RSC Advances
Paper
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1
(
1.071 g, 76%); mp 240–242 C; H-NMR (400 MHz, DMSO-d6) 128.5, 128.9, 129.3, 130.0, 131.2, 132.5, 132.5, 133.0, 133.1,
d 5.22 (s, 2H), 6.99 (d, J ¼ 8.4 Hz, 1H), 7.39–7.45 (m, 2H), 7.59 156.9, 159.2, 160.5; MS (MMES + APCI) m/z: calcd for
(
7
{
1
1
t, J ¼ 7.6 Hz, 2H), 7.66 (d, J ¼ 8.4 Hz, 2H), 7.74 (d, J ¼ 2 Hz, 1H), C24H14Cl N O 444.05 found: 443.65; elemental analysis calcd
2
4
1
3
.89 (d, J ¼ 7.6 Hz, 2H), 7.90 (d, J ¼ 8 Hz, 2H), 8.60 (s, 2H);
C
(%) for C24H14Cl N O: C, 64.73; H, 3.17; Cl, 15.92; N, 12.58; O,
2 4
1
H}-APT (100 MHz, DMSO-d6) d 44.2, 75.8, 87.4, 115.9, 116.5, 3.59 found: C, 64.98; H, 3.17; N, 12.59.
26.7, 126.8, 127.4, 128.1, 128.8, 128.9, 129.1, 131.2, 132.4,
33.1, 133.5, 138.9, 141.9, 156.9, 159.2, 160.7; MS (MMES +
General scheme and procedure for the synthesis of 6a–6d
APCI) m/z: calcd for C26
elemental analysis calcd (%) for C26
3
1
H
16Cl
2
N
4
O 470.07 found: 470.6;
O: C, 66.25; H, A mixture of 3 mmol 9-anthraldehyde, 3 mmol malononitrile
.42; Cl, 15.04; N, 11.89; O, 3.39 found: C, 66.41; H, 3.42; N, and 0.3 mmol (10 mol%) piperidinium acetate in 10 ml ethanol
1.91.
was stirred at room temperature for 5 minutes to produce ary-
-Amino-1-benzyl-4-(naphthalen-1-yl)-2-oxo-1,2-dihydropyridine- lidene malononitrile. Then, 3 mmol of N-substituted 2-cya-
,5-dicarbonitrile (5i). Off-white solid (0.742 g, 66%); mp 262– noacetamide was added to the reaction mixture and reuxed for
2 4
H16Cl N
6
3
2
5
2
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1
64 C; H-NMR (400 MHz, DMSO-d6) d 5.32 (d, J ¼ 16.8 Hz, 1H), 9 hours. Upon completion, as monitored by TLC, the reaction
.44 (d, J ¼ 16.4 Hz, 1H), 7.33 (t, J ¼ 8.0 Hz, 2H), 7.41 (t, J ¼ 7.2 Hz, mixture was cooled and poured into water. The resulting solid
H), 7.60–7.69 (m, 4H), 7.84 (d, J ¼ 9.2 Hz, 1H), 8.05–8.12 (m, 2H), was ltered off, washed with water, dried and recrystallized
13
1
8
1
1
(
.50 (s, 2H); C{ H}-APT (100 MHz, DMSO-d6) d 44.8, 77.1, 89.1, from dichloromethane to give the pure products 6a–6d.
15.4, 116.1, 124.6, 125.4, 125.9, 126.5, 126.6, 127.3, 127.4, 128.5,
3-(Anthracen-9-yl)-N-benzyl-2-cyanoacrylamide (6a). Yellow
28.5, 129.3, 129.9, 132.5, 133.0, 134.4, 156.5, 159.4, 160.2; MS solid (0.958 g, 88%); mp 220–222 C; H-NMR (400 MHz, DMSO-
MMES + APCI) m/z: calcd for C H N O 376.13 found: 375.80; d6) d 4.55 (d, J ¼ 5.6 Hz, 2H), 7.31 (t, J ¼ 7.2 Hz, 1H), 7.39–7.47
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1
24
16
16
4
elemental analysis calcd (%) for C24
4.88; O, 4.25 found: C, 76.59; H, 4.28; N, 14.88.
