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H. A. El-Sayed et al.
NMR spectrum (300 MHz, DMSO-d6) δ 1.33 (t, 3 H, J = 7.0 Hz, CH3CH2),
2.56 (s, 3 H, CH3–6), 3.13–3.64 (m, 6 H, H-6ꢁ, H-6ꢁꢁ, H-5ꢁ, H-4ꢁ, H-3ꢁ and
H-2ꢁ), 4.38 (q, 2 H, J = 7.0 Hz, CH3CH2), 4.5 (t, 1 H, J = 3.56 Hz, OH-6ꢁ),
5.09 (d, 1 H, J = 4.34 Hz, OH-4ꢁ), 5.22 (d, 1 H, J = 4.20 Hz, OH-3ꢁ), 5.47
(d, 1 H, J = 4.96 Hz, OH-2ꢁ), 5.57 (d, 1 H, J1 ,2 = 7.79 Hz, H-1ꢁ), 7.59 (d, 2
H, J = 8.3 Hz, Ar-H) 8.38 (d, 2 H, J = 8.3 Hz, Ar-H); 13C-NMR (300 MHz,
DMSO-d6) δ 13.9 and 23.3 (2 CH3), 60.7 (CH3CH2), 62.0 (C-6ꢁ), 69.6 (C-2ꢁ),
71.6 (C-3ꢁ), 78.5 (C-4ꢁ), 81.8(C-5ꢁ), 82.8 (C-1ꢁ), 121.5, 128.9, 130.2, 135.0,
136.5, 160.9, 164.83, 165.3 and 167.6 (Ar-C, 2 C=N and C=O). Anal. Calcd
for C20H23ClN2O7S (470.92): C, 56.17; H, 6.17; N, 4.9. Found: C, 56.10; H,
6.40; N, 5.07.
ꢁ
ꢁ
Ethyl 2-(4-chlorophenyl)-4-(β-D-glucopyranosyloxy)-6-methylpyrimidin-
5-ca-rboxylate (7c). As for 7a; crystallized from ethanol/water to give color-
less crystals; 85% yield; m.p. 180–182◦C; Rf = 0.42 (eluent: CH2Cl2/MeOH;
9.1 : 0.9); 1H NMR spectrum (200 MHz, DMSO-d6/D2O) δ 1.39 (t, 3 H, J =
7.2 Hz, CH3CH2), 2.58 (s, 3 H, CH3–6), 3.20–3.61 (m, 6 H, H-6ꢁ, H-6ꢁꢁ, H-5ꢁ,
H-4ꢁ, H-3ꢁ and H-2ꢁ), 4.42 (q, 2 H, J = 7.2 Hz, CH3CH2), 6.11 (d, 1 H, J1 ,2
ꢁ
ꢁ
= 7.2 Hz, H-1ꢁ), 7.67 (d, 2 H, J = 8.8 Hz, Ar-H), 8.46 (d, 2 H, J = 8.8 Hz,
Ar-H). Anal. Calcd for C20H23Cl N2O8 (454.11): C, 52.81; H, 5.10; N, 6.16.
Found: C, 53.10; H, 5.22; N, 5.86.
Ethyl
2-phenyl-4-(2ꢁ,3ꢁ,5ꢁ-tri-O-acetyl-β-D-ribofuranosylthio)-6-methyl-
pyrimidine-5-carboxylate (8a). Method B: 82% yield, as Colorless crystals
from methanol; m.p. 79–80◦C; Rf = 0.43 (eluent: CH2Cl2 /MeOH; 9.8 :
1
0.2); UV λmax. 298 nm; H NMR spectrum (200 MHz, CDCl3) δ 1.43 (t, 3
H, J = 5.20 Hz, CH3CH2), 2.06, 2.07 and 2.15 (3s, 9 H, 3 CH3CO), 2.70 (s,
3 H, CH3–6), 4.11(dd, 1 H, J4’,5’ = 3.4, J5 ,5 = 11.6 Hz, H-5ꢁ), 4.16 (dd, 1 H,
ꢁ
ꢁꢁ
J4 ,5 = 3.6, J5 ,5 = 11.6 Hz, H-5ꢁꢁ), 4.42 (m, 3 H, CH3CH2 and H-4ꢁ), 5.54
ꢁ
ꢁꢁ
ꢁ
ꢁꢁ
(dd, 1 H, J2 ,3 = 2.7, J3 ,4 = 6.6 Hz, H-3ꢁ), 5.63 (dd, 1 H, J1 ,2 = 2.6, J2 ,3
=
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
2.80 Hz, H-2ꢁ), 6.46 (d, 1 H, J 1 ,2 = 2.4 Hz, H-1ꢁ), 7.45–8.40 (m, 5 H, Ar-H);
13C NMR (200 MHz, CDCl3) δ 13.0, 19.4, 19.4, 19.7 and 23.2 (5 CH3), 61.1
(CH3CH2), 61.1 (C-5ꢁ), 69.0 (C-3ꢁ), 74.4 (C-2ꢁ), 77.9 (C-4ꢁ), 84.0 (C-1ꢁ),
127.3, 127.6, 127.9, 128.1, 131.3, 134.8, 160.7, 161.0, 164.1, 168.3, 168.5
and 169.0 (Ar-C, 2 C=N and 4 acetyl C=O). Anal. Calcd for C25H28N2O9S
(532.38): C, 56.38; H, 5.30; N, 5.26. Found: C, 56.42; H, 5.21; N, 5.33.
Ethyl 2-(4-chlorophenyl)-4-(2ꢁ,3ꢁ,5ꢁ-tri-O-acetyl-β-D-ribofuranosylthio)-6-
methylpyrimidine-5-carboxylate (8b). Method B: 79% yield, as colorless
crystals from methanol; m.p. 129–130◦C; Rf = 0.38 (eluent: CH2Cl2 /MeOH;
9.8: 0.2); UV λmax 318 and 269.5 nm; 1H NMR spectrum (200 MHz, DMSO-
d6) δ 1.40 (t, 3 H, J = 7.5 Hz, CH3CH2), 2.10, 2.15 and 2.23 (3s, 9 H, 3
ꢁ
ꢁ
ꢁ
ꢁ
ꢁꢁ
CH3CO), 2.69 (s, 3 H, CH3–6), 4.10, (dd, 1 H, J4 ,ꢁ5ꢁꢁ = 4.8, J5 ,5 = 11.2 Hz,
ꢁ
ꢁ
ꢁꢁ
ꢁ
ꢁꢁ
H-5 ), 4.17 (dd, 1 H, J4 ,5 = 4.6, J5 ,5 = 11.2 Hz, H-5 ), 4.50 (m, 3 H,CH3CH2
and H-4ꢁ), 5.48 (dd, 1 H, J2 ,3 = 3.1, J3 ,4 = 6.8 Hz, H-3ꢁ), 5.59 (dd, 1 H, J1 ,2
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
= 2.4, J2 ,3 = 3.0 Hz, H-2ꢁ), 6.44 (d, 1 H, H-1ꢁ, J1 ,2 = 2.4 Hz), 7.60 (d, 2
ꢁ
ꢁ
ꢁ
ꢁ