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CrystEngComm
CrystEngComm
1
1
1
1
.25 (t, J = 7.5 Hz, 3H). 13C NMR (125 MHz, DMSO-d
6
): δ 164.1,
C
28
H
26
N
2
O
2
DOI: 10.1039/C9CE00348G
62.90 (d, J = 247.5 Hz), 162.88 (d, J = 247.5 Hz), 158.2, 157.6, 6.60.
52.9, 135.5, 135.1, 131.80 (d, J = 5.0 Hz), 131.77 (d, J = 6.3 Hz),
30.25 (d, J = 13.8 Hz), 130.18 (d, J = 13.8 Hz), 119.68 (d, J = 30.0
Ethyl 2-cyano-2-(1-ethyl-2,6-bis((E)-4-fluorostyryl)pyridin-4(1H)-
ylidene)acetate (CMD-F). yellow-green solid (167.3 mg), 56.5%
yield, m. p. 259.0-259.4 °C. H NMR (500 MHz, DMSO-d
Hz), 119.67 (d, J = 30.0 Hz), 118.1, 115.82 (d, J = 21.3 Hz), 115.80 (d,
J = 21.3 Hz), 109.0, 107.5, 79.9, 60.0, 14.2. MS (ESI, m/z): 432.11
1
6
): δ 8.47 (d,
+
J = 2.0 Hz, 1H), 7.88-7.84 (m, 4H), 7.46-7.40 (m, 2H), 7.33-7.27 (m,
H), 6.96 (d, J = 2.0 Hz, 1H), 4.36 (q, J = 8.5 Hz, 2H), 4.08 (q, J = 7.2
[
M+H] . Anal. calcd. for C26
19 2 3
H F NO : C, 72.38; H, 4.44; N, 3.25.
6
Found: C, 72.69; H, 4.42; N, 3.23.
1
3
Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H). C NMR (125
2-(2,6-bis((E)-4-chlorostyryl)-4H-pyran-4-ylidene)-2- MHz, DMSO-d ): δ 166.3, 153.4, 148.2, 147.9, 136.8, 134.3, 133.9,
Ethyl
6
cyanoacetate (3c). Orange-yellow solid (378.8 mg), 81.6% yield, m. 129.54, 129.52, 128.82, 128.79, 121.6, 121.3, 121.2, 112.9, 112.2,
1
+
-
p. 236.4-236.7 °C. H NMR (500 MHz, DMSO-d
6
): δ 8.02 (d, J = 1.5 67.0, 58.5, 44.9, 14.6. MS (ESI, m/z): 459.29 [M+H] . FT-IR (KBr, cm
3
4
1
Hz, 1H), 7.85-7.81 (m, 4H), 7.68 (dd, J = 16.0 Hz, J = 5.5 Hz, 2H),
): 2979, 2186, 1656, 1633, 1600, 1534, 1534, 1510, 1471, 1379,
7
6
3
1
1
.52-7.50 (m, 4H), 7.42 (d, J = 16.0 Hz, 1H), 7.32 (d, J = 16.0 Hz, 1H), 1302, 1272, 1052, 978, 852, 826. Anal. calcd. for C28
24 2 2 2
H F N O : C,
.83 (d, J = 15.0 Hz, 1H), 4.18 (q, J = 7.0 Hz, 2H), 1.25 (t, J = 7.0 Hz, 73.35; H, 5.28; N, 6.11. Found: C, 72.99; H, 5.30; N, 6.08.
1
3
6
H). C NMR (125 MHz, DMSO-d ): δ 164.0, 158.0, 157.4, 152.7,
Ethyl 2-(2,6-bis((E)-4-chlorostyryl)-1-ethylpyridin-4(1H)-ylidene)-
35.3, 134.9, 134.24, 134.21, 134.1, 134.0, 129.7, 129.6, 128.83,
28.80, 120.7, 120.4, 118.0, 109.4, 107.9, 80.3, 60.1, 14.2. MS (ESI,
2
-cyanoacetate (CMD-Cl). yellow-green solid (122.1 mg), 68.1%
1
+
yield, m. p. 246.7-247.7°C. H NMR (500 MHz, DMSO-d ): δ 8.47 (d, J
m/z): 465.80 [M+H] . Anal. calcd. for C26
H19Cl
2 3
NO : C, 67.25; H, 4.12;
6
=
1
2.0 Hz, 1H), 7.82 (d, J = 8.0 Hz, 4H), 7.51-7.46 (m, 6H), 7.29 (t, J =
5.5 Hz, 2H), 6.97 (d, J = 2.0 Hz, 1H), 4.35 (q, J = 7.0 Hz, 2H), 4.08 (q,
N, 3.02. Found: C, 66.97; H, 4.10; N, 3.04.
1
3
Ethyl
2-(2,6-bis((E)-4-bromostyryl)-4H-pyran-4-ylidene)-2- J = 7.0 Hz, 2H), 1.30 (t, J = 7.0 Hz, 3H), 1.20 (t, J = 7.0 Hz, 3H). C
cyanoacetate (3d). Orange-yellow solid (453.6 mg), 82.0% yield, m. NMR (125 MHz, DMSO-d
6
): δ 166.3, 153.4, 148.2, 147.9, 136.8,
1
p. 249.7-250.5°C. H NMR (500 MHz, DMSO-d
6
): δ 8.02 (d, J = 1.0 Hz, 134.3, 133.9, 129.54, 129.52, 128.82, 128.79, 121.6, 121.3, 121.2,
+
1
7
3
1
1
H), 7.78-7.74 (m, 4H), 7.69-7.63 (m, 6H), 7.44 (d, J = 16.0 Hz, 1H), 112.9, 112.2, 67.0, 58.5, 44.9, 14.6. MS (ESI, m/z): 492.31 [M+H] .
