Ethylenediamine: A Highly Effective Catalyst for One-Pot Synthesis of Aryl Nitroalkenes
(E)-4-(2-Nitrovinyl)phenol (1k) Yellow crystals,
m.p. 165—166 ℃. H NMR (500 MHz, acetone-d6) δ:
150.22, 149.28, 145.77, 133.91, 124.80, 124.06, 113.40,
112.31, 64.44, 56.05, 14.66, 14.17; IR (KBr film) ν:
1
6.96 (d, J=8.6 Hz, 2H), 7.71 (d, J=8.6 Hz, 2H), 7.85
(d, J=13.5 Hz, 1H), 8.03 (d, J=13.5 Hz, 1H); IR (KBr
film) ν: 3365, 3050, 2510, 1598, 1485, 1340, 1280,
1255, 1160, 970, 825, 560 cm ; MS (EI) m/z (%): 165
(67) [M]+, 148 (9), 135 (2), 118 (100), 107 (15), 91 (26),
77 (9), 65 (28).
2989, 2938, 1649, 1599, 1523, 1498, 1299, 1265, 1141,
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1
1031, 913, 796, 615 cm ; MS (EI) m/z (%): 237 (100)
[M]+, 238 (11), 222 (1), 206 (3), 190 (23), 163 (11), 162
(51), 147 (26), 131 (25), 103 (40), 91 (16), 77 (13). Anal.
calcd for C12H15NO4: C 60.75, H 6.37, N 5.90; found C
60.54, H 6.48, N 6.13.
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1
(E)-3-(2-Nitrovinyl)-1H-indole (1l) Orange crys-
tals, m.p. 170—171 ℃. 1H NMR (500 MHz, acetone-d6)
δ: 7.25—7.36 (m, 2H), 7.56—7.62 (m, 1H), 7.93 (d, J=
13.4 Hz, 1H), 7.95—8.02 (m, 1H), 8.16 (s, 1H), 8.40 (d,
J=13.4 Hz, 1H); IR (KBr film) ν: 3410, 3126, 2981,
2520, 1629, 1598, 1517, 1499, 1478, 1336, 1265, 1144,
925, 800, 745 cm ; MS (EI) m/z (%): 188 (100) [M] ,
171 (8), 156 (3), 145 (27), 141 (70), 130 (13), 115 (91),
104 (10), 89 (17), 77 (7), 63 (10). Anal. calcd for
C10H8N2O2: C63.82, H 4.28, N 14.89; found C 63.66, H
4.41, N 15.12.
(E)-5-(2-Nitroprop-1-enyl)benzo[d][1,3]dioxole (1q)
Yellow crystals, m.p. 98—99 ℃. H NMR (500 MHz,
1
CDCl3) δ: 2.46 (s, 3H), 6.05 (s, 2H), 6.85 (d, J=8.1 Hz,
1H), 6.95 (s, 1H), 6.98 (dd, J1=8.1 Hz, J2=1.0 Hz, 1H),
8.02 (s, 1H); IR (KBr film) ν: 3180, 2975, 2920, 1665,
1598, 1525, 1455, 1418, 1328, 1260, 1025, 995, 920,
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+
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+
1
1
825 cm ; MS (EI) m/z: 207 (67) [M] , 176 (16), 160
(73), 149 (20), 131 (23), 119 (2), 103 (100), 102 (50),
92 (16), 77 (60), 63 (30).
(E)-1-Ethoxy-4-(2-nitroprop-1-enyl)benzene (1r)
1
Pale yellow crystals, m.p. 74—75 ℃. H NMR (400
(E)-1-Fluoro-4-(2-nitrovinyl)benzene (1m) Pale
yellow crystals, m.p. 101—102 ℃. 1H NMR (400 MHz,
CDCl3) δ: 7.12—7.18 (m, 2H), 7.51—7.62 (m, 3H),
7.99 (d, J=13.6 Hz, 1H); 13C NMR (100 MHz, CDCl3)
δ: 166.21, 163.68, 137.89, 136.87, 131.39, 131.30,
126.36, 126.33, 116.89, 116.67; IR (KBr film) ν: 3113,
1639, 1592, 1507, 1422, 1342, 1231, 1162, 963, 831,
520 cm ; MS (EI) m/z: 167 (43) [M] , 150 (9), 137 (4),
121 (16), 120 (100), 109 (40), 101 (88), 95 (21), 84 (11),
75 (31), 63 (5). Anal. calcd for C8H6FNO2: C 57.49, H
3.62, N 8.38; found C 57.36, H 3.81, N 8.19.
MHz, CDCl3) δ: 1.45 (t, J=7.0 Hz, 3H), 2.47 (s, 3H),
4.09 (q, J=7.0 Hz, 2H), 6.94 (d, J=8.4 Hz, 1H), 6.96
(d, J=8.8 Hz, 2H), 7.41 (d, J=8.8 Hz, 2H), 8.06 (s,
1H); 13C NMR (100 MHz, CDCl3) δ: 160.56, 145.55,
133.69, 132.14, 124.51, 114.94, 63.72, 14.69, 14.11; IR
(KBr film) ν: 2983, 1645, 1605, 1519, 1495, 1392, 1300,
1260, 1180, 1097, 984, 919, 845, 587, 529 cm ; MS
(EI) m/z (%): 207 (86) [M]+, 208 (10), 191 (2), 177 (3),
161 (15), 160 (100), 149 (6), 133 (83), 132 (83), 131
(69), 121 (39), 105 (56), 77 (57), 63 (15). Anal. calcd
for C11H13NO3: C 63.76, H 6.32, N 6.76; found C 63.39,
H 6.57, N 6.54.
