1H, J = 8.2), 7.74 (t, 1H, J = 2.3), 7.83 (ddd, 1H, J = 8.2, 2.3,
1.0); MS m/z (EI) 153 (Mϩ, 72%), 107 (41), 92 (76), 77 (100); IR
(KBr) 3445 (br), 1530, 1354, 1291, 1250, 1044, 901, 880, 799,
1H, J = 1.1, 7.5), 7.77 (dd, 1H, J = 7.5, 8.8), 8.47 (d, 1H,
J = 8.9), 8.90 (dd, 1H, J = 1.1, 8.8); MS (EI) m/z 248 (Mϩ,
100%), 218 (27), 155 (39), 126 (77), 114 (61); IR (KBr) 3454
(br), 1578, 1541, 1512, 1374, 1325, 1273, 1119, 1059, 967, 889,
743, 669 cmϪ1. Found: C, 53.38; H, 3.21; N, 11.21. C11H8N2O5
requires C, 53.23; H, 3.25; N, 11.29%.
737 cmϪ1
.
1,2-Dimethoxy-3,5-dinitrobenzene 7a. Mp 100–101 ЊC (lit.,25
102 ЊC). 1H NMR (CDCl3) δ 4.04 (s, 3H), 4.10 (s, 3H), 7.96 (d,
1H, J = 2.6), 8.26 (d, 1H, J = 2.6); MS m/z (EI) 228 (Mϩ, 100%),
181 (75), 92 (59); IR (KBr) 3452 (br), 3104, 2957, 1595, 1545,
1522, 1352, 1297, 1096, 1055, 984, 920, 882, 806, 789, 749, 731
1,7-Dimethoxy-4,8-dinitronaphthalene 18. Mp 213–214 ЊC.
1H NMR (CDCl3) δ 4.01 (s, 3H), 4.06 (s, 3H), 6.91 (d, 1H,
J = 8.7), 7.57 (d, 1H, J = 9.8), 8.31 (d, 1H, J = 8.7), 8.89 (d, 1H,
J = 9.8); MS (EI) m/z 278 (Mϩ, 100%), 233 (23), 215 (13), 185
(34), 156 (22); IR (KBr) 3452 (br), 1609, 1568, 1543, 1516, 1321,
1271, 1053, 903, 818, 664 cmϪ1. Found: C, 51.70; H, 3.54; N,
10.01. C12H10N2O6 requires C, 51.80; H, 3.62; N, 10.07%.
cmϪ1
.
2-Fluoro-4,6-dinitroanisole 7b. Bp 131–132 ЊC/0.1 mmHg
(lit.,26 118–120 ЊC/0.025 Torr). 1H NMR (CDCl3) δ 4.25 (d, 3H,
J = 3.8), 8.23 (dd, 1H, J = 3.3, 11.0), 8.49 (dd, 1H, J = 1.8, 3.3);
MS (EI) m/z 216 (Mϩ, 38%), 186 (100), 156 (22), 140 (25), 94
(93); IR (KBr) 3108, 2959, 1615, 1539, 1495, 1347, 1291, 1078,
1-Methoxy-4,7-dinitronaphthalene 19. Mp 181–182 ЊC. 1H
NMR (CDCl3) δ 4.20 (s, 3H), 7.00 (d, 1H, J = 8.8), 8.48 (dd,
1H, J = 9.6, 2.5), 8.62 (d, 1H, J = 8.8), 8.99 (d, 1H, J = 9.6), 9.32
(d, 1H, J = 2.5); MS (EI) m/z 248 (Mϩ, 100%), 218 (58), 202
(14), 172 (27), 155 (23), 126 (33); IR (KBr) 3450 (br), 1626, 1599,
1584, 1507, 1462, 1350, 1316, 1277, 1117, 1078, 1003, 822, 745
cmϪ1. Found: C, 53.29; H, 3.25; N, 11.19. C11H9N2O5 requires
C, 53.23; H, 3.25; N, 11.29%.
994, 901, 810 cmϪ1
.
