&
A. Stimac, J. Kobe / Carbohydrate Research 329 (2000) 317–324
323
side), which was resolved by chromatography
using 25:2, 100:9, and 10:1 mixtures of
petroleum ether–1% AcOH in EtOAc. Com-
pounds were eluted in the following order:
b-azide 12b (Rf 0.21, 10:1 petroleum ether–1%
AcOH in EtOAc), a,b-glycoside (Rf 0.17),
a-azide 12a (Rf 0.14) and b,a-glycoside (Rf
0.10).
2.414 (m, 2 H, H-2a,2b), 4.48–4.64 (m, 3 H,
H-4,5a,5b), 5.57 (m, 1 H, H-3), 5.72 (pseudo t,
1 H, J1,2a and J1,2bꢀ5.1 Hz, H-1), 7.23 and
7.24 (2 m, 4 H, H-3,5 of p-toluoyl), 7.90 and
7.98 (2 m, 4 H, H-2,6 of p-toluoyl); 13C NMR:
l 21.64 (2 ArꢀCH3), 38.61 (C-2), 64.15 (C-5),
74.84 (C-3), 82.64 (C-4), 92.05 (C-1), 126.49
and 126.88 (C-1 of p-toluoyl), 129.09 and
129.14 (C-3,5 of p-toluoyl), 129.67 and 129.70
(C-2,6 of p-toluoyl), 143.82 and 144.24 (C-4 of
p-toluoyl), 165.87 and 166.22 (2 CO); EIMS:
m/z 353 ([M−N3]+, 14%), 119 ([p-
MePhCO]+, 100), 91 ([p-MePh]+, 42). Anal.
Calcd for C21H21N3O5 (395.42): C, 63.79; H,
5.35; N, 10.63. Found: C, 63.87; H, 5.36; N,
10.58.
b-Azide 12b: 11.29 g (85%); mp 86.5–87 °C
(EtOH); IR (film): w 2114 (N3), 1724 (CꢁO),
1595, 1270 (CꢀO, ester), 1240, 1095, and 758
1
cm−1; H NMR: l 2.42 (m, 2 H, H-2a,2b),
4.51–4.65 (m, 3 H, H-4,5a,5b), 5.58 (dt, 1 H,
J 5.6, 5.6, and 2.7 Hz, H-3), 5.74 (pseudo t,
1 H, J1,2a and J1,2bꢀ5 Hz, H-1), 7.41 and
7.42 (2 m, 4 H, H-3,5 of aroyl), 7.94 and 8.02
13
(2 m, 4 H, H-2,6 of aroyl); C NMR: l 38.50
a-Azide 11a: 1.44 g (8%); Rf 0.12; mp 88–
88.5 °C (needles from EtOH); IR (film): w 2110
(N3), 1721 (CꢁO), 1272 (CꢀO, ester), 1611,
(C-2), 64.39 (C-5), 75.14 (C-3), 82.46 (C-4),
92.06 (C-1), 127.59 and 128.04 (C-1 of aroyl),
128.76 and 128.83 (C-3,5 of aroyl), 131.00
and 131.05 (C-2,6 of aroyl), 139.66 and
140.04 (C-4 of aroyl), 164.95 and 165.26 (2
CO); CIMS (NH3): m/z 453 ([M+NH4]+,
27%), 393 ([M−N3]+, 29), 156 ([p-
ClPhCO2H]+, 53), 139 ([p-ClPhCO]+, 100).
Anal. Calcd for C19H15Cl2N3O5 (436.26): C,
52.31; H, 3.47; N, 9.63. Found: C, 52.43; H,
3.53; N, 9.62.
