Arkivoc 2017, iii, 73-86
Borisova, I. A. et al.
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1221, 1151, 1077, 1038, 964, 869, 809, 757, 720, 650, 600, 559, 505. H NMR, δ, ppm: 0.94 (t, 3Н, (4`)СН3, J
7 Hz), 1.32-1.40 (m, 2Н, (3`)СН2), 1.69-1.74 (m, 2Н, (2`)СН2), 4.13 (t, 2Н, (1`)СН2, J 7 Hz), 5.57 (d, 1Н, (4)СН, 3J
13.7 Hz), 6.82 (t, 1Н, СНpy, J 6.3 Hz), 7.63 (t, 1Н, СНpy, J 7.3 Hz), 7.82 (d, 1Н, СНpy, J 9 Hz), 7.98-8.05 (m, 3Н,
NH2, CHpy), 8.38 (d, 1Н, (3)СН, 3J 13.7 Hz). 13C NMR, δ, ppm: 13.82, 19.53, 29.70, 55.17, 89.36, 94.17, 114.84,
120.54, 121.06, 138.20, 142.25, 144.80, 159.27, 190.75. Anal. calcd for C14H17N3S (259.37): C, 64.83; H, 6.61;
N, 16.20; S, 12.36. Found: C, 64.75; H, 6.57; N, 16.09; S, 12.26.
(E)-2-(2-(1-Octylpyridin-2(1H)-ylidene)ethylidene)malononitrile (6g). Yield 86%, mp 82–83 °C, orange
crystals. IR (KBr), ν, сm–1: 2957, 2919, 2855, 2188, 2175, 1634, 1569, 1528, 1497, 1478, 1440, 1406, 1322,
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1305, 1275, 1228, 1161, 1076, 1043, 991, 955, 786, 757, 716, 615, 592, 576. H NMR, δ, ppm: 0.83-0.85 (m,
3Н, (8`)СН3), 1.25-1.31 (m, 10Н, 5СН2), 1.71 (sbr, 2Н, (2`)СН2), 4.13 (t, 2Н, (1`)СН2, J 7.3 Hz), 5.56 (d, 1Н,
(2)СН, 3J 13.8 Hz), 6.87 (t, 1Н, СНpy, J 6.6 Hz), 7.63 (t, 1Н, СНpy, J 7.3 Hz), 7.88-7.95 (m, 2Н, СНpy, (1)CH), 8.07
(d, 1Н, СНpy, J 6.6 Hz). 13C NMR, δ, ppm: 14.37, 22.48, 26.14, 27.79, 28.76, 28.97, 31.51, 49.22, 55.48, 93.56,
115.42, 118.89, 121.05, 121.21, 138.55, 142.03, 149.53, 152.72. Anal. calcd for C18H23N3 (281.40): C, 76.83;
H, 8.24; N, 14.93. Found: C, 76.71; H, 8.13; N, 14.75.
Ethyl (2E,4E)-2-cyano-4-(1-octylpyridin-2(1H)-ylidene)but-2-enoate (6h). Yield 84%, mp 51–52 °C, orange
crystals. IR (KBr), ν, сm–1: 2954, 2928, 2856, 2188, 1674, 1633, 1565, 1531, 1446, 1419, 1311, 1221, 1155,
1095, 1048, 955, 883, 801, 717. 1H NMR, δ, ppm: 0.81-0.84 (sbr, 3Н, (8`)СН3), 1.17-1.31 (m, 13Н, CO2CH2СН3,
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5СН2), 1.71 (sbr, 2Н, (2`)СН2), 4.07-4.10 (m, 4Н, (1`)СН2, CO2CH2CH3), 5.53 (d, 1Н, (4)СН, J 14.0 Hz), 6.74 (t,
1Н, СНpy, J 6.5 Hz), 7.55 (t, 1Н, СНpy, J 7.7 Hz), 7.74 (d, 1Н, СНpy, J 8.9 Hz), 7.99-8.10 (m, 2Н, СНpy, (3)СН). 13C
NMR, δ, ppm: 14.34, 15.08, 22.49, 26.19, 27.66, 28.82, 29.01, 31.54, 55.25, 58.83, 59.37, 75.83, 92.65,
114.44, 120.33, 120.74, 138.08, 141.92, 147.39, 153.10, 166.32. Anal. calcd for C20H28N2O2 (328.46): C,
73.14; H, 8.59; N, 8.53. Found: C, 72.98; H, 8.42; N, 8.46.
