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4.3.7 Ethyl 2-acetyl-3-(4-methoxyphenyl)-4-nitrobutanoate 1552, 1487, 1368, 1246, 1177, 1142, 1008, 821, 717, 650 cmÀ1
;
(3g)79. Brownish oil; yield 85%; 1H NMR (300 MHz, CDCl3): MS (70 eV) m/z: 240 (5); 238 (5); 182 (3); 159 (3); 128 (1); 115 (6);
d 7.12 (d, 2H, J = 8.8 Hz), 6.83 (d, 2H, J = 8.8 Hz), 4.86–4.65 102 (4); 91 (2); 77 (5); 63 (2); 43 (100); elemental analysis:
(m, 2H), 4.23 (q, 1H, J = 7.0 Hz), 4.17–4.12 (m, 1H), 4.07 calculated for C14H16BrNO5: C, 46.95; H, 4.50; N, 3.91% found: C,
(d, 0.5H, J = 10.0 Hz), 4.01–3.94 (m, 1.5H), 3.76 (s, 3H), 2.29 46.96; H, 4.64; N, 3.99%.
(s, 1.50H), 2.05 (s, 1.50H), 1.28 (t, 1.50, J = 7.3 Hz), 1.03 (t, 1.5H,
J = 7.3 Hz); 13C NMR (75 MHz, CDCl3): d 201.2, 200.4, 167.5,
4.4 Synthesis of c-nitroesters 3l–p
166.8, 159.3, 129.0, 128.1, 127.9, 114.4, 114.2, 78.2, 78.0, 62.1, A mixture of ethyl malonate 1c (1 mmol), nitrostyrenes 2a–d,g
61.8, 61.7, 55.1, 41.9, 41.6, 30.2, 29.9, 13.9, 13.6, IR nmax (ATR): (1.1 mmol) and hydrotalcite (50 mg) in ethanol (2 mL) was
2969, 2923, 2830, 1742, 1712, 1612, 1552, 1506, 1466, 1436, stirred at reflux for 12 h. After this period, the reaction mixture
1373, 1360, 1254, 1181, 1029, 833, 733, 643 cmÀ1; MS (70 eV) was filtered through celite and the solvent evaporated in vacuo
m/z: 219 (33), 189 (35), 175 (45), 134 (41), 43 (100).
4.3.8 Ethyl 2-acetyl-4-nitro-3-(thiophen-2-yl)butanoate (3h). chromatography (hexane/EtOAc) to give the compounds 3l–p.
Brownish oil; yield 95%; 1H NMR (300 MHz, CDCl3): d 7.23–7.18 4.4.1 Diethyl (2-nitro-1-phenylethyl)-propanedioate (3l)76
to give the crude product, which was purified by column
.
(m, 1H), 6.94–6.91 (m, 2H), 4.86–4.80 (m, 2H), 4.59–4.48 Orange solid; yield 80%; m.p. 62–64 1C; 1H NMR (300 MHz,
(m, 1H), 4.24 (q, 1.03H, J = 7.0 Hz); 4.17 (d, 0.49H, J = 8.8 Hz), CDCl3): d 7.34–7.22 (m, 5H), 4.93 (dd, 1H, J = 12.9 and 5.3 Hz),
4.12–4.05 (m, 1.48H), 2.31 (s, 1.58H), 2.17 (s, 1.42H), 1.28 (t, 1.42, 4.85 (dd, 1H, J = 12.9 and 8.8 Hz), 4.27–4.18 (m, 3H), 4.00 (q, 2H,
J = 7.0 Hz), 1.13 (t, 1.58H, J = 7.0 Hz); 13C NMR (75 MHz, CDCl3): J = 7.0 Hz), 3.82 (d, 1H, J = 9.4 Hz), 1.25 (t, 3H, J = 7.0 Hz), 1.03
d 201.0, 200.1, 167.2, 166.6, 138.7, 127.1, 127.0, 126.8, 126.5, (t, 3H, J = 7.0 Hz); 13C NMR (75 MHz, CDCl3): d 167.3, 166.7,
125.4, 125.3, 78.2, 78.1, 62.4, 62.1, 37.9, 37.7, 30.2, 13.9, 13.7; IR 136.1, 128.7, 128.1, 127.9, 77.5, 62.0, 61.7, 54.8, 42.8, 13.8, 13.5;
n
max (ATR): 2923, 2838, 1740, 1720, 1553, 1460, 1376, 1260, 1144, IR nmax (ATR): 2993, 2900, 1724, 1545, 1494, 1434, 1366, 1287,
1096, 909, 845, 800, 713 cmÀ1; MS (70 eV) m/z 269(11); 268(21); 1230, 1196, 1094, 1034, 1016, 860, 766, 705 cmÀ1. MS (70 eV)
195(100); 177(27); 167(53); 151(32); 110(50); 97(10); 79(7); 65(8); m/z: 263 (18), 218 (13), 189 (100), 104 (45).
