224
C. Herbivo et al. / Dyes and Pigments 86 (2010) 217e226
4.3.3. 2-Dicyanovinyl-5-(4-ethoxyphenyl)thiophene 4c
(28), 236 (35), 213 (29), 185 (32), 155 (63), 152 (32), 129 (38), 127
(71), 111 (55), 98 (66), 97 (100), 83 (82), 71 (68). HRMS: m/z (EI) for
C18H10N2S2; calcd: 318.0285; found: 318.0291.
Red solid (62%). Mp > 185 ꢂC. UV (Dioxane): lmax nm (
3/
Mꢀ1 cmꢀ1) 416.0 (35,847). IR (KBr)
n
3038, 2948, 2224 (CN), 1614,
1581, 1501, 1382, 1052, 1180, 1253, 1052, 792 cmꢀ1. 1H NMR (DMSO-
d6)
d
1.33 (t, 3H, J ¼ 6.9 Hz, OCH2CH3), 4.09 (q, 2H, J ¼ 6.9 Hz,
4.4.2. 5-(400-Methoxyphenyl)-50-dicyanovinyl-2,20-bithiophene 6b
OCH2CH3), 7.03 (d, 2H, J ¼ 8.7 Hz, 30-H and 50-H), 7.70 (d, 1H,
J ¼ 4.5 Hz, 4-H), 7.72 (d, 2H, J ¼ 8.7 Hz, 20-H and 60-H), 7.90 (d, 1H,
J ¼ 4.5 Hz, 3-H), 8.59 (s, 1H, CH]C(CN)2). 13C NMR (DMSO-d6)
Red solid (95%). Mp > 180 ꢂC. UV (DMSO): lmax nm (
482.0 (21,738), 312.0 (6861) inf. 474.0 (2918). IR (nujol)
3
/Mꢀ1 cmꢀ1
n 2221 (CN),
)
1882, 1608, 1580, 1542, 1512, 1484, 1349, 1309, 1289, 1275, 1253,
1232, 1193, 1179, 1163, 1146, 1124, 1112, 1078, 1063, 1031, 960, 943,
884, 862, 817, 799, 785, 722, 693, 646, 630, 604, 587, 555 cmꢀ1. 1H
d
63.4, 73.6, 114.0, 114.8, 115.3, 124.3, 124.4, 128.1, 133.1, 142.7, 152.6,
155.5, 160.3. MS (EI) m/z (%): 280 (Mþ, 40), 252 (100), 223 (12), 83
(18). HRMS: m/z (EI) for C16H12N2OS; calcd: 280.0670; found:
280.0677.
NMR (DMSO-d6)
d
3.79 (s, 3H, OCH3), 7.00 (d, 2H, J ¼ 8.7 Hz, 300-H
and 500-H), 7.51 (d, 1H, J ¼ 3.9 Hz, 4-H), 7.62 (d, 1H, J ¼ 3.9 Hz, 30-H),
7.67 (m, 3H, 3-H, 200-H and 600-H), 7.90 (d, 1H, J ¼ 3.9 Hz, 40-H), 8.62
4.3.4. 2-Dicyanovinyl-5-(4-N,N-dimethylaminophenyl)
thiophene 4d
(s, 1H, CH]N)2). 13C NMR (DMSO-d6)
d 55.33, 77.80, 114.05, 114.70,
124.46, 125.06,125.27, 127.09,129.38, 132.46,133.08, 142.69, 146.54,
148.00, 152.26, 159.73. MS (EI) m/z (%): 348 (Mþ, 100), 333 (85), 305
(42), 271 (6), 203 (5), 174 (4). HRMS: m/z (EI) for C19H12 N2OS2;
calcd: 348.0391; found: 348.0395.
Green solid (83%). Mp > 209 ꢂC (lit. [12] 217 ꢂC). UV (Dioxane):
lmax nm (
3
/Mꢀ1 cmꢀ1) 485.0 (33,586). IR (KBr)
n
3025, 2943, 2211
(CN), 1701, 1607, 1579, 1503, 1439, 1365, 1062, 1231, 803 cmꢀ1
.
