A. S. Saiyed, A. V. Bedekar / Tetrahedron: Asymmetry 24 (2013) 1035–1041
1039
4.8. N-Benzyl-2-(4–phenyl–4,5-dihydrooxazol-2-yl)aniline 8
392.48 (100), 301.18 (43), 258.19 (83), 244.22 (31), 140.94 (56),
90.84 (16), 76.81 (7). Anal. Calcd for C27H24N2O C, 82.62; H, 6.16;
N, 7.14. Found: C, 82.43; H, 6.01; N, 7.42.
Yield: 71%; ½a 3D5
¼ þ137:8(c 0.40, CHCl3); mp 116–118 °C; IR
ꢁ
(KBr):
m 3248, 3062, 3026, 2966, 1632, 1584, 1521, 1493, 1269,
1168, 103, 897, 749, 730, 696 cmꢂ1
.
1H NMR (400 MHz, CDCl3): d
4.12. N-(4-Bromobenzyl)-2-(4-isopropyl-4,5-dihydrooxazol-2-
9.13–9.10 (t, J = 5.6 Hz, 1H), 7.88–7.86 (m, 1H), 7.42–7.25 (m,
11H), 6.71–6.67 (m, 2H), 5.53–5.48 (dd, J = 8.4 and 10 Hz, 1H),
4.76–4.71 (dd, J = 8.4 and 9.6 Hz, 1H), 4.55 (d, J = 5.6 Hz, 2H), 4.2–
4.15 (t, J = 8.4 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 165.33,
149.21, 142.79, 139.43, 132.75, 130.10, 128.72, 128.55, 127.54,
126.89, 126.92, 114.72, 111.01, 108.44, 72.92, 70.14, 46.88. MS
(EI): m/z (%) 328.41 (87), 327.05 (100), 223.24 (24), 208.24 (30),
179.03 (38), 146.76 (55), 105.03 (49), 90.88 (54), 76.61 (27). Anal.
Calcd for C22H20N2O C, 80.46; H, 6.14; N, 8.53. Found: C, 80.21; H,
5.79; N, 8.71.
yl)aniline 12
Yield: 81%; ½a 3D5
¼ ꢂ6:7 (c 0.70, CHCl3); mp 100–102 °C; IR
ꢁ
(KBr):
m 3243, 2958, 2864, 1632, 1488, 1455, 1239, 1308, 805,
748 cmꢂ1 1H NMR (400 MHz, CDCl3): d 9.08 (br s, 1H), 7.78–7.59
.
(dd, J = 1.6 and 7.6 Hz, 1H), 7.48–7.46 (m, 2H), 7.29–7.24 (m, 3H),
6.67–6.63 (m, 1H), 6.60 (d, J = 8.4 Hz, 1H), 4.46 (d, J = 4.4 Hz, 2H),
4.37–4.33 (q, J = 8.0 Hz, 1H), 4.15–4.11 (m, 1H), 4.05–4.01 (t,
J = 7.6 Hz, 1H), 1.82–1.74 (m, 1H), 0.99 (d, J = 6.8 Hz, 3H), 0.94 (d,
J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3): d 163.84, 148.71,
138.45, 132.47, 132.41, 131.62, 129.89, 128.82, 120.67, 114.91,
110.66, 108.90, 72.79, 68.77, 46.51, 33.27, 18.89, 18.70. MS (EI):
m/z (%) 373.62 (100), 371.82 (30), 331.18 (11), 328 (17), 287.10
(21), 285.54 (44), 272.05 (11), 270.83 (6). Anal. Calcd for C19H21-
BrN2O C, 61.13; H, 5.67; N, 7.50. Found: C, 60.67; H, 5.31; N, 7.99.
4.9. N-Benzyl-2-(4-(tert-butyl)-4,5-dihydrooxazol-2-yl)aniline 9
Yield: 80%; ½a 3D0
ꢁ
¼ ꢂ20:7 (c 0.80, CHCl3); mp 96–98 °C; IR (KBr):
m
3255, 3063, 3031, 2968, 2954, 2887, 1632, 1578, 1574, 1515, 1497,
1470, 1452, 1361, 1328, 1287, 1263, 1240, 1167, 1143, 1091, 1076,
1050, 1028, 975, 906, 749, 700, 670 cmꢂ1
.
