170
V.M. D´ıaz Pe´rez et al. / Carbohydrate Research 326 (2000) 161–175
and l 5.45 (bs, 1 H, N%H), 4.92 (s, 1 H, NH),
2.10, 2.08, 2.07, 2.05, 2.04, 2.00, 1.97 (7 s, each
3 H, 7 Ac), 1.34, 1.30, 1.27 and 1.24 (4 s, each
3 H, 4 Me); 13C NMR (75.5 MHz, CDCl3):
Table 2 and l 171.1, 170.4, 170.1 (2 C), 169.3,
169.2, 168.9, (7 CO ester), 156.4 (CO urea),
112.2 (CMe2 dioxolane), 100.9 (CMe2 diox-
ane) [38], 29.6, 29.2, 27.0, 26.4 (4 Me), 20.7,
20.6, 20.5 and 20.4 (MeCO); FAMBS m/z 943
(100%, [M+Na]+). Anal. Calcd for
C39H56N2O23: C, 50.87; H, 6.13; N, 3.04.
Found: C, 51.20; H, 5.84; N, 3.15.
H, NH), 2.10, 2.08, 2.02, 2.01, 2.00, 1.99, 1.97
(7 s, each 3 H, 7 Ac), 1.47, 1.42, 1.31 and 1.30
(4 s, each 3 H, 4 Me); 13C NMR (75.5 MHz,
CDCl3): Table 2 and l 171.0, 170.4, 170.1,
169.3, 169.2, 168.9, 169.1 (7 CO ester), 156.3
(CO urea), 109.3, 108.7 (2 CMe2), 25.8 (2 C),
24.8, 24.1 (4 Me), 20.7, 20.6, 20.5 and 20.4
(MeCO); FABMS: m/z 943 (100%, [M+
Na]+). Anal. Calcd for C39H56N2O23: C, 50.87;
H, 6.13; N, 3.04. Found: C, 50.83; H, 6.28; N,
3.04.
6-Deoxy-1,2:3,5-di-O-isopropylidene-6-(N%-
methylureido)-h- -glucofuranose (8a).—Yield:
D
Methyl
methylureido)-h-
2,3,4-tri-O-acetyl-6-deoxy-6-(N%-
155 mg (98%); [h]2D2 +14.0° (c 1.1, CH2Cl2);
Rf (3:1 CCl4–acetone) 0.23; IR (KBr): wmax
3364, 2988, 2936, 1643, 1574, 1221, 1167 and
D
-glucopyranoside
(9a).—
Yield: 180 mg (96%); [h]2D2 +96.0° (c 1.0,
CH2Cl2); Rf (1:1 CCl4–acetone) 0.41; IR
(KBr): wmax 3347, 2942, 1751, 1651, 1568,
1
1003 cm−1; H NMR (500 MHz, CDCl3):
1373, 1227 and 1045 cm−1; H NMR (500
Table 1 and l 5.15 (bs, 2 H, 2 NH), 2.73 (s, 3
H, N%Me), 1.46, 1.32, 1.31 and 1.30 (4 s, each
3 H, 4 Me); 13C NMR (125.5 MHz, CDCl3):
Table 2 and l 159.3 (CO urea), 112.0 (CMe2
dioxolane), 100.7 (CMe2 dioxane) [38], 26.8
(MeN), 26.9, 26.7, 24.0 and 23.3 (4 Me);
FABMS: m/z 339 (100%, [M+Na]+). Anal.
Calcd for C14H24N2O6: C, 53.15; H, 7.65; N,
8.85. Found: C, 53.14; H, 7.59; N, 8.85.
1
MHz, CDCl3): Table 1 and l 3.39 (s, 3 H,
OMe), 2.75 (s, 3 H, N%Me), 2.08, 2.06 and 2.00
(3 s, each H, 3 Ac); 13C NMR (125.5 MHz,
CDCl3): Table 2 and l 170.1 (2 C), 169.8 (3
CO ester), 158.9 (CO urea), 55.0 (OMe), 29.8
(MeN) and 20.4 (3 C, 3 MeCO); FABMS:
m/z 399 (100%, [M+Na]+). Anal. Calcd for
C15H24N2O9: C, 47.87; H, 6.43; N, 7.44.
