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Helvetica Chimica Acta – Vol. 93 (2010)
(s, MeO); 3.92 (s, MeO); 7.45 – 7.49 (m, 5 arom. H). 13C-NMR: 53.0 (MeO); 53.3 (MeO); 111.0 (C); 112.7
(C); 128.4 (2 CH); 128.9 (2 CH); 129.6 (CH); 129.8 (C); 130.6 (C); 138.9 (C); 150.3 (C); 159.8 (C¼O);
164.2 (C¼O). EI-MS: 303 (5), 301 (100, Mþ), 272 (85), 185 (40), 184 (60), 77 (60), 80 (10), 39 (55).
Anal. calc. for C15H11NO4S (301.31): C 59.79, H 3.68, N 4.65; found: C 59.45, H 3.60, N 4.76.
Diethyl 5-Cyano-4-phenylthiophene-2,3-dicarboxylate (3f). Yield: 0.17 g (26%). Colorless crystals.
M.p. 139 – 1408. IR: 1727, 1716, 1591, 1549, 1430, 1315, 1241, 1203, 1179, 1080, 995, 741. 1H-NMR: 1.35 (t,
J ¼ 7.0, Me); 1.40 (t, J ¼ 7.1, Me); 4.37 (q, J ¼ 7.0, CH2O); 4.41 (q, J ¼ 7.1, CH2O); 7.43 – 7.47 (m, 5 arom.
H). 13C-NMR: 13.9 (Me); 14.0 (Me); 62.5 (CH2O); 62.9 (CH2O); 111.1 (C); 112.8 (C); 128.0 (2 CH);
128.6 (2 CH); 129.7 (CH); 129.8 (C); 130.8 (C); 138.7 (C); 150.2 (C); 159.8 (C¼O); 164.2 (C¼O). EI-
MS: 331 (7, [M þ 2]þ), 329 (100, Mþ), 284 (85), 199 (40), 77 (64), 39 (50). Anal. calc. for C17H15NO4S
(329.42): C 61.99, H 4.59, N 4.25; found: C 59.95, H 4.61, N 4.66.
Dimethyl 4-(4-Chlorophenyl)-5-cyanothiophene-2,3-dicarboxylate (3g). Yield: 0.15 g (22%). Color-
less crystals. M.p. 144 – 1468. IR: 1729, 1717, 1590, 1521, 1437, 1284, 1249, 1194, 1165, 1007, 993, 960, 899,
848, 816. 1H-NMR: 3.80 (s, MeO); 3.93 (s, MeO); 7.41 (d, J ¼ 7.5, 2 arom. H); 7.45 (d, J ¼ 7.5, 2 arom. H).
13C-NMR: 53.3 (MeO); 53.4 (MeO); 111.3 (C); 112.5 (C); 129.4 (C); 129.5 (2 CH); 129.8 (2 CH); 135.8
(C); 136.3 (C); 138.7 (C); 148.9 (C); 159.6 (C¼O); 163.9 (C¼O). EI-MS: 338 (6, [M þ 2]þ), 336 (100,
Mþ), 304 (90), 217 (40), 216 (60), 111 (10), 80 (5), 77 (50), 59 (35), 39 (38). Anal. calc. for
C15H10ClNO4S (335.76): C 53.66, H 3.00, N 4.17; found: C 53.50, H 2.95, N 4.16.
Diethyl 4-(4-Chlorophenyl)-5-cyanothiophene-2,3-dicarboxylate (3h). Yield: 0.18 g (25%). Colorless
crystals. M.p. 151 – 1538. IR: 1728, 1718, 1592, 1519, 1440, 1280, 1248, 1194, 1163, 1005, 990, 962, 893, 845,
811. 1H-NMR: 1.37 (t, J ¼ 7.2, Me); 1.43 (t, J ¼ 7.2, Me); 4.40 (q, J ¼ 7.2, CH2O); 4.44 (q, J ¼ 7.2, CH2O);
7.47 (d, J ¼ 7.6, 2 arom. H); 7.57 (d, J ¼ 7.6, 2 arom. H). 13C-NMR: 13.8 (Me); 13.9 (Me); 62.7 (CH2O);
63.2 (CH2O); 110.9 (C); 111.4 (C); 129.4 (C); 129.5 (2 CH); 129.9 (2 CH); 134.7 (C); 142.3 (C); 143.9
(C); 152.1 (C); 158.4 (C¼O); 162.0 (C¼O). EI-MS: 366 (4, [M þ 2]þ), 364 (100, Mþ), 318 (95), 217 (55),
216 (65), 112 (5), 80 (10), 77 (55), 39 (48). Anal. calc. for C17H14ClNO4S (363.81): C 56.12, H 3.88, N
3.85; found: C 56.15, H 3.85, N 3.80.