-Amino-1-(2-chlorobenzyl)-4-(naphthalen-1-yl)-2-oxo-1,2- { H}-APT (100 MHz, DMSO-d6) d 43.2, 115.0, 117.1, 124.9, 125.8,
dihydropyridine-3,5-dicarbonitrile (5j). Off-white solid 126.4, 127.06, 127.12, 127.6, 128.2, 128.4, 128.9, 129.3, 130.6,
H
N
4
O: C, 76.58; H, 4.28; N, (m, 4H), 7.60–7.67 (m, 4H), 8.06 (d, J ¼ 8.4 Hz, 2H), 8.20 (d, J ¼
13
1
7.6 Hz, 2H), 8.80 (s, 1H) 9.10 (s, 1H), 9.46 (t, J ¼ 5.6 Hz, 1H);
C
1
6
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1
(
0.784 g, 64%); mp 230–232 C; H-NMR (400 MHz, DMSO-d6) 138.7, 150.1, 160.4; MS (MMES + APCI) m/z: calcd for C25
d 5.26 (d, J ¼ 17.6 Hz, 1H), 5.33 (d, J ¼ 17.6 Hz, 1H), 7.10 (d, J 362.14 found: 362.60; elemental analysis calcd (%) for
5.2 Hz, 1H), 7.35–7.40 (m, 2H), 7.55–7.58 (m, 1H), 7.61–7.71 C H N O: C, 78.86; H, 4.25; N, 13.14; O, 3.75 found: C, 78.88;
18 2
H N O
¼
2
5
18 2
(
m, 4H), 7.91 (t, J ¼ 5.6 Hz, 1H), 8.06–8.13 (m, 2H), 8.61 (s, H, 4.33; N, 13.13.
13 1
2
1
1
1
C
H); C{ H}-APT (100 MHz, DMSO-d6) d 44.5, 77.3, 88.9,
3-(Anthracen-9-yl)-N-(2-chlorobenzyl)-2-cyanoacrylamide (6b).
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1
15.5, 116.1, 124.8, 125.4, 125.5, 125.8, 126.6, 127.2, 127.4, Orange solid (1.037 g, 87%); mp 196–198 C; H-NMR (400 MHz,
28.5, 128.8, 129.3, 129.4, 129.9, 131.8, 132.1, 132.6, 133.0, DMSO-d6) d 4.63 (d, J ¼ 5.6 Hz, 2H), 7.35–7.45 (m, 2H), 7.52 (d, J ¼
56.9, 159.2, 160.4; MS (MMES + APCI) m/z: calcd for 7.6 Hz, 1H), 7.91–7.69 (m, 5H), 8.09 (d, J ¼ 8.4 Hz, 2H), 8.21 (d, J ¼
13
24
H
15ClN
4
O 410.09 found: 409.80; elemental analysis calcd 8.0 Hz, 2H), 8.80 (s, 1H), 9.14 (s, 1H), 9.47 (t, J ¼ 5.2 Hz, 1H);
C
1
(
%) for C24H15ClN O: C, 70.16; H, 3.68; Cl, 8.63; N, 13.64; O, { H}-APT (100 MHz, DMSO-d6) d 41.1, 115.0, 116.9, 125.0, 125.9,
4
3
.89 found: C, 69.99; H, 3.68; N, 13.71.
126.3, 127.2, 127.3, 128.2, 128.89, 128.94, 129.2, 129.4, 130.6, 132.1,
6
-Amino-1-(4-chlorobenzyl)-4-(naphthalen-1-yl)-2-oxo-1,2- 135.5, 150.3, 160.7; MS (MMES + APCI) m/z: calcd for C H ClN O
25
17
2
dihydropyridine-3,5-dicarbonitrile (5k). White solid (0.788 g, 396.10 found: 396.60; elemental analysis calcd (%) for
ꢀ
4%); mp 276–278 C; H-NMR (400 MHz, DMSO-d6) d 5.29 C H ClN O: C, 72.96; H, 3.72; Cl, 7.69; N, 12.16; O, 3.47 found: C,
25 17 2
1
6
(
8
d, J ¼ 16.8 Hz, 1H), 5.39 (d, J ¼ 16.4 Hz, 1H), 7.38 (d, J ¼ 73.02; H, 3.73; N, 12.18.
.0 Hz, 2H), 7.47 (d, J ¼ 8.4 Hz, 2H), 7.58–7.64 (m, 3H), 7.67 (t, 3-(Anthracen-9-yl)-N-(4-chlorobenzyl)-2-cyanoacrylamide (6c).