(2E,4E)-4-(1-Octylpyridin-2(1H)-ylidene)-2-cyanobut-2-enethioamide (6i). Yield 88%, mp 139–141 °C, red
crystals. IR (KBr), ν, сm–1: 3432, 3295, 3189, 3088, 2922, 2853, 2178, 1630, 1610, 1536, 1410, 1365, 1307,
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1236, 1217, 1148, 1056, 1036, 959, 862, 821, 757, 716, 573, 545. H NMR, δ, ppm: 0.85 (t, 3Н, (8`)СН3, J 6
Hz), 1.25-1.32 (m, 10Н, 5СН2), 1.73 (sbr, 2Н, (2`)СН2), 4.11 (t, 2Н, (1`)СН2, J 7.3 Hz), 5.57 (d, 1Н, (4)СН, 3J 13.7
Hz), 6.82 (t, 1Н, СНpy, J 6.7 Hz), 7.63 (d, 1Н, СНpy, J 7.3 Hz), 7.82 (d, 1Н, СНpy, J 9 Hz), 7.98-8.05 (m, 3Н, NH2,
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CHpy), 8.39 (d, 1Н, (3)СН, J 13.7 Hz). 13C NMR, δ, ppm: 14.39, 22.48, 26.21, 27.70, 28.82, 29.00, 31.54,
55.43, 89.38, 94.16, 114.80, 120.48, 121.05, 138.18, 142.24, 144.86, 153.27, 190.78. Anal. calcd for
C18H25N3S (315.48): C, 68.53; H, 7.99; N, 13.32; S, 10.16. Found: C, 68.48; H, 7.88; N, 13.13; S, 10.09.
tert-Butyl (E)-2-(2-(3,3-dicyanoallylidene)pyridin-1(2H)-yl)acetate (6j). Yield 65%, mp 187–189 °C, yellow
crystals. IR (KBr), ν, сm–1: 2182, 1672, 1664, 1523, 1459, 1443, 1411, 1306, 1241, 1208, 1148, 1085, 1035,
964, 807, 770, 754, 715, 650, 551, 455. 1H NMR, δ, ppm: 1.46 (s, 9H, C(СН3)3), 5.00 (s, 2Н, СН2CO2-t-Bu), 5.30
(d, 1H, (2)CH, 3J 13.6 Hz), 6.86 (t, 1H, CHpy, J 6.7 Hz), 7.62 (t, 1H, CHpy, J 7.7 Hz) 7.92-7.97 (m, 3H, (1)CH,
2CHpy). 13C NMR, δ, ppm: 27.98, 50.96, 57.20, 83.84, 93.45, 114.84, 118.40, 120.59, 121.01, 138.80, 142.44,
150.28, 153.57, 166.09. Anal. calcd for C16H17N3O2 (283.33): C, 67.83; H, 6.05; N, 14.83. Found: C, 67.71; H,
5.94; N, 14.70.
Ethyl (2E,4E)-4-(1-(2-(tert-butoxy)-2-oxoethyl)pyridin-2(1H)-ylidene)-2-cyanobut-2-enoate (6k). Yield 63%,
mp 171–173 °C, orange crystals. IR (KBr), ν, сm–1: 3090, 3055, 2986, 2974, 2904, 2187, 1731, 1669, 1637,
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1525, 1458, 1417, 1370, 1310, 1231, 1152, 1091, 1046 1023, 967, 952, 877, 801, 772, 756, 720. H NMR, δ,
ppm: 1.21 (t, 2H, CO2СН2CH3, J 7 Hz) 1.44-1.47 (m, 9H, C(СН3)3), 4.10 (q, 2Н, CO2СН2CH3, J 7 Hz), 4.94 (s, 2H,
CH2CO2t-Bu), 5.30 (d, 1H, (4)CH, 3J 13.7 Hz), 6.76 (t, 1H, CHpy, J 7.7 Hz), 7.56 (t, 1H, CHpy, J 7.7 Hz), 7.74 (d,
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1H, CHpy, J 9 Hz), 7.90 (d, 1H, CHpy, J 6.5 Hz), 8.09 (d, (3)CH, 1H, 3J 13.7 Hz). C NMR, δ, ppm: 15.03, 27.99,
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