10.1002/ejoc.201901630
European Journal of Organic Chemistry
FULL PAPER
149.0, 148.2, 142.6, 129.7, 124.0, 115.1, 108.5, 106.4, 101.4, 37.5, 36.1;
IR(KBr): 3353, 2920, 2851, 2368, 2333, 1650, 1603, 1499, 1406, 1255,
1060, 845, 649, 522 cm-1; HRMS (ESI) calcd. for C12H14NO3: [M+H]+:
220.0974, found: 220.0963.
1.41 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) 167.0,
146.1, 120.3, 37.3, 35.6, 34.5, 21.6, 13.7; IR(KBr): 3448, 2930, 2873,
1667, 1620, 1495, 1396, 1155, 1119, 980, 845 cm-1; HRMS (ESI) calcd.
for C8H16NO: [M+H]+: 142.1232, found: 142.1225.
(E)-N,N-dimethyl-3-(naphthalen-1-yl)acrylamide (3u)[9f]: Purification by
column chromatography on silica gel (Rf = 0.30, petroleum ether/ethyl
acetate = 2:1) yielded 3u (103.5 mg, 92%) as a yellow liquid; 1H NMR
(400 MHz, CDCl3) ppm: 8.50 (d, J = 15.2 Hz, 1H), 8.29 (d, J = 8.3 Hz,
1H), 7.85 (d, J = 8.3 Hz, 2H), 7.70 (d, J = 7.2 Hz, 1H), 7.57-7.50 (m, 2H),
7.49-7.44 (m, 1H), 6.93 (d, J = 15.2 Hz, 1H), 3.17 (s, 3H), 3.10 (s, 3H);
13C NMR (100 MHz, CDCl3) 166.6, 139.7, 133.6, 133.1, 131.5, 129.7,
128.5, 126.6, 126.1, 125.3, 124.5, 123.8, 120.4, 37.4, 35.9; IR(KBr):
3060, 2928, 1628, 1600, 1410, 1346, 1260, 1180, 974, 800, 778, 589 cm-
1; HRMS (ESI) calcd. for C15H16NO: [M+H]+: 226.1232, found: 226.1229.
N,N-diethylcinnamamide
(4a)[9e]
:
Purification
by
column
chromatography on silica gel (Rf = 0.26, petroleum ether/ethyl acetate =
2:1) yielded 4a (67.0 mg, 66%) as a white solid; m.p. 76.5-78.4 °C; 1H
NMR (400 MHz, CDCl3) ppm: 7.70 (d, J = 15.4 Hz, 1H), 7.51 (dd, J = 8.0,
1.8 Hz, 2H), 7.38-7.31 (m, 3H), 6.82 (d, J = 15.4 Hz, 1H), 3.47 (dt, J =
16.4, 7.1 Hz, 4H), 1.25 (t, J = 7.2 Hz, 3H), 1.18 (t, J = 7.1 Hz, 3H); 13C
NMR (100 MHz, CDCl3) 165.6, 142.2, 135.4, 129.4, 128.7, 127.7, 117.7,
42.2, 41.0, 15.0, 13.2; IR(KBr): 3406, 2931, 1650, 1560, 1459, 1130,
1031, 780 cm-1; HRMS (ESI) calcd. for C13H18NO: [M+H]+: 204.1388,
found: 204.1384.
(E)-N,N-dimethyl-3-(pyridin-2-yl)acrylamide (3v)[20c]
column chromatography on silica gel (Rf = 0.25, petroleum ether/ethyl
:
Purification by
(E)-N,N-diethyl-3-(o-tolyl)acrylamide (4b): Purification by column
chromatography on silica gel (Rf = 0.26, petroleum ether/ethyl acetate =
2:1) yielded 4b (47.6 mg, 44%) as a light yellow liquid; 1H NMR (400 MHz,
CDCl3) ppm: 7.98 (d, J = 15.2 Hz, 1H), 7.54-7.51 (m, 1H), 7.27-7.18 (m,
3H), 6.73 (d, J = 15.3 Hz, 1H), 3.49 (dt, J = 18.7, 7.0 Hz, 4H), 2.43 (s,
3H), 1.26 (t, J = 7.1 Hz, 3H), 1.20 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz,
CDCl3) 165.7, 140.0, 137.3, 134.6, 130.6, 129.1, 126.0, 119.0, 42.2, 41.0,
19.8, 15.0, 13.1; IR(KBr): 2974, 2931, 1680, 1485, 1430, 1361, 1286,
1243, 1221, 1139, 761 cm-1; HRMS (ESI) calcd. for C14H20NO: [M+H]+:
218.1545, found: 218.1544.
