Chemical reagents and solvents were purchased from Sigma Aldrich (Darmstadt, Germany). Melting points (uncorrected) of compounds 16a–h were determined by an IA 9100MK-Digital melting point apparatus (Cole-Parmer, Vernon Hills, IL, USA). Absorption bands in the infrared (IR) spectra were recorded on a RUKER TENSOR 37 FTIR spectrophotometer. Molecular ions and mass spectra (MS) of compounds 16a–h were analyzed using the Shimadzu Qp-2010 Plus mass spectrometer (EI ionization mode). The elemental analyses (C, H, and N) of compounds 16a–h were measured in a Microanalytical Center, Cairo University. 1H-NMR, 13C-NMR, and DEPT C135 spectra were recorded using BRUKER AVANCE III at 500 MHz, 125 and 125 MHz, respectively.
3.2.1. General Procedure (A) for Preparation of Compounds (16a–h)
The new compounds were prepared from compound
15a,
b according to the reported procedures [
20]. A mixture of the pyrrolizine
15a,
b (3.4 mmol), the appropriate aldehyde (4.4 mmol), and glacial acetic acid (0.5 mL) in absolute ethanol (30 mL) was refluxed for 4–6 h. The reaction mixture was then concentrated and set aside to cool. The solid product obtained was recrystallized from acetone-chloroform.
7-Cyano-6-((4-(dimethylamino)benzylidene)amino)-N-(4-methoxyphenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16a)
Compound 15a (1 g, 3.4 mmol) was refluxed with 4-(dimethylamino)benzaldehyde (0.65 g, 4.4 mmol) according to the general procedure A to afford compound 16a as a yellow solid product, m.p. 226-8 °C, yield 58%. IRʋmax/cm−1 3218 (NH), 3076, 3002, (aromatic C-H), 2958, 2904, 2830 (aliphatic C-H), 2209 (CN), 1656 (C=O), 1583, 1539, 1509 (C=C, C=N). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.55 (m, 2H, CH2-2), 3.04 (t, 2H, J = 6.8 Hz, CH2-1), 3.13 (s, 6H, N(CH3)2), 3.83 (s, 3H, OCH3), 4.52 (t, 2H, J = 7.4 Hz, CH2-3), 6.79 (d, 2H, J = 7.6 Hz, phenyl B CH-3+CH-5), 6.92 (d, 2H, J = 7.2 Hz, phenyl A CH-3+CH-5), 7.62 (d, 2H, J = 7.4 Hz, phenyl B CH-2+CH-6), 7.82 (d, 2H, J = 7.7 Hz, phenyl A CH-2+CH-6), 8.98 (s, 1H, (N=CH), 10.82 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.59 (CH2-2), 25.43 (CH2-2), 40.27 (N(CH3)2), 49.98 (CH2-3), 55.53 (OCH3), 111.85 (phenyl B CH-3 + CH-5), 114.22 (phenyl A CH-3 + CH-5), 116.71 (C-7), 116.76 (CN), 121.25 (phenyl A CH-2 + CH-6), 122.06 (phenyl B CH-2 + CH-6), 123.15 (C-6), 130.90 (phenyl A C-1), 131.87 (phenyl B C-1), 147.61 (C-5), 153.17 (C-7a), 155.94 (phenyl B C-4), 158.75 (phenyl A C-4), 159.59 (N=CH), 163.43 (CO). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 24.59 (CH2-2), 25.43 (CH2-2), 40.28 (N(CH3)2), 49.98 (CH2-3), 55.54 (OCH3), 111.86 (phenyl B CH-3 + CH-5), 114.22 (phenyl A CH-3 + CH-5), 121.25 (phenyl A CH-2 + CH-6), 122.06 (phenyl B CH-2 + CH-6), 159.59 (N=CH). MS (EI): m/z (%) 427 (M+, 28), 411 ([M-16]+, 43), 402 (33), 312 ([M-15]+, 52), 287 (88), 261 (81), 256 (85), 227 (38), 218 (42), 191 (67), 147 (33), 72 (57), 52 (100). Anal. Calcd. for C25H25N5O2 (427.50): C, 70.24; H, 5.89; N, 16.38. Found: C, 69.85; H, 5.62; N, 16.84.
