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3H), 6.70–7.15 (m, 12H), 7.91 (dd, J¼4.3, 1.3 Hz, 1H), 9.6
(br s, 2H). MS (EI 70 eV, m/z, %): 302 (91) [Mþ], 227 (12),
210 (100), 107 (20), 93 (14); HRMS for C19H18N4 calcd
302.1532, found 302.1527.
7.28–7.37 (m, 3H), 7.52–7.58 (m, 1H), 7.68–7.73 (m, 1H),
8.10 (dd, J¼7.9, 1.5 Hz, 1H), 8.30 (br s, 1H). 13C NMR
(100 MHz): d¼22.9, 43.7, 107.8, 110.1, 111.4, 114.5, 119.3,
124.1, 124.5, 129.2, 132.7, 141.8, 147.6, 149.1, 163.4. IR
(KBr) n: 3294, 2961, 1623, 1601, 1588, 1542, 1526, 1476,
1457, 1383, 1332, 1323, 1246, 1197, 1183, 1169, 1127,
1052, 1029, 923. MS (EI 70 eV, m/z, %): 252 (35, Mþ), 237
(100), 222 (4), 219 (3), 210 (3), 195 (4), 145 (12), 144 (22),
130 (5), 126 (5), 111 (10). HRMS for C16H16N2O calcd
252.1263, found 252.1261.
3.2.2. N-Methyl-2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-
2-yl)aniline (7). Yield 16%. Oil. 1H NMR (400 MHz):
d¼1.36 (s, 6H), 2.93 (s, 3H), 3.97 (s, 2H), 6.60 (ddd, J¼7.8,
7.2, 1.1 Hz, 1H), 6.65 (d, J¼8.4 Hz, 1H), 7.30 (ddd, J¼8.4,
7.2, 1.8 Hz, 1H), 7.71 (dd, J¼7.8, 1.8 Hz, 1H), 8.25 (br s,
1H). 13C NMR (100 MHz): d¼28.7, 29.5, 67.8, 77.1, 108.5,
109.7, 114.1, 129.6, 132.3, 149.8, 162.3. IR (film) n: 3272,
2963, 2929, 1632, 1586, 1527, 1467, 1426, 1357, 1332,
1283, 1211, 1193, 1173, 1120, 1074, 1038, 965. MS (EI
70 eV, m/z, %): 204 (100, Mþ), 189 (20), 173 (4), 160 (10),
149 (16), 147 (42), 132 (94), 131 (47), 118 (22), 105 (21).
HRMS for C14H13N4O2 calcd 204.1263, found 204.1261.
3.2.7. 2-[2-(Isopropylamino)phenyl]perimidine (15). Yel-
low crystals. Mp 131–1328C. 1H NMR (400 MHz): d¼1.30
(d, J¼6.2 Hz, 6H), 3.70 (sept, J¼6.2 Hz, 1H), 6.54 (br s,
1H), 6.64 (ddd, J¼8.1, 7.1, 1.2 Hz, 1H), 6.75 (br d,
J¼8.4 Hz, 1H), 7.11–7.20 (m, 4H), 7.25–7.28 (m, 2H),
7.29 (ddd, J¼8.4, 7.1, 1.5 Hz, 1H), 7.39 (dd, J¼8.1, 1.5 Hz,
1H), 8.0 (br s, 1H). 13C NMR (100 MHz): d¼22.8, 43.3,
112.5, 113.5, 114.6, 119.5, 119.6, 121.0, 126.1, 128.2,
128.3, 132.2, 135.3, 148.2, 153.1. IR (KBr) n: 2964, 1634,
1613, 1598, 1574, 1522, 1457, 1406, 1372, 1337, 1273,
1242, 1177, 1163, 1132, 822, 770, 747. MS (EI 70 eV, m/z,
%): 301 (100, Mþ), 287 (22), 286 (98), 270 (11), 260 (11),
259 (59), 258 (14), 244 (77), 166 (17), 143 (18). HRMS for
C20H19N3 calcd 301.1579, found 301.1585.
3.2.3. 2-[2-(Methylamino)phenyl]benzimidazole (11).
Light brown crystals. Mp 205–2078C, lit.19 Mp 208–
1
2098C. H NMR (400 MHz): d¼3.03 (s, 3H), 6.71 (ddd,
J¼8.2, 7.2, 1.1 Hz, 1H), 6.79 (d, J¼8.0 Hz, 1H), 7.18–7.28
(m, 4H), 7.34 (ddd, J¼8.4, 7.2, 1.5 Hz, 1H), 7.55 (dd,
J¼7.5, 1.5 Hz, 1H), 7.8 (br s, 2H, N–H). IR (KBr) n: 3385,
2885, 1625, 1607, 1582, 1534, 1514, 1486, 1468, 1452,
1439, 1429, 1394, 1322, 1279, 1225, 1174, 1122, 1062. MS
(EI 70 eV, m/z, %): 223 (100, Mþ), 222 (47), 221 (7), 220
(6), 207 (15), 206 (15), 205 (11), 195 (17), 194 (30), 193
(10), 131 (5), 119 (13), 112 (14). HRMS for C14H13N3 calcd
223.1110, found 223.1109.
3.2.8. 2-[3-(Methylamino)-2-pyridyl]benzimidazole (16).