elemental analysis: calculated for C12H15NO5S: C, 50.52; H, 5.30;
N, 4.91% found: C, 50.63; H, 5.42; N, 4.92%.
4.4.2 Diethyl [1-(3,4-dimethoxyphenyl)-2-nitroethyl]-propane-
dioate (3m). Orange solid; yield 68%; m.p. 85–87 1C; 1H NMR
4.3.9 Ethyl
2-acetyl-3-(4-fluorophenyl)-4-nitrobutanoate (300 MHz, CDCl3): d 6.72–6.67 (m, 3H), 4.86–4.73 (m, 2H), 4.23–
(3i)80. Yellowish oil; yield 71%; 1H NMR (300 MHz, CDCl3): 4.01 (m, 3H), 3.96 (q, 2H, J = 7.0 Hz), 3.79 (s, 3H), 3.77 (s, 3H), 3.75
d 7.23–7.18 (m, 2H), 7.04–6.98 (m, 2H), 4.89–4.66 (m, 2H), 4.28– (d, 1H, J = 9.4 Hz), 1.20 (t, 3H, J = 7.0 Hz), 1.02 (t, 3H, J = 7.0 Hz);
4.17 (m, 2H), 4.08 (d, 0.55H, J = 10.0 Hz); 4.01–3.94 (m, 1.45H), 13C NMR (75 MHz, CDCl3): d 167.4, 166.8, 149.0, 148.8, 128.5,
2.30 (s, 1.69H), 2.08 (s, 1.31H); 1.28 (t, 1.31H, J = 7.0 Hz); 1.03 120.0, 111.3, 111.2, 77.8, 62.0, 61.8, 55.8, 55.7, 55.0, 42.6, 13.9,
(t, 1.69H, J = 7.0 Hz); 13C NMR (75 MHz, CDCl3): d 200.8, 200.0, 13.8; IR nmax (ATR): 2993, 2938, 1726, 1591, 1551, 1520, 1469,
167.3, 166.6, 163.7 (d, J = 247.5 Hz); 132.1 (d, J = 3.0 Hz); 129.6 1439, 1378, 1297, 1264, 1237, 1166, 1142, 1095, 1078, 1020, 872,
(t, J = 7.5 Hz), 116.0 (d, J = 17.2 Hz), 115.7 (d, J = 16.5 Hz), 77.8, 804, 767, 642 cmÀ1; MS (70 eV) m/z: 369 (M+, 31) 322 (41) 249
77.6, 62.2, 62.0, 61.9, 61.6, 41.7, 41.5, 30.1, 29.8, 13.8, 13.6; (100), 164 (90); elemental analysis: calculated for C17H23NO8:
IR nmax (ATR): 2993, 2915, 1739, 1715, 1608, 1555, 1510, 1430, C, 55.28; H, 6.28; N, 3.79% found: C, 55.25; H, 6.19; N, 3.79%.
1368, 1167, 1100, 1020, 836, 739, 711, 625 cmÀ1, MS (70 eV)
m/z: 251 (0.4), 207 (20), 163 (20), 122 (14), 43 (100).