7-Cyano-6-((4-(dimethylamino)benzylidene)amino)-N-(4-fluorophenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16b)
Compound 15b (0.96 g, 3.4 mmol) was refluxed with 4-(dimethylamino)benzaldehyde (0.65 g, 4.4 mmol) according to the general procedure A to afford compound 16b as a yellow solid product, m.p. 244-6 °C, yield 54%. IRʋmax/cm−1 3236 (NH), 3061 (aromatic C-H), 2997, 2907, 2822 (aliphatic C-H), 2213 (CN), 1660 (C=O), 1611, 1580, 1529 (C=C, C=N). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.57 (m, 2H, CH2-2), 3.05 (t, 2H, J = 6.5 Hz, CH2-1), 3.17 (s, 6H, N(CH3)2), 4.49 (t, 2H, J = 6.4 Hz, CH2-3), 6.86 (d, 2H, J = 7.4 Hz, phenyl B CH-3+CH-5), 7.05 (d, 2H, J = 8.3 Hz, phenyl A CH-3 + CH-5), 7.72 (broad s, 2H, phenyl B CH-2 + CH-6), 7.95 (broad s, 2H, phenyl A CH-2 + CH-6), 8.77 (s, H, N=CH), 11.00 (s, H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.72 (CH2-2), 25.48 (CH2-1), 40.67 (N(CH3)2), 49.98 (CH2-3), 111.19 (phenyl B CH-3 + CH5), 112.56 (phenyl B CH-2 + CH-6), 115.57 (d, J = 22.3 Hz, phenyl A CH-3 + CH-5), 115.92 (C-7), 116.54 (CN), 117.21 (C-6), 121.58 (d, J = 7.8 Hz, phenyl A CH-2 + CH6), 130.46 (phenyl B C-1), 132.34 (C-5), 134.59 (d, J = 2.8 Hz, phenyl A C-1), 147.62 (C-7a), 152.24 (phenyl B C-4), 158.43 (N=CH), 159.11 (d, J = 242.7 Hz, phenyl A C-4), 160.48 (CO). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 24.72 (CH2-2), 25.48 (CH2-1), 40.67 (N(CH3)2), 49.98 (CH2-3), 111.19 (phenyl B CH-3 + CH5), 112.61 (phenyl B CH-2 + CH6), 115.57 (d, J = 22.3 Hz, phenyl A CH-3 + CH5), 121.58 (d, J = 7.8 Hz, phenyl A CH-2 + CH6), 158.43 (N=CH). MS (EI): m/z (%) 415 (M+, 17), 412 ([M-3]+, 48), 395 (37), 384 (100), 346 (34), 301 (48), 295 (86), 253 (49), 223 (37), 199 (49), 173 (62), 144 (68), 105 (79). Anal. Calcd. for C24H22FN5O (415.46): C, 69.38; H, 5.34; N, 16.86. Found: C, 68.91; H, 5.77; N, 17.14.
7-Cyano-N-(4-methoxyphenyl)-6-((4-methylbenzylidene)amino)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16c)
Compound 15a (1 g, 3.4 mmol) was refluxed with 4-methylbenzaldehyde (0.53 g, 4.4 mmol) according to the general procedure A to afford compound 16c as a yellow solid product, m.p. 231-3°C, yield 61%. IRʋmax/cm−1 3230 (NH), 3061, 3000 (aromatic C-H), 2948, 2830 (aliphatic C-H), 2209 (CN), 1663 (C=O), 1600, 1549, 1509 (C=C, C=N). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.47 (s, 3H, CH3), 2.54 (m, 2H, CH2-2), 3.01 (t, 2H, J = 7.1 Hz, CH2-1), 3.83 (s, 3H, OCH3), 4.51 (t, 2H, J = 7.3 Hz, CH2-3), 6.91 (d, 2H, J = 7.8 Hz, phenyl A CH-3′+CH-5′), 7.34 (d, 2H, J = 7.1 Hz, phenyl B CH-3″+CH-5″), 7.58 (d, 2H, J = 7.8 Hz, phenyl A CH-2′+CH-6′), 7.80 (d, 2H, J = 7.1 Hz, phenyl B CH-2″+CH-6″), 9.11 (s, 1H, N=CH), 10.60 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 21.78 (CH3), 24.50 (CH2-2), 25.41 (CH2-1), 50.08 (CH2-3), 55.53 (OCH3), 114.25 (phenyl A CH-3 + CH-5), 116.40 (C-7), 117.75 (CN), 121.08 (phenyl A CH-2 + CH-6), 128.75 (phenyl B CH-2 + CH-6), 129.73 (C-6), 129.90 (phenyl B CH-3 + CH-5), 131.61 (phenyl A C-1), 132.79 (phenyl B C-1), 139.10 (C-5), 143.24 (C-7a), 148.04 (phenyl B C-4), 156.07 (phenyl A C-4), 158.32 (CO), 159.49 (N=CH). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 21.78 (CH3), 24.50 (CH2-2), 25.41 (CH2-1), 50.08 (CH2-3), 55.53 (OCH3), 114.25 (phenyl A CH-3 + CH-5), 121.08 (phenyl A CH-2 + CH-6), 128.75 (phenyl B CH-2 + CH-6), 129.90 (phenyl B CH-3 + CH-5), 159.49 (N=CH). MS (EI): m/z (%) 399 ([M+1]+, 13), 393 ([M-5]+, 17), 382 ([M-16]+, 14), 377 (56), 364 (31), 336 (37), 318 (89), 287 (100), 275 (34), 240 (13), 212 (26), 198 (31), 171 (23), 154 (22), 92 (24). Anal. Calcd. for C24H22N4O2 (398.46): C, 72.34; H, 5.57; N, 14.06. Found: C, 72.81; H, 5.69; N, 13.84.
7-Cyano-N-(4-fluorophenyl)-6-((4-methylbenzylidene)amino)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16d)
Compound 15b (0.96 g, 3.4 mmol) was refluxed with 4-methylbenzaldehyde (0.53 g, 4.4 mmol) according to the general procedure A to afford compound 16d as a yellow solid product, m.p. 241-3 °C, yield 59%. IRʋmax/cm−1 3235 (NH), 3066 (aromatic C-H), 2955, 2924, 2858 (aliphatic C-H), 2214 (CN), 1664 (C=O), 1601 1551, 1506 (C=C, C=N), 1208 (C-F). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.47 (s, 3H, CH3), 2.56 (m, 2H, CH2-2), 3.02 (t, 2H, J = 6.2 Hz, CH2-1), 4.51 (t, 2H, J = 6.9 Hz, CH2-3), 7.05 (d, 2H, J = 8.1 Hz, phenyl A CH-3′+CH-5′), 7.34 (d, 2H, J = 6.9 Hz, phenyl B CH-3″+CH-5″), 7.62 (d, 2H, J = 7.8 Hz, phenyl A CH-2′+CH-6′), 7.80 (d, 2H, J = 6.6 Hz, phenyl B CH-2″+CH-6″), 9.11 (s, 1H, N=CH), 10.71 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 21.79 (CH3), 24.53 (CH2-2), 25.40 (CH2-1), 50.11 (CH2-3), 115.71 (d, J = 22.4 Hz, phenyl A CH-3 + CH-5), 116.25 (C-7), 117.46 (CN), 121.09 (d, J = 7.9 Hz, phenyl A CH-2 + CH-6), 128.75 (phenyl B CH-2+ CH-6), 129.73 (C-6), 129.95 (phenyl B CH-3 + CH-5), 132.69 (phenyl B C-1), 134.46 (d, J = 2.8 Hz, phenyl A C-1), 139.37 (C-5), 143.45 (C-7a), 148.23 (phenyl B C-4), 158.10, 158.46 (CO), 159.07 (d, J = 243.0 Hz, phenyl A C-4), 159.77 (N=CH). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 21.79 (CH3), 24.53 (CH2-2), 25.40 (CH2-1), 50.11 (CH2-3), 115.71 (d, J = 22.4 Hz, phenyl A CH-3 + CH-5), 121.09 (d, J = 7.9 Hz, phenyl A CH-2 + CH-6), 128.76 (phenyl B CH-2+ CH-6), 129.95 (phenyl B CH-3 + CH-5), 159.77 (N=CH). MS (EI): m/z (%) 386 (M+, 51), 383 ([M-3]+, 2), 370 ([M-16]+, 73), 356 ([M-30]+, 38), 341 (65), 326 (22), 308 (33), 285 (29), 247 (26), 216 (17), 193 (100), 165 (61), 133 (44), 110 (58). Anal. Calcd. for C23H19FN4O (386.42): C, 71.49; H, 4.96; N, 14.50. Found: C, 71.62; H, 4.69; N, 14.43.