2-Chloro-4,6-dinitroanisole 7c. Mp 34–35 ЊC (lit.,27 34.8–
35.2 ЊC). 1H NMR (CDCl3) δ 4.20 (s, 3H), 8.66 (d, 1H, J = 2.2),
8.59 (d, 1H, J = 2.2); MS (EI) m/z 234 (Mϩ ϩ 2, 14%), 232 (Mϩ,
38), 204 (34), 202 (100); IR (KBr) 3098, 1597, 1538, 1478, 1426,
1345, 1269, 1076, 982, 932, 907, 758 cmϪ1
.
1,5-Dimethoxy-4,6-dinitronaphthalene 20. Mp 152–153 ЊC.
1H NMR (CDCl3) δ 3.91 (s, 3H), 4.05 (s, 3H), 7.52 (d, 1H,
J = 9.2), 7.65 (d, 1H, J = 9.0), 7.81 (d, 1H, J = 9.0), 7.98 (d, 1H,
J = 9.2); MS (EI) m/z 278 (Mϩ, 100%), 247 (15), 173 (18), 157
(21); IR (KBr) 3450 (br), 1599, 1534, 1509, 1464, 1368, 1347,
1277, 1071, 842 cmϪ1. Found: C, 52.20; H, 3.45; N, 10.22.
C12H10N2O6 requires C, 51.80; H, 3.62; N, 10.07%.
2-Bromo-4,6-dinitroanisole 7d. Mp 46–47 ЊC (lit.,28 45–46 ЊC).
1H NMR (CDCl3) δ 4.13 (s, 3H), 8.64 (d, 1H, J = 2.7), 8.68 (d,
1H, J = 2.7); MS (EI) m/z 278 (Mϩ ϩ 2, 21%), 276 (Mϩ, 22), 248
(50), 246 (52), 75 (100); IR (KBr) 3096, 1593, 1541, 1474, 1420,
1341, 1264, 1152, 1075, 978, 907 cmϪ1
.
2-Iodo-4,6-dinitroanisole 7e. Mp 66–67 ЊC. 1H NMR (CDCl3)
δ 4.08 (s, 3H), 8.69 (d, 1H, J = 2.2), 8.84 (d, 1H, J = 2.2); MS
(EI) m/z 324 (Mϩ, 45%), 294 (44), 75 (100), 62 (78); IR (KBr)
3447 (br), 1586, 1538, 1516, 1466, 1343, 1258, 982, 970, 716
cmϪ1. Found: C, 26.15; H, 1.62; N, 8.42. C7H8IN2O5 requires C,
25.95; H, 1.56; N, 8.65%.
Reaction of nitroquinolines 21–24 with potassium methoxide.
General procedure
To a stirred suspension of potassium methoxide (24 mmol) in
THF (10 mL) was added slowly a nitroquinoline (3.0 mmol)
over 6 h. The resulting mixture was stirred for an additional 8 h
at room temperature and then diluted with water. The organic
phase was extracted with Et2O (3 × 30 mL), evaporated, and
chromatographed on silica gel using a mixture of hexane and
ethyl acetate as the solvent to obtain methoxynitroquinolines
25–28.
2-Methoxy-3,5-dinitrobenzonitrile 7f. Mp 72–73 ЊC (lit.,29
1
73 ЊC). H NMR (CDCl3) δ 4.37 (s, 3H), 8.69 (d, 1H, J = 2.2),
8.84 (d, 1H, J = 2.2); MS (EI) m/z 223 (Mϩ, 29%), 193 (100), 117
(22), 104 (68); IR (KBr) 3092, 2953, 2244, 1617, 1592, 1538,
1487, 1416, 1347, 1271, 1092, 978, 920 cmϪ1
.