4.4.3 Diethyl [2-nitro-1-(thiophen-2-yl)ethyl]-propanedioate
(3n)81. Brownish oil; yield 75%; 1H NMR (300 MHz, CDCl3):
4.3.10 Ethyl 2-acetyl-3-(4-chlorophenyl)-4-nitrobutanoate d 7.16 (d, 1H, J = 4.7 Hz), 6.89–6.84 (m, 2H), 4.91–4.76 (m, 2H),
(3j)77. Yellowish oil; yield 85%; 1H NMR (300 MHz, CDCl3): 4.52–4.45 (m, 1H), 4.20–4.01 (m, 4H), 3.87 (d, 1H, J = 8.2 Hz), 1.27
d 7.30 (d, 2H, J = 8.2 Hz), 7.16 (d, 2H, J = 8.2 Hz), 4.88–4.67 (t, 3H, J = 7.0 Hz), 1.16 (t, 3H, J = 7.0 Hz); 13C NMR (75 MHz,
(m, 2H), 4.27–4.16 (m, 2H), 4.08 (d, 0.55H, J = 10.0 Hz), 4.00–3.96 CDCl3): d 167.1, 166.6, 138.4, 126.9, 126.8, 125.6, 125.4, 78.0,
(m, 1.45H), 2.31 (s, 1.69H), 2.09 (s, 1.31H), 1.29 (t, 1.3 1H, J = 62.2, 62.1, 55.6, 55.4, 38.4, 13.8, 13.7; IR nmax (ATR): 2923, 2838,
7.0 Hz), 1.05 (t, 1.69H, J = 7.0 Hz); 13C NMR (75 MHz, CDCl3) 1726, 1557, 1466, 1436, 1372, 1259, 1180, 1150, 1093, 1025, 852,
d 200.7, 199.9, 167.2, 166.6, 134.9, 134.2, 129.4, 129.3, 129.2, 796, 701, 600 cmÀ1. MS (70 eV) m/z: 269 (11), 268 (21), 195 (100),
129.0, 77.6, 77.4, 62.3, 62.1, 61.7, 61.5, 41.7, 41.6, 30.2, 29.9, 13.9, 177 (27), 167 (53), 151 (32), 110 (50), 97 (10), 79 (7), 65 (8).
13.6; IR nmax (ATR): 2993, 2923, 1734, 1717, 1551, 1486, 1432,
1412, 1374, 1245, 1178, 1093, 1011, 821, 716, 665 cmÀ1; MS (70 eV) dioate (3o)81. Yellowish oil; yield 75%; 1H NMR (300 MHz,
m/z: 267 (0.6), 223 (16), 179 (11), 138 (8), 43 (100). CDCl3): d 7.27–7.20 (m, 2H), 7.05–6.97 (m, 2H), 4.92 (dd, 1H,
4.4.4 Diethyl [1-(4-fluorophenyl)-2-nitroethyl]-propane-
4.3.11 Ethyl 2-acetyl-3-(4-bromophenyl)-4-nitrobutanoate J = 12.9 and 4.7 Hz), 4.82 (dd, 1H, J = 12.9 and 9.4 Hz), 4.28–4.18
(3k). Yellowish oil; yield 70%; 1H NMR (300 MHz, CDCl3): (m, 3H), 4.02 (q, 2H, J = 7.0 Hz), 3.78 (d, 1H, J = 9.4 Hz), 1.27
d 7.45 (d, 2H, J = 8.3 Hz), 7.10 (d, 2H, J = 8.3 Hz), 4.88–4.67 (t, 3H, J = 7.0 Hz), 1.07 (t, 3H, J = 7.0 Hz); 13C NMR (75 MHz,
(m, 2H), 4.27–3.96 (m, 4H), 2.30 (s, 1.65 H); 2.09 (s, 1.35H), 1.28 CDCl3): d 167.2, 166.6, 162.4, (d, J = 246 Hz), 131.9 (d, J = 3.7 Hz),
(t, 1.35H, J = 7.3 Hz), 1.05 (t, 1.65H, J = 7.3 Hz); 13C NMR (75 MHz, 129.7 (d, J = 8.2 Hz), 115.9 (d, J = 21 Hz), 77.6, 62.2, 61.9, 54.9,
CDCl3): d 200.7, 199.9, 167.2, 166.5, 135.5, 135.4, 132.2, 132.0, 42.2, 13.9, 13.7; IR nmax (ATR): 2923, 2846, 1727, 1606, 1554,
129.6, 129.5, 122.3, 122.2, 77.5, 77.4, 62.3, 62.1, 61.6, 61.4, 41.8, 1508, 1463, 1437, 1373, 1229, 1150, 1098, 1018, 842, 747 cmÀ1
.
41.6, 30.2, 29.9, 13.9, 13.6, IR nmax (ATR): 2985, 2907, 1739, 1716, MS (70 eV) m/z 327 (M+, 1), 281 (16), 207 (100), 122 (57).
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