-1
.34 (d, J = 16.5 Hz, 1H), 4.18 (q, J = 7.0 Hz, 2H), 1.25 (t, J = 7.0 Hz, FT-IR (KBr, cm ): 2977, 2183, 1657, 1635, 1616, 1599, 1534, 1474,
1
3
6 2 2 2
H). C NMR (125 MHz, DMSO-d ): δ 164.0, 158.0, 157.4, 152.7, 1378, 1268, 1052, 968, 815, 808. Anal. calcd. for C28H24Cl N O : C,
35.4, 135.0, 134.43, 134.38, 131.8, 131.7, 129.9, 129.8, 123.1, 68.44; H, 4.92; N, 5.70. Found: C, 68.71; H, 4.94; N, 5.67.
23.0, 120.7, 120.5, 118.0, 109.4, 108.0, 80.4, 60.1, 14.2. MS (ESI,
+
Ethyl 2-(2,6-bis((E)-4-bromostyryl)-1-ethylpyridin-4(1H)-ylidene)-
-cyanoacetate (CMD-Br). yellow-green solid (195.9 mg), 67.5%
yield, m. p. 246.6-247.6°C. H NMR (500 MHz, DMSO-d
m/z): 554.31 [M+H] . Anal. calcd. for C26
3
2 3
H19Br NO : C, 56.45; H,
2
.46; N, 2.53. Found: C, 56.19; H, 3.48; N, 2.52.
1
6
): δ 8.47 (d, J
Synthesis of the CMD derivatives
= 2.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 4H), 7.64 (d, J = 8.5 Hz, 4H), 7.50
3
4
(dd, J = 16.0 Hz, J = 7.5 Hz, 2H), 7.28 (t, J = 16.0 Hz, 2H), 6.97 (d, J =
General procedure: Compound 3a/3b/3c/3d (0.5 mmol) and
ethylamine (0.8 mL) were dissolved in 6 mL of acetonitrile. The
mixture was heated at 80 ° C for 6 h under N atmosphere. After
2
2
=
.0 Hz, 1H), 4.35 (q, J = 7.0 Hz, 2H), 4.08 (q, J = 7.0 Hz, 2H), 1.29 (t, J
7.0 Hz, 3H), 1.20 (t, J = 7.0 Hz, 3H). C NMR (125 MHz, DMSO-d ):
6
13
δ 166.2, 153.4, 148.1, 147.8, 136.9, 134.6, 131.71, 131.69, 129.8,
cooling to room temperature, the precipitate was filtered and
washed with methanol, and dried to afford pure target compounds.
The characterization data of CMD-H, CMD-F, CMD-Cl, and CMD-Br
are as follows:
1
1
1
8
29.7, 122.7, 121.7, 121.3, 121.1, 112.8, 112.2, 67.0, 58.4, 44.9,
4.6. MS (ESI, m/z): 581.02 [M+H] . FT-IR (KBr, cm ): 2985, 2204,
698, 1641, 1616, 1546, 1511, 1487, 1318.46, 1241, 1043, 946, 851,
+
-1
2
07. Anal. calcd. for C28H24Br N
2
O
2
: C, 57.95; H, 4.17; N, 4.83.
Found: C, 58.22; H, 4.19; N, 4.80.
Ethyl
2-cyano-2-(1-ethyl-2,6-di((E)-styryl)pyridin-4(1H)-
ylidene)acetate (CMD-H). yellow solid (122.1 mg), 57.8% yield, m. p.
1
2
1
4
74.7-275.4 °C. H NMR (500 MHz, DMSO-d
6
): δ 8.49 (d, J = 2.0 Hz,
Results and discussion
3
H), 7.78 (d, J = 7.5 Hz, 2H), 7.50-7.39 (m, 8H), 7.29 (dd, J = 15.5 Hz,
J = 10.0 Hz, 2H), 6.98 (d, J = 2.0 Hz, 1H), 4.37 (q, J = 6.5 Hz, 2H), 4.08 Synthesis and characterization
(
q, J = 7.5 Hz, 2H), 1.32 (t, J = 7.0 Hz, 3H), 1.21 (t, J = 7.0 Hz, 3H). 13
NMR (125 MHz, DMSO-d ): δ 166.3, 153.5, 148.4, 148.1, 138.2,
C
6
1
1
38.1, 135.3, 129.5, 128.83, 128.80, 127.8, 121.2, 120.8, 120.5,
12.8, 112.1, 66.8, 58.4, 44.9, 14.62, 14.55. MS (ESI, m/z): 423.40
+
-1
[
M+H] . FT-IR (KBr, cm ): 2988, 2186, 1672, 1637, 1618, 1601,
534, 1472, 1379, 1269, 1052, 967, 755, 691. Anal. calcd. for
1
This journal is © The Royal Society of Chemistry 20xx
Scheme 2. Synthetic route towards the CMD derivatives
CrystEngComm, 2015, 00, 1-3 | 3
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