1H
NMR (DMSO-d6)
d
2.99 (s, 6H, N(CH3)2), 6.76 (d, 2H, J ¼ 8.7 Hz, 30-H
and 50-H), 7.61 (d, 1H, J ¼ 3.9 Hz, 4-H), 7.64 (d, 2H, J ¼ 8.7 Hz, 20-H
4.4.3. 5-(400-N,N-Dimethylaminophenyl)-50-dicyanovinyl-2,
20-bithiophene 6d
and 60-H), 7.85 (d, 1H, J ¼ 3.9 Hz, 3-H), 8.49 (s, 1H, CH]C(CN)2). 13C
NMR (DMSO-d6)
d
46.4, 73.6, 114.0, 114.7, 115.4, 124.4, 124.5, 128.0,
Brown solid (95%). Mp > 180 ꢂC (lit. [12] 215 ꢂC). UV (DMSO):
133.4, 142.5, 152.4, 155.6, 160.7. MS (EI) m/z (%): 279 (Mþ, 100), 278
(66), 263 (21). HRMS: m/z (EI) for C16H13N3S; calcd: 279.0830;
found: 279.0832.
lmax nm (
(7308). IR (nujol)
1352,1310,1266,1231,1201,1146,1075, 959, 939, 876, 810, 790, 745,
3
/Mꢀ1 cmꢀ1) 530.0 (18,868), 364.5 (13,732) inf. 421.0
n
2223 (CN), 1872, 1606, 1578, 1551, 1542, 1486,
721, 687, 629, 608, 573, 550 cmꢀ1. 1H NMR (DMSO-d6)
d 3.05 (s, 6H,
4.3.5. 2-Dicyanovinyl-5-(4-pyrrolidinophenyl)thiophene 4f
N(CH3)2) 6.84 (d, 2H, J ¼ 9.0 Hz, 300-H and 500-H), 7.38 (d, 1H,
J ¼ 3.9 Hz, 4-H), 7.56 (d, 1H, J ¼ 3.9 Hz, 30-H), 7.62 (d, 2H, J ¼ 9.0 Hz,
200-H and 600-H), 7.64 (d, 1H, J ¼ 3.9 Hz, 3-H), 7.94 (d, 1H, J ¼ 3.9 Hz,
Green solid (42%). Mp > 226 ꢂC. UV (DMSO): lmax nm (
3/
Mꢀ1 cmꢀ1) 503.0 (42,143). IR (KBr)
1604, 1565, 1493, 1411, 1391, 1067, 1191, 797 cmꢀ1. 1H NMR (DMSO-
n 3027, 2968, 2215 (CN), 1656,
40-H), 8.40 (s, 1H, CH]C(CN)2). 13C NMR (DMSO-d6)
d 73.0, 112.0,
d6)
d
1.97 (m, 4H, N(CH2CH2)2), 3.31 (m, 4H, N(CH2CH2)2), 6.62 (d,
113.8, 114.4, 120.1, 122.4, 124.3, 126.4, 129.1, 130.7, 132.4, 142.0,
148.0, 150.3, 151.6. MS (EI) m/z (%): 361 (Mþ, 100), 345 (100), 318
(15), 180 (5), 172 (4), 97 (4). HRMS: m/z (EI) for C20H15N3S2; calcd
361.0707; found: 361.0708. Anal. calcd for C20H15N3S2: C, 66.45; H,
4.18; N, 11.62; S, 17.74. Found: C, 66.01; H, 4.05; N, 11.47; S, 17.39.
2H, J ¼ 8.7 Hz, 30-H and 50-H), 7.59 (d, 1H, J ¼ 3.9 Hz, 4-H), 7.64 (d,
2H, J ¼ 8.7 Hz, 20-H and 60-H), 7.85 (d, 1H, J ¼ 3.9 Hz, 3-H), 8.48 (s,
1H, CH]C(CN)2). 13C NMR (DMSO-d6)
d 24.9, 47.3,112.1,114.6,115.3,
118.5, 122.3, 127.9, 131.2, 143.5, 149.0, 151.8, 158.2. MS (EI) m/z (%):
305 (Mþ, 100), 304 (74), 301 (17), 262 (11), 249 (35), 235 (11), 164
(11), 149 (15). HRMS: m/z (EI) for C18H10N2S2; calcd 305.0987;
found: 305.0992.
4.4.4. 5-(400-N,N-Diethylaminophenyl)-50-dicyanovinyl-2,
20-bithiophene 6e
Green solid (87%). Mp > 184 ꢂC. UV (DMSO): lmax nm
4.4. General procedure for the synthesis of 5-aryl-50-dicyanovinyl-
2,20bithiophenes 6 from the corresponding 5-aryl-50-formyl-
2,20bithiophenes 5 by Knoevenagel condensation with malononitrile
(3
/Mꢀ1 cmꢀ1) 546.5 (18,298), 369.0 (14,277) inf. 430.0 (8079). IR
(nujol)
1054, 955, 932, 880, 806, 776, 740, 732, 684, 628, 605, 568, 549,
517 cmꢀ1 1H NMR (DMSO-d6)
n 2219 (CN), 1603, 1572, 1541, 1272, 1193, 1159, 1093, 1072,
.
d
1.22 (t, 6H, J ¼ 5.4 Hz, N
To a solution of malononitrile (0.08 g, 1.2 mmol) and 5-aryl-50-
formyl-bithiophenes 5 (1.0 mmol) in dichloromethane (25 ml) was
added piperidine (1 drop). The solution was stirred at room
temperature during different reaction times (15 mine2 h), then
petroleum ether was added and the 5-aryl-50-dicyanovinyl-2,20-
bithiophenes 6 precipitate and were filtrate. The crude residue was
submitted to silica gel column chromatography using mixtures of
chloroform and light petroleum of increasing polarity. The fractions
containing the purified product were collected and evaporated
under vacuum.