1H NMR (400 MHz,
4.13. N-(3,5-Dibromobenzyl)-2-(4-isopropyl-4,5-dihydrooxazol-
CDCl3): d 9.08 (br s, 1H), 7.77–7.75 (dd, J = 0.8 and 7.6 Hz, 1H),
7.42 (d, J = 7.2 Hz, 2H), 7.38–7.34 (t, J = 7.6 Hz, 2H), 7.30–7.27 (q,
J = 4.8 and 7.6 Hz, 2H), 6.70–6.63 (m, 2H), 4.51 (d, J = 4.8 Hz, 2H),
4.30–4.23 (m, 1H), 4.15–4.07 (m, 2H), 0.91 (s, 9H). 13C NMR
2-yl)aniline 13
Yield: 61%; ½a 3D5
¼ ꢂ17:15 (c 0.50, CHCl3); mp 118–120 °C; IR
ꢁ
(KBr):
m 3216, 3085, 2959, 2899, 2864, 1637, 1586, 1520, 1463,
(100 MHz, CDCl3):
d
163.74, 148.98, 139.25, 132.34, 129.78,
1357, 1328, 1080, 1049, 964, 849, 744, 682, 632, 588, 537 cmꢂ1
.
128.57, 127.27, 127.01, 114.53, 110.59, 108.72, 76.27, 66.80,
47.18, 33.86, 25.86. MS (EI): m/z (%) 307.83 (100), 250.79 (63),
207.77 (57), 194.14 (21), 90.85 (10). Anal. Calcd for C20H24N2O C,
77.89; H, 7.84; N, 9.08. Found: C, 77.64; H, 7.43; N, 9.44.
1H NMR (400 MHz, CDCl3): d 9.15 (br s, 1H), 7.79–7.77 (dd,
J = 1.6 and 8.0 Hz, 1H), 7.58–7.57 (m, 1H), 7.48–7.47 (m, 2H),
7.29–7.25 (m, 1H), 6.71–6.67 (m, 1H), 6.55 (d, J = 8.0 Hz, 1H),
4.51–4.41 (q, J = 15.6 Hz, 2H), 4.39–4.34 (m, 1H), 4.17–4.11 (m,
1H), 4.07–4.03 (t, J = 8.0 Hz, 1H), 1.84–1.77 (m, 1H), 1.02 (d,
J = 6.8 Hz, 3H), 0.96 (d, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3):
d 163.82, 148.44, 143.83, 132.70, 132.48, 129.94, 128.78, 123.19,
115.32, 110.59, 109.16, 76.74, 72.77, 68.78, 46.25, 18.97, 18.69.
MS (EI): m/z (%) 453.70 (74), 452.37 (48), 451.81 (31), 450.95
(100), 449.22 (91), 410.12 (17), 409.03 (28), 408.10 (31), 406.35
(33), 368.18 (26), 367.12 (30), 365.54 (99), 363.46 (53), 146.51
(39), 104.51 (36), 76.75 (18). Anal. Calcd for C19H20Br2N2O C,
50.47; H, 4.46; N, 6.20. Found: C, 50.05; H, 3.98; N, 6.45.
4.10. 2-(4-Isopropyl-4,5-dihydrooxazol-2-yl)-N-(naphthalen-2-
ylmethyl)aniline 10
Yield: 62%; ½a 3D0
¼ ꢂ24:3 (c 0.80, CHCl3); mp 128–130 °C; IR
ꢁ
(KBr):
m 3250, 3053, 2959, 2927, 2898, 2871, 1631, 1586, 1523,
1463, 1362, 1318, 1273, 1236, 1163, 1144, 1087, 1049, 967, 904,
853, 816, 748, 686 cmꢂ1 1H NMR (400 MHz, CDCl3): d 9.17–9.14
.
(t, J = 4.8 Hz, 1H), 7.83–7.78 (m, 4H), 7.76–7.74 (dd, J = 1.6 and
8.0 Hz, 1H), 7.51–7.49 (dd, J = 1.6 and 8.4 Hz, 1H), 7.48–7.42 (m,
2H), 7.25–7.20 (m, 1H), 6.68 (d, J = 8.4 Hz, 1H), 6.64–6.60 (m,
1H), 4.69–4.60 (m, 2H), 4.35–4.28 (m, 1H), 4.13–4.09 (m, 1H),
4.03–3.99 (t, J = 7.6 Hz, 1H), 1.80–1.72 (m, 1H), 0.96 (d, J = 6.8 Hz,
3H), 0.91 (d, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3): d 163.83,
148.99, 136.87, 133.51, 132.67, 132.37, 129.80, 128.28, 127.77,
127.68, 126.03, 125.54, 125.52, 125.41, 114.67, 110.79, 108.85,
72.87, 68.72, 47.31, 33.30, 18.91, 18.72. MS (EI): m/z (%) 345.20
(60), 344.19 (100), 302.37 (39), 233.31 (23), 144.01 (15), 91.90
(10). Anal. Calcd for C23H24N2O C, 80.20; H, 7.02; N, 8.13. Found:
C, 79.94; H, 6.87; N, 8.47.