7-Cyano-6-((4-fluorobenzylidene)amino)-N-(4-methoxyphenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16e)
Compound 15a (1 g, 3.4 mmol) was refluxed with 4-flourobenzaldehyde (0.54 g, 4.4 mmol) according to the general procedure A to afford compound 16e as a yellow solid product, m.p. 239-41 °C, yield 67%. IRʋmax/cm−1 3233 (NH), 3070, 3007 (aromatic C-H), 2955, 2890 (aliphatic C-H), 2210 (CN), 1662 (C=O), 1600, 1584, 1509 (C=C, C=N), 1229 (C-F). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.57 (m, 2H, CH2-2), 3.05 (t, 2H, J = 7.1 Hz, CH2-1), 3.84 (s, 3H, OCH3), 4.54 (t, 2H, J = 7.1 Hz, CH2-3), 6.93 (d, 2H, J = 8.9 Hz, phenyl A CH-3 + CH-5), 7.23 (d, 2H, J = 8.3 Hz, phenyl B CH-3 + CH-5), 7.56 (d, 2H, J = 8.8 Hz, phenyl A CH-2 + CH-6), 7.93 (d, 2H, J = 7.0 Hz, phenyl B CH-2+CH-6), 9.14 (s, 1H, N=CH), 10.46 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.54 (CH2-2), 25.45 (CH2-1), 50.15 (CH2-3), 55.54 (OCH3), 114.33 (phenyl A CH-3 + CH-5), 114.80 (C-7), 116.50 (d, J 22.2 Hz, phenyl B CH-3 + CH-5), 117.97 (CN), 121.19 (phenyl A CH-2 + CH-6), 129.59 (C-6), 130.73 (d, J = 8.9 Hz, phenyl B CH-2 + CH-6), 131.39 (phenyl C-1), 131.80 (d, J = 3.0 Hz, phenyl B C-1), 132.23 (C-5), 138.80 (C-7a), 148.10 (phenyl A C-4), 156.22 (CO), 158.16 (N=CH), 165.27 (d, J = 254.5 Hz, phenyl B C-4). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 24.54 (CH2-2), 25.45 (CH2-1), 50.15 (CH2-3), 55.54 (OCH3), 114.34 (phenyl A CH-3 + CH-5), 116.51 (d, J = 22.2 Hz, phenyl B CH-3 + CH-5), 121.19 (phenyl A CH-2 + CH-6), 130.73 (d, J = 8.9 Hz, phenyl B CH-2 + CH-6), 158.16 (N=CH). MS (EI): m/z (%) 403 ([M+1]+, 52), 402 (M+, 28), 401 ([M-1]+, 12), 386 ([M-16]+, 100), 375 ([M-28]+, 19), 356 (68), 331 (23), 315 (64), 252 (58), 226 (17), 178 (23), 165 (23), 137 (49), 99 (24). Anal. Calcd. for C23H19FN4O2 (402.42): C, 68.65; H, 4.76; N, 13.92. Found: C, 68.31; H, 4.32; N, 13.84.