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1
J ¼ 8.0 Hz, 1H), 7.84 (d, J ¼ 7.2 Hz, 1H), 8.05–8.11 (m, 2H), Yellow solid (1.024 g, 86%); mp 224–226 C; H-NMR (400 MHz,
1
3
1
8
8
1
1
.50 (s, 2H); C{ H}-APT (100 MHz, DMSO-d6) d 44.4, 77.3, DMSO-d6) d 4.54 (d, J ¼ 6 Hz, 2H), 7.45–7.50 (m, 4H), 7.60–7.67 (m,
9.0, 115.4, 116.1, 124.7, 125.4, 125.8, 126.6, 127.2, 128.3, 4H), 8.06 (d, J ¼ 8.4 Hz, 2H), 8.20 (d, J ¼ 8.4 Hz, 2H), 8.80 (s, 1H),
13
1
28.4, 128.7, 129.2, 129.3, 129.9, 132.0, 132.5, 133.0, 133.6, 9.11 (s, 1H), 9.47 (t, J ¼ 5.6 Hz, 1H); C{ H}-APT (100 MHz, DMSO-
56.5, 159.4, 160.2; MS (MMES + APCI) m/z: calcd for d6) d 42.6, 115.0, 116.9, 124.9, 125.8, 126.3, 127.1, 128.2, 128.3,
C
24
H
15ClN
4
O 410.09 found: 409.70; elemental analysis calcd 128.9, 129.4, 129.5, 130.6, 131.6, 137.8, 150.3, 160.5; MS (MMES +
15ClN O: C, 70.16; H, 3.68; Cl, 8.63; N, 13.64; O, APCI) m/z: calcd for C H ClN O 396.10 found: 396.60; elemental
.89 found: C, 69.99; H, 3.68; N, 13.65.
-Amino-1-(2,4-dichlorobenzyl)-4-(naphthalen-1-yl)-2-oxo- 12.16; O, 3.47 found: C, 72.99; H, 3.72; N, 12.15.
,2-dihydropyridine-3,5-dicarbonitrile (5l). White solid
3-(Anthracen-9-yl)-2-cyano-N-(2,4-dichlorobenzyl)acrylamide
(
%) for C24
H
4
2
5
17
2
3
2
analysis calcd (%) for C25H17ClN O: C, 72.96; H, 3.72; Cl, 7.69; N,
6
1
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1
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1
(
0.822 g, 62%); mp 294–296 C; H-NMR (400 MHz, DMSO-d6) (6d). Yellow solid (1.126 g, 87%); mp 242–244 C; H-NMR (400
d 5.21 (d, J ¼ 18 Hz, 1H), 5.27 (d, J ¼ 17.6 Hz, 1H), 7.17 (d, J ¼ MHz, DMSO-d6) d 4.89 (d, J ¼ 5.6 Hz, 2H), 7.52 (dd, J ¼ 2 Hz, J ¼
8
3
5
2
1
.0 Hz, 1H), 7.44 (dd, J ¼ 2.0 Hz, J ¼ 8.4 Hz 1H), 7.59–7.66 (m, 8.4 Hz, 1H), 7.62–7.70 (m, 6H), 8.08 (d, J ¼ 8.4 Hz, 2H), 8.21 (d, J
H), 7.69 (t, J ¼ 8.0 Hz, 1H), 7.76 (d, J ¼ 2 Hz, 1H), 7.92 (t, J ¼ ¼ 8.0 Hz, 2H), 8.81 (s, 1H), 9.13 (s, 1H), 9.46 (t, J ¼ 5.6 Hz, 1H);
1
3
1
.2 Hz, 1H), 8.06–8.08 (m, 1H), 8.11 (d, J ¼ 8.4 Hz, 1H), 8.62 (s,
C{ H}-APT (100 MHz, DMSO-d6) d 40.7, 115.0, 116.8, 125.0,
1
3
1
H); C{ H}-APT (100 MHz, DMSO-d6) d 44.4, 77.4, 89.0, 125.9, 126.3, 127.2, 127.5, 128.2, 128.7, 129.0, 129.2, 130.6,
15.4, 116.0, 124.8, 125.4, 125.8, 126.6, 127.1, 127.2, 127.4, 130.7, 132.5, 134.8, 150.4, 160.7; MS (MMES + APCI) m/z: calcd
28892 | RSC Adv., 2019, 9, 28886–28893
This journal is © The Royal Society of Chemistry 2019