Pale yellow crystals. Mp 135–1378C. 1H NMR (200 MHz):
d¼3.11 (s, 3H), 7.16 (dd, J¼8.5, 1.2 Hz, 1H), 7.24–7.39 (m,
4H), 7.80–7.85 (m, 1H), 7.99 (dd, J¼4.4, 1.3 Hz, 1H), 8.89
(br s, 1H), 11.65 (br s, 1H). MS (EI 70 eV, m/z, %): 224
(100) [Mþ], 223 (49), 208 (6), 195 (25), 119 (15), 69 (8).
HRMS for C13H12N4 calcd 224.1062, found 224.1051.
3.2.4. 2-[2-(Methylamino)phenyl]benzoxazole (12). Light
brown crystals. Mp 80–828C. 1H NMR (400 MHz): d¼3.06
(s, 3H), 6.75 (ddd, J¼8.1, 7.2, 1.1 Hz, 1H), 6.79 (d,
J¼8.2 Hz, 1H), 7.29–7.35 (m, 2H), 7.40 (ddd, J¼8.6, 7.0,
1.6 Hz, 1H), 7.53–7.58 (m, 1H), 7.68–7.73 (m, 1H), 8.11
(ddd, J¼7.8, 1.6, 0.4 Hz, 1H), 8.25 (br s, 1H). 13C NMR
(100 MHz): d¼29.8, 107.9, 110.2, 110.4, 114.9, 119.1,
124.2, 124.6, 128.9, 132.8, 141.7, 149.1, 149.3, 163.3. IR
(KBr) n: 3318, 2818, 1620, 1589, 1542, 1523, 1475, 1465,
1454, 1425, 1324, 1269, 1244, 1177, 1073, 1030. MS (EI
70 eV, m/z, %): 224 (75, Mþ), 207 (9), 195 (6), 167 (4), 146
(5), 131 (7), 117 (100), 112 (6). HRMS for C14H12N2O
calcd 224.0950, found 224.0950.
3.2.9. 2-[2-(3-Propylamino)pyridyl]benzoxazole (17).
Light brown crystals. Mp 107–1088C. 1H NMR
(400 MHz): d¼1.11 (t, J¼7.5 Hz, 3H), 1.77–1.88 (m,
2H), 3.28–3.34 (m, 2H), 7.15 (dd, J¼8.6, 1.3 Hz, 1H),
7.27 (dd, J¼8.6, 4.4 Hz, 1H), 7.35–7.40 (m, 2H), 7.66–7.70
(m, 1H), 7.73–7.79 (m, 1H), 8.11 (dd, J¼4.4, 1.3 Hz, 1H),
8.41 (br s, 1H). 13C NMR (100 MHz): d¼11.7, 22.4, 44.4,
111.1, 118.2, 119.6, 124.5, 125.4, 126.5, 126.6, 136.8,
141.3, 145.5, 149.6, 162.3. IR (KBr) n: 3310, 2967, 2934,
1595, 1575, 1537, 1509, 1473, 1452, 1409, 1348, 1316,
1299, 1247, 1225, 1182, 1154, 1127, 1045. MS (EI 70 eV,
m/z, %): 253 (100, Mþ), 238 (24), 236 (40), 225 (14), 224
(86), 207 (7), 196 (35), 169 (9), 146 (21), 145 (36), 118 (4),
105 (9). HRMS for C15H15N3O calcd 253.1215, found
253.1216.
3.2.5. 2-[(2-Isopropylamino)phenyl]benzimidazole (13).
Yellow crystals. Mp 130–1328C. 1H NMR (400 MHz):
d¼1.36 (d, J¼6.4 Hz, 6H), 3.79 (sept, J¼6.4 Hz, 1H), 6.67
(ddd, J¼8.2, 7.1, 1.2 Hz, 1H), 6.70–6.73 (m, 2H), 6.80 (d,
J¼8.4 Hz, 1H), 7.29 (ddd, J¼8.4, 7.2, 1.6 Hz, 1H), 7.23–
7.27 (m, 2H), 7.54 (dd, J¼7.9, 1.6 Hz, 1H), 7.60 (br s, 1H),
9.0 (br s, 1H). 13C NMR (100 MHz): d¼22.9, 43.8, 110.5,
112.0, 114.4, 116.7, 120.3, 122.6, 126.8, 131.2, 134.7,
147.3, 152.2. IR (KBr) n: 3385, 2978, 1626, 1607, 1582,
1503, 1475, 1450, 1432, 1401, 1368, 1322, 1272, 1248,
1221, 1176, 961, 744. MS (EI 70 eV, m/z, %): 251 (37, Mþ),
236 (100), 221 (17), 220 (11), 194 (28), 126 (6), 111 (13).
HRMS for C16H17N3 calcd 251.1423, found 251.1421.
References
1. Wojciechowski, K. Eur. J. Org. Chem. 2001, 3587–3605.
2. Wojciechowski, K. Synlett 1991, 571–572.
3. Wojciechowski, K. Tetrahedron 1993, 49, 7277–7286.
4. Wojciechowski, K. Tetrahedron 1993, 49, 10017–10026.
´
5. Kosinski, S.; Wojciechowski, K. Eur. J. Org. Chem. 2000,
1263–1270.
3.2.6. 2-[2-(Isopropylamino)phenyl]benzoxazole (14).
Yellow crystals. Mp 86–878C. 1H NMR (400 MHz):
d¼1.38 (d, J¼6.4 Hz, 6H), 3.84 (sept, J¼6.4 Hz, 1H),
6.69 (ddd, J¼8.1, 7.1, 1.0 Hz, 1H), 6.81 (d, J¼8.4 Hz, 1H),
´
6. Wojciechowski, K.; Kosinski, S. Eur. J. Org. Chem. 2002,
947–954.