RSC Advances
Paper
Ethyl
4-(4-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8- vacuum. The pure nal products were afforded by evapora-
hexahydroquinoline-3-carboxylate (4i). Melting point: 251– tion of the solvent followed by recrystallization from the
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7
2
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53 C; H NMR (300 MHz, CDCl
3
) d 7.35–7.28 (m, 2H), 7.24– ethanol-water mixture. All products were characterized by
.13 (m, 2H), 5.70 (s, 1H), 5.01 (s, 1H), 4.05 (q, J ¼ 7.1 Hz, 2H), spectral data and compared with their physical data given in
.46–2.08 (m, 7H), 1.19 (t, J ¼ 7.1 Hz, 3H), 1.08 (s, 3H), 0.93 (s, the literature.
H).
Ethyl
hexahydroquinoline-3-carboxylate (4j). Melting point: 232–
4-(3-bromophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
Selected data for typical compounds
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34 C; H NMR (500 MHz, CDCl
.1 Hz, 1H), 7.24 (d, J ¼ 8.0 Hz, 1H), 7.08 (t, J ¼ 7.8 Hz, 1H), 6.77 47 C; FT-IR (KBr, cm ): 3031, 2981, 2224, 1727, 1608, 1447,
3
) d 7.43 (s, 1H), 7.27 (d, J ¼
Ethyl (E)-2-cyano-3-phenylacrylate (5a). Melting point: 46–
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(
(
s, 1H), 5.03 (s, 1H), 4.09–4.05 (m, 2H), 2.35 (s, 3H), 2.30–2.15 1259, 1203, 1090, 768, 684; H NMR (400 MHz, CDCl
m, 4H), 1.23 (t, J ¼ 7.1 Hz, 3H), 1.08 (s, 3H), 0.96 (s, 3H).
3
) d 8.28 (s,
1H), 8.01 (dd, J ¼ 5.3, 3.5 Hz, 2H), 7.62–7.48 (m, 3H), 4.42 (q, J ¼
Ethyl
4-(2,4-dichlorophenyl)-2,7,7-trimethyl-5-oxo- 7.1 Hz, 2H), 1.43 (t, J ¼ 7.1 Hz, 3H).
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,4,5,6,7,8-hexahydroquinoline-3-carboxylate (4k). Melting
Ethyl (E)-2-cyano-3-(4-nitrophenyl)acrylate (5b). H NMR
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point: 240–242 C; H NMR (300 MHz, CDCl ) d 7.33 (d, J ¼ (300 MHz, CDCl
) d 8.32–8.26 (m, 2H), 8.24 (s, 1H), 8.10–8.04
3
3
8
1
¼
.4 Hz, 1H), 7.26 (s, 1H), 7.10 (dd, J ¼ 8.3, 2.2 Hz, 1H), 5.79 (s, (m, 2H), 4.36 (q, J ¼ 7.1 Hz, 2H), 1.36 (t, J ¼ 7.1 Hz, 3H).
H), 5.33 (s, 1H), 4.12–3.96 (m, 2H), 2.39–2.12 (m, 7H), 1.18 (t, J
7.1 Hz, 3H), 1.08 (s, 3H), 0.95 (s, 3H).
Ethyl
4-(3-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8- 1606, 1530, 1356, 1268, 1207, 1097, 812, 765, 671; H NMR (400
hexahydroquinoline-3-carboxylate (4l). Melting point: 203– MHz, CDCl
) d 8.72 (s, 1H), 8.43 (dd, J ¼ 9.8, 4.4 Hz, 2H), 8.33 (s,
) d 7.19 (t, J ¼ 1.8 Hz, 1H), 7.15 1H), 7.76 (t, J ¼ 8.1 Hz, 1H), 4.45 (q, J ¼ 7.1 Hz, 2H), 1.44 (t, J ¼
Ethyl (E)-2-cyano-3-(3-nitrophenyl)acrylate (5c). Melting
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point: 130–131 C; FT-IR (KBr, cm ): 3071, 2989, 2227, 1720,
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05 C; H NMR (500 MHz, CDCl
3
(
d, J ¼ 7.6 Hz, 1H), 7.06 (t, J ¼ 7.7 Hz, 1H), 7.03–6.99 (m, 1H), 7.1 Hz, 3H).