Found: C, 47.63; H, 6.29; N, 7.63.
6-Deoxy-1,2:3,5-di-O-isopropylidene-6-[N%-
(2,3,4,6-tetra-O-acetyl-i- -glucopyranosyl)-
D
Methyl
(2,3,4,6-tetra-O-acetyl-i-
2,3,4-tri-O-acetyl-6-deoxy-6-[N%-
-glucopyranosyl)-
ureido]-h- -glucofuranose (8b).—Yield: 310
D
D
mg (98%); [h]2D2 +6.9° (c 1.1, CH2Cl2); Rf (3:1
CCl4–acetone) 0.27; IR (KBr): wmax 3383,
2991, 2943, 1753, 1697, 1562, 1230 and 1035
ureido]-h- -glucopyranoside (9b).—Yield: 336
D
mg (97%); [h]2D2 +61.0° (c 0.8, CH2Cl2); Rf
(1:1 CCl4–acetone) 0.64; IR (KBr): wmax 3406,
2960, 2851, 1753, 1648, 1560, 1228 and 1035
1
cm−1; H NMR (500 MHz, CDCl3): Table 1
and l 5.87 (bs, 1 H, N%H), 3.37 (bs, 1 H, NH),
1.99, 1.97, 1.95, 1.93 (4 s, each 3 H, 4 Ac),
1.40, 1.29, 1.25 and 1.24 (4 s, each 3 H, 4 Me);
13C NMR (125.5 MHz, CDCl3): Table 2 and l
170.8, 170.7, 169.9, 169.7 (4 CO ester), 156.8
(CO urea), 112.2 (CMe2 dioxolane), 101.0
(CMe2 dioxane) [38], 27.1, 26.5, 23.9, 23.8, (4
Me), 20.8, 20.7, 20.6 and 20.5 (4 MeCO);
FABMS: m/z 655 (100%, [M+Na]+). Anal.
Calcd for C27H40N2O15: C, 51.26; H, 6.37; N,
4.43. Found: C, 51.14; H, 6.44; N, 4.42.
1
cm−1; H NMR (500 MHz, CDCl3): Table 1
and l 5.45 (bs, 1 H, N%H), 5.15 (t, 1 H,
J6a,NH=J6b,NH 6.1 Hz, NH), 3.35 (s, 3 H,
OMe), 2.06, 2.04 (2 C), 2.01, 1.99, 1.98 and
1.95 (6 s, each 3 H, 7 Ac); 13C NMR (125.5
MHz, CDCl3): Table 2 and l 171.3, 170.7,
170.4, 170.1, 170.0, 169.9, 169.7, (7 CO ester),
156.3 (CO urea), 55.5 (OMe), 20.7 (2 C) y 20.6
(5 C) (7 MeCO); FABMS: m/z 715 (100%,
[M+Na]+). Anal. Calcd for C28H40N2O18: C,
48.55; H, 5.82; N, 4.04. Found: C, 48.14; H,
5.74; N, 4.29.
6 - Deoxy - 6 - [N% - (2,3,6,2%,3%,4%,6% - hepta - O-
acetyl-i-cellobiosyl)ureido]-1,2:3,5-di-O-iso-
Methyl
2,3,4-tri-O-acetyl-6-deoxy-6-[N%-
propylidene-h- -glucofuranose (8c).—Yield:
D
442 mg (96%); [h]2D2 −2.2° (c 0.8, CH2Cl2); Rf
(3:1 CCl4–acetone) 0.25; IR (KBr): wmax 3389,
2928, 2857, 1753, 1645, 1377, 1231 and 1038
(2,3,6,2%,3%,4%,6%-hepta-O-acetyl-i-cellobiosyl)-
ureido]-h- -glucopyranoside (9c).—Yield: 485
D
mg (99%); [h]2D2 +40.4° (c 1.1, CH2Cl2); Rf
1
cm−1; H NMR (500 MHz, CDCl3): Table 1
(1:1 EtOAc–petroleum ether) 0.15; IR (KBr):