7-Cyano-6-((4-fluorobenzylidene)amino)-N-(4-fluorophenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16f)
Compound 15b (0.96 g, 3.4 mmol) was refluxed with 4-flourobenzaldehyde (0.54 g, 4.4 mmol) according to the general procedure A to afford compound 16f as a yellow solid product, m.p. 253-5°C, yield 66%. IRʋmax/cm−1 3222 (NH), 3072, 3003 (aromatic C-H), 2966, 2905 (aliphatic C-H), 2212 (CN), 1664 (C=O), 1600, 1585, 1553, 1507 (C=C, C=N), 1230 (C-F). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.59 (m, 2H, CH2-2), 3.08 (t, 2H, J = 6.8 Hz, CH2-1), 4.55 (t, 2H, J = 7.1 Hz, CH2-3), 7.07 (d, 2H, J = 7.9 Hz, phenyl A CH-3 + CH-5), 7.25 (d, 2H, J = 7.9 Hz, phenyl B CH-3 + CH-5), 7.61 (d, 2H, J = 8.4 Hz, phenyl A CH-2 + CH-6), 7.95 (d, 2H, J = 8.5 Hz, phenyl B CH-2 + CH-6), 9.16 (s, 1H, N=CH), 10.57 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.60 (CH2-2), 25.46 (CH2-3), 50.18 (CH2-3), 115.82 (d, J = 22.4 Hz, phenyl B CH-3 + CH-5), 116.15 (C-7), 116.31 (CN), 116.60 (d, J = 22.2 Hz, phenyl A CH-3 + CH-5), 117.69 (C-6), 121.27 (d, J = 7.6 Hz, phenyl A CH-2 + CH-6), 130.50 (d, J = 8.4 Hz, F-Ph (B) C-1), 130.83 (d, J = 8.3 Hz, phenyl B CH-2+CH-3), 131.65 (C-5), 132.27 (d, J = 9.5 Hz), 134.23 (C-7a), 158.39 (CO), 158.63 (N=CH), 159.21 (d, J = 243.6 Hz, F-Ph (A) C-4), 163.42 (d, J = 240.0 Hz, F-Ph (B) C-4). DEPT C135 (CDCl3-125 MHz, δ (ppm): δ 24.60 (CH2-2), 25.46 (CH2-3), 50.18 (CH2-3), 115.82 (d, J = 22.4 Hz, phenyl B CH-3 + CH-5), 116.60 (d, J = 22.2 Hz, phenyl A CH-3 + CH-5), 121.27 (d, J = 7.6 Hz, phenyl A CH-2 + CH-6), 130.83 (d, J = 8.3 Hz, phenyl B CH-2 + CH-3), 158.63 (N=CH). MS (EI): m/z (%) 391 ([M+1]+, 27), 388 ([M-2]+, 12), 352 (12), 341 (100), 328 (15), 300 (34), 287 (24), 257 (35), 208 (26), 192 (32), 164 (48), 149 (38), 110 (20), 83 (27). Anal. Calcd. for C22H16F2N4O (390.39): C, 67.69; H, 4.13; N, 14.35. Found: C, 68.16; H, 3.67; N, 14.76.
6-((4-Chlorobenzylidene)amino)-7-cyano-N-(4-methoxyphenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16g)
Compound 15a (1 g, 3.4 mmol) was refluxed with 4-chlorobenzaldehyde (0.62 g, 4.4 mmol) according to the general procedure A to afford compound 16g as a yellow solid product, m.p. 241-3 °C, yield 72%. IRʋmax/cm−1 3281, 3238, 3133 (NH), 3057, 3000 (aromatic C-H), 2970, 2907, 2830 (aliphatic C-H), 2209 (CN), 1663 (C=O), 1592, 1550, 1509 (C=C, C=N), 825 (C-Cl). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.56 (m, 2H, CH2-2), 3.02 (t, 2H, J = 7.2 Hz, CH2-1), 3.84 (s, 3H, OCH3), 4.52 (t, 2H, J = 7.1 Hz, CH2-3), 6.92 (d, 2H, J = 7.2 Hz, phenyl A CH-3 + CH-5), 7.51 (d, 2H, J = 8.0 Hz, phenyl A CH-2 + CH-6), 7.55 (d, 2H, J = 7.9 Hz, phenyl B CH-3 + CH-5), 7.83 (d, 2H, J = 7.8 Hz, phenyl B CH-2 + CH-6), 9.11 (s, 1H, N=CH), 10.42 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.50 (CH2-2), 25.41 (CH2-1), 50.17 (CH2-3), 55.53 (OCH3), 114.33 (phenyl A CH-3 + CH-5), 116.30 (C-7), 118.17 (CN), 121.07 (phenyl A CH-2 + CH-6), 129.51 (phenyl B CH-3 + CH-5), 129.69 (phenyl B CH-2 + CH-6), 130.93 (C-6), 131.37 (phenyl A C-1), 133.88 (C-5), 138.47 (phenyl B C-1), 138.48 (C-7a), 148.26 (phenyl B C-4), 156.20 (phenyl A C-4), 157.89 (N=CH), 158.10 (CO). DEPT135 (CDCl3-125 MHz, δ (ppm): δ (ppm): 24.49 (CH2-2), 25.41 (CH2-1), 50.17 (CH2-3), 55.53 (OCH3), 114.33 (phenyl A CH-3 + CH-5), 121.06 (phenyl A CH-2 + CH-6), 129.51 (phenyl B CH-3 + CH-5), 129.69 (phenyl B CH-2 + CH-6), 157.89 (N=CH). MS (EI): m/z (%) 418 (M+, 21), 417 ([M-1]+, 20), 413 ([M-5]+, 10), 412 ([M-6]+, 16), 368 (88), 354 (100), 328 (49), 317 (26), 292 (19), 278 (13), 229 (11), 179 (10), 165 (11), 113 (10), 97 (9). Anal. Calcd. for C23H19ClN4O2 (418.88): C, 65.95; H, 4.57; N, 13.38. Found: C, 66.34; H, 4.93; N, 13.24.