6-Methoxy-5-nitroquinoline 25. Mp 104–105 ЊC (lit.,31 104–
105 ЊC). 1H NMR (CDCl3) δ 4.22 (s, 3H), 7.09 (d, 1H, J = 8.9),
7.71 (dd, 1H, J = 4.2, 8.9), 8.56 (d, 1H, J = 8.9), 9.04 (dd, 1H,
J = 1.6, 4.2), 9.25 (dd, 1H, J = 1.6, 8.9); MS (EI) m/z 204 (Mϩ,
64%), 174 (55), 157 (37), 128 (100); IR (KBr) 3453 (br), 1561,
Reaction of mono- and dinitronaphthalenes 8–13 with potassium
methoxide. General procedure
To a stirred suspension of potassium methoxide (24 mmol) in
THF (10 mL) was added slowly a given nitronaphthalene (3.0
mmol) over 6 h. The mixture was stirred for an additional 8 h
at room temperature and then diluted with water. The organic
phase was extracted with Et2O (3 × 30 mL) and the combined
extracts were evaporated to leave a residue, which was chrom-
atographed on silica gel using a mixture of hexane and ethyl
acetate as the solvent to give the methoxylated nitronaph-
thalenes 14–20.
1505, 1333, 1306, 1109, 830, 810 cmϪ1
.
5-Methoxy-6-nitroquinoline 26. Mp 130–131 ЊC (lit.,32 125–
126.5 ЊC). 1H NMR (CDCl3) δ 4.16 (s, 3H), 7.58 (dd, 1H,
J = 4.2, 8.6), 7.95 (d, 1H, J = 9.4), 8.15 (d, 1H, J = 9.4), 8.65 (dd,
1H, J = 1.7, 8.6), 9.07 (dd, 1H, J = 1.7, 4.2); MS (EI) m/z 204
(Mϩ, 83%), 157 (100), 128 (79), 115 (56); IR (KBr) 3456 (br),
1595, 1526, 1493, 1364, 1345, 1312, 1256, 1084, 970, 835, 822,
1-Methoxy-4-nitronaphthalene 14. Mp 83–84 ЊC (lit.30 83 ЊC).
1H NMR (CDCl3) δ 4.05 (s, 3H), 6.73 (d, 1H, J = 8.8), 7.49–7.80
(m, 2H), 8.25–8.40 (m, 2H), 8.76 (dd, 1H, J = 7.6, 1.2); MS (EI)
m/z 203 (Mϩ, 72%), 107 (41), 92 (76), 77 (100); IR (KBr) 1569,
808, 789 cmϪ1
.
8-Methoxy-7-nitroquinoline 27. Mp 109–110 ЊC. 1H NMR
(CDCl3) δ 4.38 (s, 3H), 7.57 (dd, 1H, J = 4.2, 8.3), 7.63 (d, 1H,
J = 9.0), 7.87 (d, 1H, J = 9.0), 8.23 (dd, 1H, J = 1.6, 8.4), 9.07
(dd, 1H, J = 1.6, 4.2); MS (EI) m/z 204 (Mϩ, 3%), 174 (100), 144
(34), 116 (83); IR (KBr) 3455 (br), 1580, 1518, 1489, 1370, 1347,
1092, 976, 839, 803, 712 cmϪ1. Found: C, 58.96; H, 3.78; N,
13.68. C10H8N2O3 requires C, 58.82; H, 3.95; N, 13.72%.
1513, 1499, 1461, 1423, 1307, 1268, 1095, 1005, 758 cmϪ1
.
1-Methoxy-2-nitronaphthalene 16. Mp 80–81 ЊC (lit.,30
1
80 ЊC). H NMR (CDCl3) δ 4.15 (s, 3H), 7.64–7.71 (m, 3H),
7.88–7.92 (m, 2H), 8.30–8.34 (m, 1H); MS (EI) m/z 203 (Mϩ,
78%), 156 (75), 127 (100), 114 (56); IR (KBr) 3442 (br), 1586,
1524, 1341, 1320, 1262, 1086, 976, 816, 760 cmϪ1
.
7-Methoxy-8-nitroquinoline 28. Mp 177–178 ЊC (lit.,33
178 ЊC). 1H NMR (CDCl3) δ 4.08 (s, 3H), 7.40 (dd, 1H, J = 4.3,
8.3), 7.43 (d, 1H, J = 9.2), 7.94 (d, 1H, J = 9.2), 8.17 (dd, 1H,
1-Methoxy-4,8-dinitronaphthalene 17. Mp 159–160 ЊC. 1H
NMR (CDCl3) δ 4.05 (s, 3H), 7.00 (d, 1H, J = 8.8), 7.64 (dd,
J. Chem. Soc., Perkin Trans. 1, 2000, 1259–1264
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