
ꢁ29.5 (c 0.63, CH Cl ). H NMR (CDCl , 300 MHz):
2
2
3
From compound 6 (1.06 g), oil (2.04 g, 75%) [a] : ꢁ9.0 (c
d 6.60 (s, 1H, NH), 5.52 (d, 1H, J 5.1, H ), 4.59 (dd, 1H,
1,2 1
D
1
0
.73, CH Cl ). H NMR (CDCl , 300 MHz): d 5.47 (2d, 1H, J
J3,4 8.0, J3,2 2.3, H ), 4.31 (dd, 1H, J 5.1, J2,3 2.3, H2),
3 2,1
2
2
3
4
H ), 3.92 (m, 1H, H ), 3.67e3.00 (m, 4H, H , H ), 2.40e2.27
.6, H ), 4.55 (2dd, 1H, J 8.0, H ), 4.24 (m, 4H, H , H ,
4.16 (dd, 1H, J4,3 8.0, J4,5 1.8, H ), 3.92 (m, 1H, H ), 3.38
4 5
(m, 3H, NH, H ), 2.97e2.82 (m, 4H, H , H ), 2.16 (t, 2H,
8 7 6
1
,2
1
3,4
3
2
4
8
5
6
7
(
m, 4H, H , H
0
), 1.60 (m, 4H, H , H
0
), 1.48e1.44 (4 s, 6H,
CH3i-Pr), 1.35e1.26 (m, 54H, CH3i-Pr., CH2aliph), 0.88 (t, 6.7,
H , J
7.4), 1.60 (m, 2H, H ), 1.53, 1.42 (s, 1H, CH3i-Pr),
9,10 10
9
9
10
10
9
1.32e1.24 (m, 34H, CH3i-Pr, CH2aliph), 0.86 (t, 3H, J 6.4,
1
H, CH3aliph); C NMR (CDCl , 75.0 MHz): d 176.0 and
3
13
CH3aliph); C NMR (CDCl , 75.0 MHz): d 173.6 (CO),
6
3
3
7
and 71.4 (C-4)*, 71.1 and 70.7 (C-3)*, 70.6 and 70.0 (C-
2.0 (CO), 109.7 and 108.8 (Ci-Pr), 96.6 and 96.5 (C-1), 72.0
109.4, 108.7 (Ci-Pr), 96.5 (C-1), 71.8 (C-4), 70.8 (C-3), 70.4
(C-2), 66.1 (C-5), 48.7 (C-6), 48.1 (C-7), 38.2 (C-8), 36.7
(C-9), 31.9e22.6 (CH3i-Pr, CH2aliph), 14.1 (CH3aliph). IR (n,
2
)*, 66.3 and 66.2 (C-5), 62.3 and 62.1 (C-8), 49.0 and 48.4
0
ꢁ1
(
C-6), 48.0 and 45.3 (C-7), 35.6 and 34.5 (C-9 )*, 34.4 and
cm , KRS-5): 3300, 2919, 2851, 1651 and 1071. Anal.
Calcd. for C H N O : C, 67.57; H, 10.63; N, 4.92. Found.
C, 67.19; H 10.29; N, 4.63.
3
IR (n, cm , KRS-5): 2924, 2854, 1741, 1646 and 1071.
4.2 (C-9)*, 32.1e22.9 (CH3i-Pr, CH2aliph), 14.3 (CH3aliph).
ꢁ
32
60 2 6
1