Dimethyl 5-Cyano-4-(4-nitrophenyl)thiophene-2,3-dicarboxylate (3i). Yield: 0.11 g (16%). Pale
yellow crystals. M.p. 161 – 1638. IR: 1735, 1724, 1593, 1521, 1434, 1346, 1283, 1246, 1200, 1170, 1105, 1107,
1005, 990, 866, 835, 744. 1H-NMR: 3.80 (s, MeO); 3.94 (s, MeO); 7.65 (d, J ¼ 7.7, 2 arom. H); 8.31 (d, J ¼
7.7, 2 arom. H). 13C-NMR: 53.4 (MeO); 53.5 (MeO); 112.0 (C); 112.3 (C); 124.1 (2 CH); 127.2 (C); 129.7
(2 CH); 136.5 (C); 137.0 (C); 147.5 (C); 148.6 (C); 159.3 (C¼O); 163.5 (C¼O). EI-MS: 348 (4, [M þ
2]þ), 346 (100, Mþ), 315 (61), 287 (40), 77 (20), 39 (10). Anal. calc. for C15H10N2O6S (346.31): C
54.02, H 2.91, N 8.09; found: C 54.50, H 3.00, N 8.22.
Diethyl 5-Cyano-4-(4-nitrophenyl)thiophene-2,3-dicarboxylate (3j). Yield: 0.12 g (16%). Pale yellow
crystals. M.p. 154 – 1568. IR: 1735, 1724, 1593, 1521, 1434, 1346, 1283, 1246, 1200, 1170, 1105, 1107, 1005,
990, 866, 835, 744. 1H-NMR: 1.40 (t, J ¼ 7.0, Me); 1.45 (t, J ¼ 7.1, Me); 4.42 (q, J ¼ 7.0, CH2O); 4.46 (q, J ¼
7.1, CH2O); 7.64 (d, J ¼ 7.7, 2 arom. H); 8.30 (d, J ¼ 7.7, 2 arom. H). 13C-NMR: 14.2 (Me); 14.6 (Me); 63.0
(CH2O); 63.3 (CH2O); 112.1 (C); 112.2 (C); 124.1 (2 CH); 127.0 (C); 129.6 (2 CH); 136.6 (C); 136.8 (C);
147.2 (C); 148.2 (C); 159.4 (C¼O); 163.6 (C¼O). EI-MS: 376 (6, [M þ 2]þ), 374 (100, Mþ), 329 (61), 301
(40), 77 (24), 39 (15). Anal. calc. for C17H14N2O6S (374.43): C 54.54, H 3.77, N 7.48; found: C 54.40, H
3.67, N 7.52.
Dimethyl 5,5-Dicyano-4-(4-methoxyphenyl)-3-{[(E)-(4-methoxyphenyl)methylidene]amino}cyclo-
penta-1,3-diene-1,2-dicarboxylate (4a). Yield: 0.23 g (24%). Orange crystals. M.p. 180 – 1828. IR (KBr):
1735, 1728, 1593, 1564, 1525, 1501, 1427, 1323, 1297, 1254, 1232, 1181, 1024, 950, 828, 788, 729, 694.
1H-NMR: 3.79 (s, MeO); 3.86 (s, MeO); 3.87 (s, MeO); 3.95 (s, MeO); 6.93 (d, J ¼ 8.4, 2 arom. H); 6.98
(d, J ¼ 8.3, 2 arom. H); 7.78 (d, J ¼ 8.4, 2 arom. H); 7.81 (d, 3J ¼ 8.3, 2 arom. H); 8.35 (s, CH). 13C-NMR:
29.6 (C); 53.1 (MeO); 53.2 (MeO); 55.3 (MeO); 55.5 (MeO); 110.8 (CN); 114.6 (2 CH); 114.8 (2 CH);
121.9 (C); 124.9 (C); 127.6 (C); 127.8 (C); 129.8 (2 CH); 131.4 (2 CH); 147.9 (C); 150.8 (C); 159.1 (C);
160.6 (C); 162.6 (C¼N); 163.9 (C¼O); 165.2 (C¼O). EI-MS: 471 (82, Mþ), 456 (21), 440 (15), 412 (18),
205 (7), 107 (100), 77 (64), 39 (55). Anal. calc. for C26H21N3O6 (471.47): C 66.24, H 4.49, N 8.91; found: C
66.30, H 4.50, N 8.80.
X-Ray Crystal-Structure of 4a. Structure-determination and refinement data: C26H21N3O6, Mr 471.46,
crystal size, 0.30 ꢁ 0.20 ꢁ 0.20 mm3, monoclinic, a ¼ 14.5839(7) ꢂ, b ¼ 8.9554(4) ꢂ, c ¼ 19.7705(10) ꢂ;