acetate = 2:1) yielded 3v (34.3 mg, 39%) as a yellow solid; m.p. 96.1-
1
96.9 °C; H NMR (400 MHz, CDCl3) ppm: 8.61 (d, J = 4.1 Hz, 1H), 7.68
(td, J = 7.7, 1.8 Hz, 1H), 7.63 (d, J = 15.0 Hz, 1H), 7.51 (d, J = 15.0 Hz,
1H), 7.35 (d, J = 7.8 Hz, 1H), 7.23 (ddd, J = 5.8, 4.8, 1.0 Hz, 1H), 3.21 (s,
3H), 3.07 (s, 3H); 13C NMR (100 MHz, CDCl3) 166.5, 153.5, 149.9, 140.7,
136.9, 124.9, 123.8, 121.5, 37.6, 35.9; IR(KBr): 3454, 2926, 1655, 1613,
1397, 1142, 979, 784, 588 cm-1; HRMS (ESI) calcd. for C10H13N2O:
[M+H]+: 177.1028, found: 177.1020.
(E)-3-(furan-2-yl)-N,N-dimethylacrylamide (3w)[9f]
:
Purification by
(E)-3-(3-chlorophenyl)-N,N-diethylacrylamide (4c)[20d]: Purification by
column chromatography on silica gel (Rf = 0.25, petroleum ether/ethyl
acetate = 2:1) yielded 4c (69.9 mg, 59%) as a light yellow liquid; 1H NMR
(400 MHz, CDCl3) ppm: 7.64 (d, J = 15.4 Hz, 1H), 7.51 (s, 1H), 7.39-7.36
(m, 1H), 7.32-7.30 (m, 2H), 6.83 (d, J = 15.4 Hz, 1H), 3.53-3.45 (m, 4H),
1.27 (t, J = 7.2 Hz, 3H), 1.19 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz,
CDCl3) 165.2, 140.7, 137.3, 134.7, 130.0, 129.3, 127.1, 126.2, 119.1,
42.3, 41.1, 15.1, 13.1; IR(KBr): 2975, 2932, 1650, 1606, 1561, 1479,
1431, 1245, 1140, 1095, 1079, 978, 785, 650 cm-1; HRMS (ESI) calcd.
for C13H17ClNO: [M+H]+: 238.0999, found: 238.0994.
column chromatography on silica gel (Rf = 0.29, petroleum ether/ethyl
acetate = 2:1) yielded 3w (75.1 mg, 91%) as a dark yellow liquid; 1H
NMR (400 MHz, CDCl3) ppm: 7.43-7.40 (m, 2H), 6.78 (d, J = 15.2 Hz,
1H), 6.51 (d, J = 3.4 Hz, 1H), 6.42 (dd, J = 3.4, 1.8 Hz, 1H), 3.13 (s, 3H),
3.03 (s, 3H); 13C NMR (100 MHz, CDCl3) 166.5, 151.7, 143.8, 129.2,
114.9, 113.7, 112.1, 37.4, 35.9; IR(KBr): 3100, 2920, 1630, 1600, 1558,
1497, 1397, 1397, 1261, 1143, 972, 928, 814, 750, 618, 595 cm-1; HRMS
(ESI) calcd. for C9H12NO2: [M+H]+: 166.0868, found: 166.0860.
(E)-N,N-dimethyl-3-(thiophen-2-yl)acrylamide (3x)[9f]
: Purification by
column chromatography on silica gel (Rf = 0.26, petroleum ether/ethyl
acetate = 2:1) yielded 3x (67.9 mg, 75%) as a yellow solid; m.p. 92.2-
93.1 °C; 1H NMR (400 MHz, CDCl3) ppm: 7.78 (d, J = 15.1 Hz, 1H), 7.29
(d, J = 5.1 Hz, 1H), 7.20 (d, J = 3.5 Hz, 1H), 7.01 (dd, J = 5.0, 3.6 Hz, 1H),
6.68 (d, J = 15.1 Hz, 1H), 3.14 (s, 3H), 3.04 (s, 3H); 13C NMR (100 MHz,
CDCl3) 166.3, 140.5, 135.1, 130.2, 128.0, 127.1, 116.2, 37.4, 35.9;
IR(KBr): 3422, 2924, 1657, 1602, 1396, 1138, 968, 828, 704 cm-1; HRMS
(ESI) calcd. for C9H12NOS: [M+H]+: 182.0640, found: 182.0636.
(E)-N,N-diethyl-3-(4-methoxyphenyl)acrylamide (4d)[20e]
: Purification
by column chromatography on silica gel (Rf = 0.24, petroleum ether/ethyl
acetate = 2:1) yielded 4d (57.1 mg, 49%) as a light yellow liquid; 1H NMR
(400 MHz, CDCl3) ppm: 7.64 (d, J = 15.3 Hz, 1H), 7.47-7.43 (m, 2H),
6.89-6.85 (m, 2H), 6.68 (d, J = 15.4 Hz, 1H), 3.80 (s, 3H), 3.49-3.41 (m,
4H), 1.23 (t, J = 7.0 Hz, 3H), 1.16 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) 165.9, 160.6, 141.8, 129.2, 128.1, 115.2, 114.1, 55.2, 42.2, 40.9,
15.0, 13.2; IR(KBr): 2973, 2931, 1665, 1610, 1512, 1458, 1288, 1250,
1165, 1139, 1031, 982, 826 cm-1; HRMS (ESI) calcd. for C14H20NO2:
[M+H]+: 234.1494, found: 234.1490.
