10.1002/ejoc.201901512
European Journal of Organic Chemistry
FULL PAPER Accepted Article
J = 7.0 Hz, 1H, C6H4), 7.60–7.54 (m, 1H, C6H4), 7.11 (s, 1H, thiophene),
6.63 (s, 2H, NH2), 3.72 (s, 3H, OCH3), 2.61 (s, 3H, C(O)CH3) ppm. 13C
NMR (126 MHz, [D6]DMSO): δ = 197.6, 163.9, 155.2, 146.4, 137.5, 133.2,
130.0, 129.8, 128.8, 124.8, 117.2, 97.5, 51.1, 26.9 ppm. IR (ATR): 3418,
3344, 1710, 1642, 1582, 1518, 1449, 1324, 1301, 1274, 1184, 1104, 1080,
1034, 834, 814, 753, 731, 681, 644, 510 cm–1. MS (ESI): m/z = 276.1
[M+H]+. Elemental analysis calcd for C14H13NO3S: C 61.07, H 4.76, N 5.09,
found: C 60.99, H 4.65, N 4.94.
246.7 Hz), 155.1, 143.4, 139.3, 129.7 (d, J = 2.9 Hz), 128.4, 127.6 (d, J =
8.2 Hz), 123.0, 120.7, 117.1, 116.3 (d, J = 21.9 Hz), 100.2 ppm. IR (ATR):
3473, 3363, 3252, 3202, 1615, 1581, 1524, 1462, 1435, 1320, 1270, 1229,
1158, 1096, 1074, 1012, 911, 837, 821, 754, 694, 611, 576, 563, 541, 511,
495, 440 cm–1. MS (ESI): m/z = 313.1 [M+H]+. Elemental analysis calcd for
C17H13FN2OS: C, 65.37, H 4.19, N, 8.97, found: C 65.40, H 4.07, N 8.90.
3-Amino-N-phenyl-5-(3-(trifluoromethyl)phenyl)thiophene-2-
carboxamide (6Be): Yield 0.944 g, 87%, cream-colored crystals, m.p.
167–168 °C. 1H NMR (500 MHz, [D6]DMSO): δ = 9.38 (s, 1H, NH), 7.96 (d,
J = 7.6 Hz, 1H, Ar), 7.91 (s, 1H, Ar), 7.76 (d, J = 7.6 Hz, 1H, Ar), 7.72 (d,
J = 7.7 Hz, 1H, Ar), 7.71–7.66 (m, 2H, Ar), 7.30 (t, J = 7.9 Hz, 2H, Ar), 7.18
Methyl
3-amino-5-(3-(methoxycarbonyl)phenyl)thiophene-2-
carboxylate (6Ag): Yield 0.715 g, 82%, off-white crystals, m.p. 124–
126 °C. 1H NMR (500 MHz, [D6]DMSO): δ = 8.11 (d, J = 1.3 Hz, 1H, 2H-
C6H4), 7.95 (dd, J = 7.7, 1.1 Hz, 1H, 6H-C6H4), 7.93–7.87 (m, 1H, C6H4),
7.61 (t, J = 7.8 Hz, 1H, C6H4), 7.09 (s, 1H, thiophene), 5.82-5.34 (br.s, 2H,
NH2), 3.88 (s, 3H, CH3), 3.74 (s, 3H, CH3) ppm. 13C NMR (126 MHz,
[D6]DMSO): δ = 165.7, 163.9, 155.8, 146.0, 133.3, 130.6, 130.2, 130.0,
129.6, 125.8, 117.1, 98.5, 52.5, 51.1 ppm. IR (ATR): 3433, 1670, 1634,
1590, 1550, 1515, 1463, 1428, 1365, 1313, 1268, 1235, 1075, 948, 900,
832, 782, 748, 690, 677, 590, 492, 434 cm–1. MS (ESI): m/z = 292.1 [M+H]+.
Elemental analysis calcd for C14H13NO4S: C 57.72, H 4.50, N 4.81, found:
C 57.59, H 4.43, N 4.74.
(s, 1H, thiophene), 7.04 (t, J = 7.3 Hz, 1H, Ar), 6.71 (s, 2H, NH2) ppm. 13
C
NMR (126 MHz, [D6]DMSO): δ = 163.1, 155.1, 142.3, 139.3, 134.1, 130.7,
130.1 (q, J = 32.5 Hz), 129.4, 128.5, 125.3 (q, J = 3.4 Hz), 123.1, 121.8 (q,
J = 278.5 Hz), 121.7 (q, J = 3.6 Hz), 120.7, 118.3, 101.0 ppm. IR (ATR):
3473, 1616, 1575, 1464, 1436, 1319, 1124, 803, 749, 725, 693, 676, 510,
428, 415 cm–1. MS (ESI): m/z = 363.1 [M+H]+. Elemental analysis calcd for
C18H13F3N2OS: C 59.66, H 3.62, N 7.73, found: C 59.49, H 3.54, N 7.68.