4.14. 2-(4-Benzyl-4,5-dihydrooxazol-2-yl)-N-(3,5-dibromobenzyl)
aniline 14
Yield: 59%; ½a 3D5
¼ þ4:4 (c 0.71, CHCl3); mp 112–114 °C; IR (KBr):
ꢁ
m
3210, 3067, 3027, 2844, 1636, 1553, 1526, 1468, 1365, 1238, 1028,
847, 750, 693, 571, 541 cmꢂ1. 1H NMR (400 MHz, CDCl3): d 9.01 (br s,
1H), 7.79–7.77 (dd, J = 1.6 and 7.6 Hz, 1H), 7.59–7.58 (t, J = 1.6 Hz,
1H), 7.48–7.47 (m, 2H), 7.34–7.24 (6H), 6.71–6.66 (m, 1H), 6.52 (d,
J = 8.0 Hz, 1H), 4.68–4.64 (m, 1H), 4.46 (d, J = 4.8 Hz, 2H), 4.36–
4.32 (t, J = 8.4 Hz, 1H), 4.11–4.08 (q, J = 7.2 Hz, 1H), 3.17–3.12 (dd,
J = 6.4 and 13.6 Hz, 1H), 2.87–2.82 (dd, J = 7.6 and 13.6 Hz, 1H). 13
C
4.11. 2-(4-Benzyl-4,5-dihydrooxazol-2-yl)-N-(naphthalen-2-yl-
methyl)aniline 11
NMR (100 MHz, CDCl3): d 164.93, 149.51, 139.83, 138.72, 138.50,
132.95, 130.21, 129.68, 129.02, 128.88, 126.95, 125.12, 114.93,
111.21, 108.92, 70.40, 68.62, 47.43, 43.10. MS (EI): m/z (%) 501.64
(57), 500.05 (70), 499.07 (50), 497.99 (52), 410.59 (66), 409.00
(71), 407.71 (100), 405.98 (51), 367.75 (31), 363.81 (19), 362.63
(26), 351.91 (30), 350.67 (25), 349.59 (16), 248.46 (12), 90.87 (8).
Anal. Calcd for C23H20Br2N2O C, 55.22; H, 4.03; N, 5.60. Found: C,
54.88; H, 3.71; N, 5.93.
Yield: 58%; ½a 3D5
ꢁ
¼ þ10:1 (c 0.70, CHCl3); mp 124 °C; IR (KBr):
m
3255, 3056, 3024, 2885, 2851, 1627, 1580, 1516, 1452, 1363, 1328,
1281, 1240, 1166, 1080, 1034, 983, 905, 867, 819, 750 cmꢂ1 1H
.
NMR (400 MHz, CDCl3): d 9.11 (br s, 1H), 7.88–7.78 (m, 5H),
7.54–7.49 (m, 3H), 7.28–7.18 (m, 6H), 6.71–6.65 (m, 2H), 4.70–
4.64 (m, 3H), 4.34–4.31 (t, J = 8.4 Hz, 1H), 4.10–4.06 (t, J = 7.6 Hz,
1H), 3.15–3.10 (dd, J = 6.4 and 13.6 Hz, 1H), 2.85–2.79 (dd, J = 7.6
and 13.6 Hz, 1H). 13C NMR (100 MHz, CDCl3): d 164.45, 149.05,
138.22, 136.90, 133.54, 132.71, 132.62, 129.93, 129.25, 128.44,
128.34, 127.81, 127.71, 126.43, 126.09, 125.59, 125.41, 114.80,
110.98, 108.62, 70.19, 67.97, 47.23, 42.26. MS (EI): m/z (%)
4.15. N-(3,5-Dimethylbenzyl)-2-(4-isopropyl-4,5-dihydro oxaz-
ol-2-yl)aniline 15
Yield: 55%; ½a 3D5
¼ ꢂ36:9(c 0.60, CHCl3); mp 102–104 °C; IR
ꢁ
(KBr):
m 3230, 2892, 1639, 1519, 1455, 1356, 1332, 1271, 1236,