Methoxy TEMPO Substituted Pyrimidine Nucleoside
1733
1
3
0
7
2
.94 (s, 3H, CH -TEMPO). C-NMR(CDCl ); d 164.2, 150.9, 137.8, 109.3, 83.9, 82.8,
3
3
1.3, 65.9, 61.1, 59.5, 55.7, 44.9, 34.5, 33.4, 32.2, 21.1, 12.4. IR(KBr); 3557, 3198, 2976,
À1
+
939, 1686, 1466, 1376, 1265, 1170, 1094 cm . HRMS: (M + Na) calcd. for
C H N O Na; 404.2161. Found; 404.2161.
19 31 3 5
5
-Methyl-1-{3-[(2,2,6,6-tetramethyl-4-methoxypiperidin-1-yl)oxy]tetrahydro-
H-pyran-2-yl}pyrimidine-2,4-(1H,3H)-dione (8). HPLC (65% MeOH/35% H O)
2
2
1
ret. time = 6.49 min. H-NMR(CDCl ); d 10.02 (s, 1H, NH), 7.48 (s, 1H, vinylic H),
3
5.63 (d, 1H, J = 1.8, CH), 4.17 (dt, 2H, CH ), 3.72 (dt, 1H, CH), 3.40 (tt, 1H, CH-
TEMPO), 3.30 (s, 3H, OCH ), 2.55 (d, 1H, CH), 1.97 (ddd, 2H, CH ), 1.93 (s, 3H,
2
3
2
Thy-CH ), 170 (dd, 2H, CH ), 1.41 (m, 3H, CH + CH ), 1.27 (s, 3H, CH -TEMPO),
2
3
2
3
1
3
1
1
1
.15 (s, 3H, CH -TEMPO), 1.00 (s, 6H, 2 CH ’s-TEMPO). C-NMR(CDCl ); d 164.2,
3
3
3
50.4, 139.1, 109.3, 83.6, 75.4, 71.3, 69.3, 61.3, 59.8, 55.7, 45.4, 34.0, 25.9, 21.8, 20.4,
À1
2.3. IR(KBr); 3186, 2974, 2940, 1706, 1676, 1466, 1376, 1297, 1262, 1097 cm
+
.
HRMS: (M + Na) calcd. for C H N O Na; 418.2318. Found; 418.2310.
20 33 3 5
1-{1-Isobutoxy-2-[(2,2,6,6-tetramethyl-4-methoxypiperidin-1-yl)oxy]ethyl}-5-
methyl-pyrimidine-2,4-(1H,3H)-dione (7). HPLC (75% MeOH/25% H O) ret.
2
1
time = 5.70 min. H-NMR(CDCl ); d 9.31 (s, 1H, NH), 7.28 (s, 1H, vinylic H), 5.78
3
(
t, 1H, J = 4.4, CH), 3.95 (d, 2H, J = 5.1, CH ), 3.41 (ddd, 1H, CH-TEMPO), 3.31 (s,
2
3H, OCH ), 3.25 (d, 2H, J = 6.3, CH ), 1.95 (s, 3H, Thy-CH ), 1.91–1.81 (m, 3H,
CH + CH -TEMPO), 1.35 (dd, 2H, CH ), 1.18 (s, 3H, CH -TEMPO), 1.14 (s, 3H, CH -
3 2 3
2
2
3
3
TEMPO), 1.11 (s, 3H, CH -TEMPO), 1.08 (s, 3H, CH -TEMPO), 0.92 (d, 6H, J = 6.6,
3
3
1
3
CH(CH ) ). C-NMR(CDCl ); d 163.0, 149.9, 134.8, 109.2, 81.4, 75.3, 74.6, 70.2,
3
3
3
5
1
4
8.9, 54.5, 43.2, 31.6, 26.9, 19.7, 17.9, 17.8, 11.2. IR(KBr); 3176, 3053, 2971, 1681,
À1
+
645, 1468, 1375, 1260, 1100, 1069 cm . HRMS: (M+H) calcd. for C H N O ;
12.2811. Found; 412.2802.
2
1 38 3 5
1-{1-(9H-carbazol-9-yl)-2-[(2,2,6,6-tetramethyl-4-methoxypiperidin-1-
yl)oxy]ethyl}5-methylpyrimidine-2,4-(1H,3H)-dione (9). HPLC (80% MeOH/20%
1
H O) ret. time = 6.76 min. H-NMR(CDCl ); d 9.79 (s, 1H, NH), 8.07 (d, 2H, J = 7.7,
2
3
arom.), 7.70 (d, 2H, J = 8.5, arom.), 7.49 (t, 2H, J = 7.3, arom.), 7.30 (t, 3H, J = 7.7,
CH + arom.), 7.24 (s, 1H, Thy. vinylic), 4.92 (t, 1H, J = 7.5, CH), 4.78 (dd, 1H, CH),
3.41 (ddd, 1H, CH-TEMPO), 3.31 (s, 3H, OCH ), 1.87(dd, 2H, CH -TEMPO), 1.78 (s,
3 2
3H, Thy-CH ), 1.38 (dd, 2H, CH -TEMPO), 1.19 (s, 3H, CH -TEMPO), 1.13 (s, 3H,
CH -TEMPO), 1.08 (s, 3H, CH -TEMPO), 1.07 (s, 3H, CH -TEMPO).
3
2
3
1
3
C-
3
3
3
NMR(CDCl ); d 163.8, 150.8, 139.8, 136.2, 126.7, 124.1, 120.8, 120.5, 111.8, 110.2,
3
7
2
5.7, 71.4, 64.8, 60.5, 60.4, 55.8, 44.5, 33.0, 21.0, 12.7. IR(KBr); 3514, 3179, 3058,
À1
+
975, 2937, 1686, 1449, 1376, 1327, 1257, 1214, 1092 cm . HRMS: (M+H) calcd.
for C H N O ; 505.2815. Found; 505.2799.
29 37 4 4
5-Methyl-1-{2-[(2,2,6,6-tetramethyl-4-methoxypiperidin-1-yl)oxy]-1-(2-oxoaze-
pan-1-yl)ethyl}pyrimidine-2,4-(1H,3H)-dione (10). HPLC (65% MeOH/35% H O)
2
1
ret. time = 4.86 min. H-NMR(CDCl ); d 10.10 (s, 1H, NH), 7.52 (s, 1H, Thy. vinylic),
3
5.76 (t, 1H, CH), 4.40 (t, 2H, J = 7.3, CH ), 3.62 (m, 2H, CH ), 3.41 (ddd, 1H, CH-
TEMPO), 3.32 (s, 3H, OCH ), 2.54 (quintet, 2H, CH ), 1.91 (s, 3H, Thy. CH ), 1.86 (m,
2 2
3
2
3
2
H, CH ), 1.71 (brd. s. 6H, 3 CH ’s), 1.36 (m, 2H, CH ), 1.21 (s, 3H, CH -TEMPO), 1.13
2 2 2 3
1
3
(
s, 6H, 2 CH ’s-TEMPO), 1.06 (s, 3H, CH -TEMPO). C-NMR(CDCl ); d 177.9, 164.5,
3
3
3