5-(3-Acetylphenyl)-3-amino-N-phenylthiophene-2-carboxamide (6Bf):
Yield 0.786 g, 78%, light yellow crystals, m.p. 187–188 °C. 1H NMR (500
MHz, [D6]DMSO): δ = 9.37 (s, 1H, NH), 8.16 (s, 1H, 2H-C6H4), 7.98 (d, J =
7.7 Hz, 1H, Ar), 7.92 (d, J = 8.4 Hz, 1H, Ar), 7.69 (d, J = 7.7 Hz, 2H, Ar),
7.63 (t, J = 7.7 Hz, 1H, Ar), 7.30 (t, J = 7.9 Hz, 2H, Ar), 7.14 (s, 1H,
thiophene), 7.04 (t, J = 7.3 Hz, 1H, Ar), 6.72 (s, 2H, NH2), 2.64 (s, 3H, CH3)
ppm. 13C NMR (126 MHz, [D6]DMSO): δ = 197.6, 163.1, 155.2, 143.3,
139.3, 137.6, 133.4, 129.9, 129.7, 128.7, 128.5, 124.6, 123.1, 120.7, 117.6,
100.5, 26.9 ppm. IR (ATR): 3433, 3400, 3311, 1671, 1634, 1590, 1551,
1515, 1463, 1428, 1365, 1313, 1269, 1235, 1071, 948, 900, 830, 786, 748,
717, 690, 677, 592, 492, 437 cm–1. MS (ESI): m/z = 337.1 [M+H]+.
Elemental analysis calcd for C19H16N2O2S: C 67.84, H 4.79, N 8.33, found:
C 67.73, H 4.70, N 8.25.
3-Amino-N,5-diphenylthiophene-2-carboxamide (6Ba): Yield 0.714 g,
81%, white crystals, m.p. 203–204 °C. 1H NMR (500 MHz, [D6]DMSO): δ
= 9.33 (s, 1H, NH), 7.68 (d, J = 8.4 Hz, 2H, Ph), 7.65 (d, J = 8.1 Hz, 2H,
Ph), 7.47 (t, J = 7.2 Hz, 2H, Ph), 7.42–7.37 (m, 1H, Ph), 7.29 (t, J = 7.3 Hz,
2H, Ph), 7.06–7.01 (m, 2H, Ph, thiophene), 6.82–6.54 (br.s, 2H, NH2) ppm.
13C NMR (126 MHz, [D6]DMSO): δ = 163.2, 155.1, 144.5, 139.4, 133.0,
129.4, 129.0, 128.4, 125.4, 123.0, 120.7, 116.9, 100.2 ppm. IR (ATR):
3473, 3364, 3250, 3054, 1616, 1585, 1514, 1489, 1464, 1432, 1320, 1307,
1274, 1233, 1097, 1072, 907, 824, 747, 684, 636, 510 cm–1. MS (ESI): m/z
= 295.1 [M+H]+. Elemental analysis calcd for C17H14N2OS: C 69.36, H 4.79,
N 9.52, found: C 69.28, H 4.70, N 9.40.
3-Amino-5-(3-methylphenyl)-N-phenylthiophene-2-carboxamide
(6Bb): Yield 0.803 g, 87%, light yellow crystals, m.p. 171–172 °C. 1H NMR
(500 MHz, [D6]DMSO): δ = 9.30 (s, 1H, NH), 7.68 (d, J = 7.7 Hz, 2H, Ar),
7.48–7.42 (m, 2H, Ar), 7.35 (t, J = 7.5 Hz, 1H, Ar), 7.29 (t, J = 7.8 Hz, 2H,
Ar), 7.21 (d, J = 7.6 Hz, 1H, Ar), 7.03 (t, J = 7.3 Hz, 1H, Ar), 7.00 (s, 1H,
thiophene), 6.68 (s, 2H, NH2), 2.36 (s, 3H, CH3) ppm. 13C NMR (126 MHz,
[D6]DMSO): δ = 163.2, 155.1, 144.7, 139.4, 138.6, 133.0, 129.6, 129.2,
128.4, 126.0, 123.0, 122.6, 120.7, 116.8, 100.0, 21.0 ppm. IR (ATR): 3471,
3362, 3264, 1622, 1581, 1533, 1499, 1456, 1434, 1316, 1267, 1234, 1176,
1093, 1072, 903, 872, 826, 781, 748, 722, 686, 636, 616, 543, 513, 489,
432 cm–1. MS (ESI): m/z = 309.1 [M+H]+. Elemental analysis calcd for
C18H16N2OS: C 70.10, H 5.23, N 9.08, found: C 70.00, H 5.14, N 8.97.