(CH2CH3)2), 3.38 (q, 4H, J ¼ 5.4 Hz, N(CH2CH3)2), 6.71 (d, 2H,
J ¼ 6.6 Hz, 300-H and 500-H), 7.32 (d, 1H, J ¼ 3.0 Hz, 4-H), 7.49 (d,
2H, J ¼ 6.6 Hz, 200-H and 600-H), 7.52 (d, 1H, J ¼ 3.0 Hz, 3-H), 7.58
(d, 1H, J ¼ 3.0 Hz, 30-H); 7.88 (d, 1H, J ¼ 3.0 Hz, 40-H), 8.50 (s, 1H,
CH]C(CN)2). 13C NMR (DMSO-d6)
d 43.4, 72.8, 111.5, 113.8, 114.4,
119.2, 122.0, 124.1, 126.6, 129.1, 130.4, 132.3, 142.0, 147.7, 148.2,
148.4, 151.5. MS (EI) m/z (%): 389 (Mþ, 56), 374 (100), 345 (59),
326 (36), 236 (24), 152 (18), 137 (20), 129 (29), 123 (32), 111 (50),
97 (90), 83 (92), 81 (78), 71 (72). HRMS: m/z (EI) for C22H19N3S2;
calcd 389.1020; found: 389.1009. Anal. calcd for C22H19N3S2: C,
67.83; H, 4.92; N, 10.79; S, 16.46. Found: C, 67.40; H, 4.84; N, 10.65;
S, 16.37.
4.4.1. 5-Phenyl-50-dicyanovinyl-2,20-bithiophene 6a
Dark red solid (93%). Mp > 84 ꢂC. UV (DMSO): lmax nm (
3/
M
n
ꢀ1 cmꢀ1) 463.5 (21,575), 321.5 (9966) inf. 376.5 (2242). IR (nujol)
2223 (CN), 1572, 1539, 1482, 1461, 1449, 1367, 1346, 1261, 1227,
4.4.5. 5-(400-Pyrrolidinophenyl)-50-dicyanovinyl-2,
20-bithiophene 6f
1187, 1147, 1078, 1056, 934, 882, 788, 755, 722, 697, 684, 608 cmꢀ1
.
Brown solid (89%). Mp > 214 ꢂC. UV (DMSO): lmax nm
1H NMR (DMSO-d6)
d
7.34 (m, 1H, 400-H), 7.44 (m, 2H, 300-H and 500-
(3
/Mꢀ1 cmꢀ1) 544.5 (18,365), 369.5 (14,309) inf. 429.0 (7329). IR
H), 7.61 (d, 1H, J ¼ 3.9 Hz, 4-H), 7.65 (d, 1H, J ¼ 3.9 Hz, 30-H), 7.71 (d,
1H, J ¼ 3.9 Hz, 3-H), 7.73 (m, 2H, 200-H and 600-H), 7.90 (d, 1H,
J ¼ 3.9 Hz, 40-H), 8.64 (s, 1H, CH]C(CN)2). 13C NMR (DMSO-d6)
(nujol)
n 2214 (CN), 1603, 1569, 1548, 1538, 1512, 1487, 1438, 1231,
1212, 1188, 1164, 1144, 1061, 966, 927, 880, 862, 814, 789, 775, 722,
688, 645, 634, 602 cmꢀ1.1H NMR (DMSO-d6)
d 1.96 (m, 4H, N
d
74.2, 113.9, 114.6, 125.3, 125.6, 128.6, 129.2, 132.5, 133.3, 133.6,
(CH2CH2)2), 3.72 (m, 4H, N(CH2CH2)2), 6.57 (d, 2H, J ¼ 8.7 Hz, 300-H
142.4, 146.1, 147.5, 152.2. MS (EI) m/z (%): 318 (Mþ, 15), 283 (17), 257
and 500-H), 7.37 (d, 1H, J ¼ 3.9 Hz, 4-H), 7.52 (d, 2H, J ¼ 8.7 Hz, 200H