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+
1
(E)-2,4-Dichloro-1-(2-nitrovinyl)benzene (1n) Yel-
1
low crystals, m.p. 108—109 ℃. H NMR (400 MHz,
(E)-1-Ethoxy-3-(2-nitroprop-1-enyl)benzene (1s)
1
CDCl3) δ: 7.34 (dd, J1=2.0 Hz, J2=8.5 Hz, 1H), 7.52
(d, J=2.0 Hz, 1H), 7.54 (d, J=8.5 Hz, 1H), 7.58 (d,
J=13.7 Hz, 1H), 8.15 (d, J=13.7 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ: 139.03, 138.47, 136.66, 133.97,
130.64, 129.32, 128.05, 127.09; IR (KBr film) ν: 3105,
1633, 1587, 1501, 1469, 13587, 1340, 1278, 1105, 971,
Pale yellow oil. H NMR (400 MHz, CDCl3) δ: 1.44 (t,
J=7.0 Hz, 3H), 2.44 (s, 3H), 4.06 (q, J=7.0 Hz, 2H),
6.93 (s, 1H), 6.95 (d, J=7.8 Hz, 2H), 6.99 (d, J=7.8
Hz, 1H), 7.35 (t, J=7.9 Hz, 1H), 8.06 (s, 1H); IR (KBr
film) ν: 2989, 2940, 1658, 1597, 1575, 1529, 1442,
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1
1388, 1333, 1274, 1169, 1048, 955, 795, 695 cm ; MS
(EI) m/z (%): 207 (100) [M]+, 208 (10), 192 (2), 178 (2),
162 (15), 160 (13), 150 (8), 133 (11), 132 (20), 131 (28),
105 (21), 121 (17), 103 (19), 77 (14).
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+
1
816, 786 cm ; MS (EI) m/z (%): 217 (50) [M] , 218
(5), 184 (33), 182 (100), 172 (47), 170 (71), 154 (30),
152 (87), 136 (53), 99 (44), 83 (7), 75 (16). Anal. calcd
for C8H5Cl2NO2: C 44.07, H 2.31, N 6.42; found C
44.31, H 2.43, N 6.25.
(E)-1-(Benzyloxy)-4-(2-nitroprop-1-enyl)benzene
1
(1t) Yellow crystals, m.p. 144—145 ℃. H NMR
(E)-1,2-Dimethoxy-4-(2-nitroprop-1-enyl)benzene
(1o) Yellow crystals, m.p. 73—74 ℃. H NMR (500
(400 MHz, CDCl3) δ: 2.45 (s, 3H), 5.11 (s, 2H), 7.03 (d,
J=8.7 Hz, 2H), 7.31—7.44 (m, 7H), 8.05 (s, 1H); 13C
NMR (101 MHz, CDCl3) δ: 160.27, 145.83, 136.29,
133.56, 132.13, 128.74, 128.27, 127.50, 125.00, 115.37,
70.17, 14.14; IR (KBr film) ν: 2941, 1645, 1602, 1517,
1495, 1386, 1294, 1255, 1178, 1169, 1003, 979, 928,
762, 705, 620 cm ; MS (EI) m/z (%): 269 (9) [M] ,
270 (2), 223 (1), 178 (1), 115 (2), 103 (2), 92 (6), 91
(100), 77 (1), 65 (4). Anal. calcd for C16H15NO3: C
71.36, H 5.61, N 5.20; found C 71.53, H 5.47, N 5.36.
1
MHz, CDCl3) δ: 2.50 (s, 3H), 3.92 (s, 3H), 3.94 (s, 3H),
6.91—6.98 (m, 2H), 7.14 (dd, J1=8.3 Hz, J2=1.5 Hz,
1H), 8.07 (s, 1H); IR (KBr film) ν: 3128, 2926, 1645,
1600, 1525, 1340, 1284, 1118, 1035, 982, 926, 845, 820,
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+
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+
1
1
605 cm ; MS (EI) m/z (%): 223 (100) [M] , 224 (12),
208 (3), 192 (13), 176 (75), 161 (32), 146 (30), 131 (37),
119 (23), 115 (21), 103 (22), 91 (27), 77 (18), 65 (13).
(E)-1-Ethoxy-2-methoxy-4-(2-nitroprop-1-enyl)-
1
benzene (1p) Yellow crystals, m.p. 111—112 ℃. H
(E)-4-(2-Nitroprop-1-enyl)phenol (1u)
Yellow
NMR (400 MHz, CDCl3) δ: 1.50 (t, J=7.0 Hz, 3H),
2.49 (s, 3H), 3.91 (s, 3H), 4.16 (q, J=7.0 Hz, 2H), 6.94
(d, J=8.4 Hz, 1H), 6.97 (s, 1H), 7.07 (d, J=8.4 Hz,
1H), 8.06 (s, 1H); 13C NMR (100 MHz, CDCl3) δ:
crystals, m.p. 123—124 ℃. 1H NMR (500 MHz,
CDCl3) δ: 2.48 (s, 3H), 5.70 (s, 1H), 6.94 (d, J=8.7 Hz,
2H), 7.38 (d, J=8.7 Hz, 2H), 8.08 (s, 1H); IR (KBr film)
ν: 3300, 2926, 1650, 1600, 1532, 1435, 1288, 1200,
Chin. J. Chem. 2012, 30, 2827—2833
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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