(E)-N,N,2-trimethyl-3-phenylacrylamide (3y)[9f]: Purification by column
chromatography on silica gel (Rf = 0.28, petroleum ether/ethyl acetate =
2:1) yielded 3y (73.7 mg, 78%) as a colorless liquid; H NMR (400 MHz,
CDCl3) ppm: 7.38-7.35 (m, 2H), 7.33-7.29 (m, 2H), 7.28-7.25 (m, 1H),
6.53 (s, 1H), 3.06 (s, 6H), 2.10 (d, J = 1.5 Hz, 3H); 13C NMR (100 MHz,
CDCl3) 173.6, 136.0, 133.3, 129.6, 128.9, 128.2, 127.3, 38.8, 34.8, 15.9;
IR(KBr): 2923, 1610, 1520, 1448, 1394, 1263, 1094, 1027, 698 cm-1;
HRMS (ESI) calcd. for C12H16NO: [M+H]+: 190.1232, found: 190.1228.
1
(E)-N,N-diethyl-3-(4-fluorophenyl)acrylamide (4e)[20d]: Purification by
column chromatography on silica gel (Rf = 0.25, petroleum ether/ethyl
acetate = 2:1) yielded 4e (87.3 mg, 79%) as a colorless liquid; 1H NMR
(400 MHz, CDCl3) ppm: 7.67 (d, J = 15.4 Hz, 1H), 7.52-7.49 (m, 2H),
7.08-7.03 (m, 2H), 6.75 (d, J = 15.4 Hz, 1H), 3.52-3.45 (m, 4H), 1.26 (t, J
= 7.1 Hz, 3H), 1.19 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3) 165.5,
163.4 (d, J = 248.3 Hz), 141.0, 131.6 (d, J = 3.1 Hz), 129.5 (d, J = 8.4
Hz), 117.5 (d, J = 2.0 Hz), 115.8 (d, J = 21.7 Hz), 42.3, 41.1, 15.0, 13.2;
IR(KBr): 2976, 2933, 1667, 1610, 1511, 1439, 1379, 1316, 1231, 1140,
1096, 981, 829, 520 cm-1; HRMS (ESI) calcd. for C13H17FNO: [M+H]+:
222.1294, found: 222.1288.
N,N-dimethylbenzamide
(3z)[15b]
:
Purification
by
column
chromatography on silica gel (Rf = 0.27, petroleum ether/ethyl acetate =
2:1) yielded 3z (55.9 mg, 75%) as a colorless liquid; H NMR (400 MHz,
CDCl3) ppm: 7.39-7.34 (m, 5H), 3.08 (s, 3H), 2.95 (s, 3H); 13C NMR (100
MHz, CDCl3) 171.6, 136.2, 129.5, 128.3, 127.0, 39.5, 35.3; IR(KBr): 3540,
2980, 1620, 1506, 1446, 1264, 1084, 792, 737, 716 cm-1; HRMS (ESI)
calcd. for C9H12NO: [M+H]+: 150.0919, found: 150.0911.
1
(E)-N,N-diethyl-3-(4-(trifluoromethyl)phenyl)acrylamide
(4f)[20f]
:
Purification by column chromatography on silica gel (Rf = 0.25, petroleum
ether/ethyl acetate = 2:1) yielded 4f (88.1 mg, 65%) as a light yellow
solid; m.p. 74.5-76.1 °C; 1H NMR (400 MHz, CDCl3) ppm: 7.69 (d, J =
15.4 Hz, 1H), 7.59-7.59 (m, 4H), 6.88 (d, J = 15.4 Hz, 1H), 3.51-3.43 (m,
4H), 1.25 (t, J = 7.2 Hz, 3H), 1.17 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz,
CDCl3) 165.0, 140.5, 138.8, 130.9 (q, J = 32.4 Hz), 127.8, 125.6 (dd, J =
7.6, 3.7 Hz), 123.9 (q, J = 270.6 Hz), 120.3, 42.3, 41.1, 15.0, 13.1;
(E)-N,N-dimethylhex-2-enamide
(3a'):
Purification by column
chromatography on silica gel (Rf = 0.25, petroleum ether/ethyl acetate =
2:1) yielded 3a' (40.2 mg, 57%) as a yellow liquid; 1H NMR (400 MHz,
CDCl3) ppm: 6.82 (dt, J = 14.8, 7.0 Hz, 1H), 6.21 (dt, J = 15.1, 1.5 Hz,
1H), 3.04 (s, 3H), 2.96 (s, 3H), 2.15 (ddd, J = 8.6, 7.2, 1.4 Hz, 2H), 1.50-
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