1
1179, 1103, and 752 cm−1 (p-toluoyl); H
NMR: l 2.23 (ddd, 1 H, H-2a), 2.405
and 2.414 (2 s, each 3 H, 2 ArꢀCH3), 2.55
(ddd, 1 H, H-2b), 4.52 (dd, 1 H, H-5a), 4.62
(dd, 1 H, H-5b), 4.71 (ddd, 1 H, H-4), 5.50
(ddd, 1 H, H-3), 5.71 (dd, 1 H, H-1), 7.23 and
7.25 (2 m, 4 H, H-3,5 of p-toluoyl), 7.91 and
7.96 (2 m, 4 H, H-2,6 of p-toluoyl); J1,2a 1.2,
J1,2b 6.4, J2a,2b 14.7, J2a,3 1.5, J2b,3 7.3, J3,4 2.7,
J4,5a 4.4, J4,5b 3.4, J5a,5b 12.0 Hz; 13C NMR:
l 21.62 and 21.65 (2 ArꢀCH3), 38.78 (C-2),
63.93 (C-5), 74.52 (C-3), 83.52 (C-4), 91.98
(C-1), 126.62 and 126.80 (C-1 of p-toluoyl),
129.15 (C-3,5 of p-toluoyl), 129.61 and
129.77 (C-2,6 of p-toluoyl), 143.94 and 144.17
(C-4 of p-toluoyl), 166.07 and 166.22 (2 CO);
CIMS (NH3): m/z 413 ([M+NH4]+, 1.3%),
368 ([MH−N2]+, 1.7), 353 ([M−N3]+, 14),
136 ([p-MePhCO2H]+, 46), 119 ([p-MePh-
CO]+, 100), 91 ([p-MePh]+, 50). Anal.
Calcd for C21H21N3O5 (395.42): C, 63.79; H,
5.35; N, 10.63. Found: C, 63.69; H, 5.37; N,
10.55.
a-Azide 12a: 0.52 g (4%); mp 97.5–98.5 °C
(needles from EtOH); IR (film): w 2111 (N3),
1723 (CꢁO), 1595, 1269 (CꢀO, ester), 1240,
1
1093, and 758 cm−1; H NMR: l 2.24 (ddd, 1
H, H-2a), 2.53 (ddd, 1 H, H-2b), 4.53 (dd, 1
H, H-5a), 4.62 (dd, 1 H, H-5b), 4.70 (ddd, 1
H, H-4), 5.48 (ddd, 1 H, H-3), 5.73 (dd, 1 H,
H-1), 7.42 and 7.44 (2 m, 4 H, H-3,5 of aroyl),
7.96 and 8.00 (2 m, 4 H, H-2,6 of aroyl); J1,2a
1.0, J1,2b 6.2, J2a,2b 14.7, J2a,3 1.3, J2b,3 7.3, J3,4
2.7, J4,5a 4.6, J4,5b 3.9, J5a,5b 12.0 Hz; 13C
NMR: l 38.65 (C-2), 64.17 (C-5), 74.81 (C-3),
83.22 (C-4), 91.97 (C-1), 127.72 and 127.94
(C-1 of aroyl), 128.84 and 128.86 (C-3,5 of
aroyl), 130.98 and 131.14 (C-2,6 of aroyl),
139.78 and 140.02 (C-4 of aroyl), 165.18 and
165.30 (2 CO); CIMS (NH3): m/z 453 ([M+
NH4]+, 0.8%), 393 ([M−N3]+, 5), 156 ([p-
ClPh-CO2H]+, 70), 139 ([p-ClPhCO]+, 100).
Anal. Calcd for C19H15Cl2N3O5 (436.26): C,
52.31; H, 3.47; N, 9.63. Found: C, 52.46; H,
3.53; N, 9.46.
3,5-Di-O-(4-chlorobenzoyl)-2-deoxy-i- (12b)
and -h- -erythro-pentofuranosyl azide (12a).
D
—The reaction of the chloride 6a (15.0 g,
containing 13.2 mmol of the pure material), as
described for 5a, afforded the crude product
mixture (14.84 g, b:a=87:13, containing also
ꢀ10% of methyl 3,5-di-O-(4-chlorobenzoyl) -
2 - deoxy - a,b -
D
- erythro - pentofurano-