6-((4-Chlorobenzylidene)amino)-7-cyano-N-(4-fluorophenyl)-2,3-dihydro-1H-pyrrolizine-5-carboxamide (16h)
Compound 15b (0.96 g, 3.4 mmol) was refluxed with 4-chlorobenzaldehyde (0.62 g, 4.4 mmol) according to the general procedure A to afford compound 16h as a yellow solid product, m.p. 262-4 °C, yield 63%. IRʋmax/cm−1 3274 (NH), 3073, 3005 (aromatic C-H), 2955 (aliphatic C-H), 2209 (CN), 1669 (C=O), 1612, 1554, 1504 (C=C, C=N), 1205 (C-F), 835 (C-Cl). 1H-NMR (CDCl3-500 MHz, δ ppm): δ 2.56 (m, 2H, CH2-2), 3.06 (t, 2H, J = 6.8 Hz, CH2-1), 4.54 (t, 2H, J = 6.9 Hz, CH2-3), 7.09 (d, 2H, J = 8.2 Hz, phenyl A CH-3 + CH-5), 7.53 (d, 2H, J = 8.0 Hz, phenyl B CH-3 + CH-5), 7.60 (d, 2H, J = 7.1 Hz, phenyl A CH-2 + CH-6), 7.85 (d, 2H, J = 8.2 Hz, phenyl B CH-2 + CH-6), 9.15 (s, 1H, N=CH), 10.54 (s, 1H, CONH). 13C-NMR (CDCl3-125 MHz, δ ppm): δ 24.57 (CH2-2), 25.45 (CH2-1), 50.20 (CH2-3), 115.84 (d, J = 22.4 Hz, phenyl A CH-3 + CH-5), 116.15 (C-7), 117.88 (CN), 121.20 (d, J = 7.0 Hz, phenyl CH-2 + CH-6), 129.49 (C-6), 129.59 (phenyl B CH-3 + CH-5), 129.72 (phenyl B CH-2 + CH-6), 130.94 (C-5), 133.83 (C-7a), 143.22 (d, J = 2.8 Hz, phenyl A C-1), 138.86 (phenyl B C-1), 148.42 (phenyl B C-4), 158.32 (CO), 158.33 (N=CH), 159.20 (d, J = 243.2 Hz, phenyl A C-4). DEPT C135 (CDCl3-125 MHz, δ ppm): δ 24.57 (CH2-2), 25.45 (CH2-1), 50.20 (CH2-3), 115.84 (d, J = 22.4 Hz, phenyl A CH-3 + CH-5), 121.20 (d, J = 7.0 Hz, phenyl A CH-2 + CH-6), 129.60 (phenyl B CH-3 + CH-5), 129.72 (phenyl B CH-2 + CH-6), 158.33 (N=CH). MS (EI): m/z (%) 406 (M+, 8), 403 ([M-3]+, 41), 387 (14), 365 (16), 341 (100), 317 (24), 273 (68), 260 (36), 202 (28), 136 (35), 121 (52), 95 (44). Anal. Calcd. for C22H16ClFN4O (406.84): C, 64.95; H, 3.96; N, 13.77. Found: C, 64.79; H, 4.28; N, 13.92.