Methyl
3-(4-amino-5-(phenylcarbamoyl)thiophen-2-yl)benzoate
(6Bg): Yield 0.792 g, 75%, light yellow crystals, m.p. 152–153 °C. 1H NMR
(500 MHz, [D6]DMSO): δ = 9.37 (s, 1H, NH), 8.17 (s, 1H, 2H-C6H4), 8.00–
7.91 (m, 2H, Ar), 7.69 (d, J = 7.2 Hz, 2H, Ar), 7.65–7.56 (m, 1H, Ar), 7.37–
7.24 (m, 2H, Ar), 7.13 (s, 1H, thiophene), 7.07–6.99 (m, 1H, Ar), 6.72 (s,
2H, NH2), 3.90 (s, 3H, CH3) ppm. 13C NMR (126 MHz, [D6]DMSO): δ =
165.8, 163.1, 155.2, 142.9, 139.3, 133.5, 130.6, 130.0, 129.9, 129.3, 128.5,
125.7, 123.1, 120.7, 117.6, 100.5, 52.5 ppm. IR (ATR): 3413, 3351, 3314,
1718, 1634, 1576, 1520, 1436, 1321, 1301, 1277, 1229, 1108, 1082, 1003,
959, 904, 819, 752, 688, 642, 548, 508, 469, 409 cm–1. MS (ESI): m/z =
353.1 [M+H]+. Elemental analysis calcd for C19H16N2O3S: C 64.76, H 4.58,
N 7.95, found: C 64.61, H 4.49, N 7.90.
3-Amino-5-(4-methylphenyl)-N-phenylthiophene-2-carboxamide
(6Bc): Yield 0.720 g, 78%, light yellow crystals, m.p. 205–206 °C. 1H NMR
(500 MHz, [D6]DMSO): δ = 9.29 (s, 1H, NH), 7.68 (d, J = 7.6 Hz, 2H, Ar),
7.54 (d, J = 8.1 Hz, 2H, Ar), 7.32–7.27 (m, 4H, Ar), 7.03 (t, J = 7.4 Hz, 1H,
3-Amino-N-(2-fluorophenyl)-5-phenylthiophene-2-carboxamide
(6Ca): Yield 0.692 g, 74%, light yellow crystals, m.p. 148–149 °C. 1H NMR
(500 MHz, [D6]DMSO): δ = 9.17 (s, 1H, NH), 7.65 (d, J = 7.3 Hz, 2H, Ar),
7.54 (t, J = 7.5 Hz, 1H, Ar), 7.47 (t, J = 7.5 Hz, 2H, Ar), 7.40 (t, J = 7.2 Hz,
1H, Ar), 7.28–7.13 (m, 3H, Ar), 7.02 (s, 1H, thiophene), 6.64 (s, 2H, NH2)
ppm. 13C NMR (126 MHz, [D6]DMSO): δ = 163.0, 156.0 (d, J = 246.6 Hz),
154.9, 144.9, 133.0, 129.4, 129.0, 127.1, 126.4 (d, J = 7.8 Hz), 126.1 (d, J
= 12.0 Hz), 125.5, 124.2 (d, J = 3.5 Hz), 117.0, 115.7 (d, J = 20.2 Hz),
100.2 ppm. IR (ATR): 3424, 3313, 1646, 1617, 1595, 1520, 1459, 1446,
1327, 1255, 1186, 1117, 1074, 1032, 936, 826, 766, 745, 726, 691, 534,
499, 457 cm–1. MS (ESI): m/z = 313.1 [M+H]+. Elemental analysis calcd for
C17H13FN2OS: C 65.37, H 4.19, N 8.97, found: C 65.39, H 4.11, N, 8.88,
Ar), 6.97 (s, 1H, thiophene), 6.68 (s, 2H, NH2), 2.33 (s, 3H, CH3). ppm. 13
C
NMR (126 MHz, [D6]DMSO): δ = 163.2, 155.2, 144.7, 139.4, 138.6, 130.3,
129.9, 128.4, 125.4, 123.0, 120.7, 116.3, 99.7, 20.9 ppm. IR (ATR): 3470,
3358, 1616, 1582, 1520, 1499, 1460, 1433, 1319, 1270, 1232, 1177, 1100,
1074, 1018, 811, 750, 692, 567, 541, 511 cm–1. MS (ESI): m/z = 309.1
[M+H]+. Elemental analysis calcd for C18H16N2OS: C 70.10, H 5.23, N 9.08,
found: C 69.96, H 5.15, N 8.94.
3-Amino-5-(4-fluorophenyl)-N-phenylthiophene-2-carboxamide
(6Bd): Yield 0.814 g, 87%, white crystals, m.p. 226–227 °C. 1H NMR (500
MHz, [D6]DMSO): δ = 9.32 (s, 1H, NH), 7.75–7.63 (m, 4H, Ar), 7.35–7.26
(m, 4H, Ar), 7.03 (t, J = 7.3 Hz, 1H, Ar), 6.98 (s, 1H, thiophene), 6.69 (s,
2H, NH2) ppm. 13C NMR (126 MHz, [D6]DMSO): δ = 163.2, 162.4 (d, J =
3-Amino-N-(2-fluorophenyl)-5-(3-methylphenyl)thiophene-2-
carboxamide (6Cb): Yield 0.596 g, 61%, yellow crystals, m.p. 131–132 °C.
1H NMR (400 MHz, [D6]DMSO): δ = 9.14 (s, 1H, NH), 7.60–7.53 (m, 1H,
Ar), 7.49–7.42 (m, 2H, Ar), 7.35 (t, J = 7.6 Hz, 1H, Ar), 7.29–7.15 (m, 4H,
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