Molecules 2021, 26, 4002
26 of 32
3
.84 (s, 3H, OCH ), 4.54 (t, 2H, J = 7.1 Hz, CH -3), 6.93 (d, 2H, J = 8.9 Hz, phenyl A CH-3 +
3
2
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 (CDCl -125 MHz, δ ppm): δ 24.54 (CH -2), 25.45 (CH -1), 50.15
3 2 2
(
CH -3), 55.54 (OCH ), 114.33 (phenyl A CH-3 + CH-5), 114.80 (C-7), 116.50 (d, J 22.2 Hz,
2
3
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 C1 (CDCl -125 MHz,
35
δ
ppm):
δ
24.54 (CH -2),
(
3
2
2
5.45 (CH -1), 50.15 (CH -3), 55.54 (OCH ), 114.34 (phenyl A CH-3 + CH-5), 116.51 (d,
2 2 3
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),
+
+
+
4
2
6
01 ([M-1] , 12), 386 ([M-16] , 100), 375 ([M-28] , 19), 356 (68), 331 (23), 315 (64), 252 (58),
26 (17), 178 (23), 165 (23), 137 (49), 99 (24). Anal. Calcd. for C H FN O (402.42): C,
23
19
4
2
8.65; H, 4.76; N, 13.92. Found: C, 68.31; H, 4.32; N, 13.84.
7
5
-Cyano-6-((4-fluorobenzylidene)amino)-N-(4-fluorophenyl)-2,3-dihydro-1H-pyrrolizine-
-carboxamide (16f)
Compound 15b (0.96 g, 3.4 mmol) was refluxed with 4-flourobenzaldehyde (0.54 g,
.4 mmol) according to the general procedure A to afford compound 16f as a yellow solid
4
◦
−1
product, m.p. 253-5 C, yield 66%. IRʋmax/cm 3222 (NH), 3072, 3003 (aromatic C-H),
2
966, 2905 (aliphatic C-H), 2212 (CN), 1664 (C=O), 1600, 1585, 1553, 1507 (C=C, C=N), 1230
1
(C-F). H-NMR (CDCl -500 MHz,
δ
ppm):
δ
2.59 (m, 2H, CH -2), 3.08 (t, 2H, J = 6.8 Hz,
3
2
CH -1), 4.55 (t, 2H, J = 7.1 Hz, CH -3), 7.07 (d, 2H, J = 7.9 Hz, phenyl A CH-3 + CH-5), 7.25
2
2
(
7
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),
.95 (d, 2H, J = 8.5 Hz, phenyl B CH-2 + CH-6), 9.16 (s, 1H, N=CH), 10.57 (s, 1H, CONH).
1
3
C-NMR (CDCl -125 MHz,
δ
ppm):
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
δ 24.60 (CH -2), 25.46 (CH -3), 50.18 (CH -3), 115.82
3
2 2 2
(
(
(
(
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 (CDCl -125 MHz,
δ
(ppm):
δ
3
2
4.60 (CH -2), 25.46 (CH -3), 50.18 (CH -3), 115.82 (d, J = 22.4 Hz, phenyl B CH-3 + CH-5),
2
2
2
1
16.60 (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 C H F2N O (390.39): C,
22
16
4
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
◦
−1
solid product, m.p. 241-3 C, yield 72%. IRʋmax/cm 3281, 3238, 3133 (NH), 3057, 3000
(
(
(
aromatic C-H), 2970, 2907, 2830 (aliphatic C-H), 2209 (CN), 1663 (C=O), 1592, 1550, 1509
1
C=C, C=N), 825 (C-Cl). H-NMR (CDCl -500 MHz,
δ
ppm):
δ
2.56 (m, 2H, CH -2), 3.02
3
2
t, 2H, J = 7.2 Hz, CH -1), 3.84 (s, 3H, OCH ), 4.52 (t, 2H, J = 7.1 Hz, CH -3), 6.92 (d, 2H,
2
3
2
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),
.11 (s, 1H, N=CH), 10.42 (s, 1H, CONH). 13C-NMR (CDCl -125 MHz,
ppm): 24.50
CH -2), 25.41 (CH -1), 50.17 (CH -3), 55.53 (OCH ), 114.33 (phenyl A CH-3 + CH-5), 116.30
(
9
δ
δ
3
(
(
(
2
2
2
3
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