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.51–6.49 (m, 1H), 4.97 (s, 1H), 4.07–3.94 (m, 2H), 2.29 (s, 3H),
.25 (d, J ¼ 16.7 Hz, 1H), 2.16 (dd, J ¼ 16.6, 6.2 Hz, 2H), 2.09 (d, J (300 MHz, CDCl
16.3 Hz, 1H), 1.14 (t, J ¼ 7.1 Hz, 3H), 1.00 (s, 3H), 0.88 (s, 3H). (m, 2H), 4.32 (q, J ¼ 7.1 Hz, 2H), 1.33 (t, J ¼ 7.1 Hz, 3H).
Ethyl 4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-
Ethyl (E)-2-cyano-3-(4-uorophenyl)acrylate (5e). Melting
hexahydroquinoline-3-carboxylate (4m). Melting point: 243– point: 92–94 C; FT-IR (KBr, cm ): 3038, 2996, 2227, 1719,
Ethyl (E)-3-(4-chlorophenyl)-2-cyanoacrylate (5d). H NMR
2
¼
3
) d 8.13 (s, 1H), 7.92–7.82 (m, 2H), 7.49–7.35
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45 C; H NMR (300 MHz, CDCl
3
) d 7.26–7.20 (m, 2H), 7.20– 1595, 1510, 1203, 1088, 843; H NMR (400 MHz, CDCl ) d 8.23 (s,
3
.12 (m, 2H), 5.93 (s, 1H), 5.02 (s, 1H), 4.05 (q, J ¼ 7.1 Hz, 2H), 1H), 8.10–8.00 (m, 2H), 7.27–7.16 (m, 2H), 4.41 (q, J ¼ 7.1 Hz,
.42–2.09 (m, 7H), 1.19 (t, J ¼ 7.1 Hz, 3H), 1.08 (s, 3H), 0.93 (s, 2H), 1.42 (t, J ¼ 7.1 Hz, 3H).
1
H).
Ethyl
Ethyl (E)-3-(4-bromophenyl)-2-cyanoacrylate (5f). H NMR
2,7,7-trimethyl-5-oxo-4-(thiophen-2-yl)-1,4,5,6,7,8- (300 MHz, CDCl
3
) d 8.12 (s, 1H), 7.78 (t, J ¼ 5.4 Hz, 2H), 7.62–
hexahydroquinoline-3-carboxylate (4n). Melting point: 238– 7.54 (m, 2H), 4.32 (q, J ¼ 7.1 Hz, 2H), 1.33 (t, J ¼ 7.1 Hz, 3H).
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5
¼
40 C; H NMR (300 MHz, DMSO) d 9.24 (s, 1H), 7.17 (dd, J ¼
Ethyl (E)-2-cyano-3-(p-tolyl)acrylate (5g). Melting point: 89–
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.1, 1.2 Hz, 1H), 6.82 (dd, J ¼ 5.1, 3.5 Hz, 1H), 6.70–6.61 (m, 1H), 91 C; FT-IR (KBr, cm ): 3029, 2992, 2217, 1725, 1596, 1272,
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.16 (s, 1H), 4.06 (q, J ¼ 7.1 Hz, 2H), 2.46–2.00 (m, 7H), 1.19 (t, J 1191, 1094, 816; H NMR (400 MHz, CDCl
3
) d 8.24 (s, 1H), 7.92
7.1 Hz, 3H), 1.02 (s, 3H), 0.94 (s, 3H).
Ethyl
4-(furan-2-yl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8- 2H), 2.46 (s, 3H), 1.42 (t, J ¼ 7.1 Hz, 3H).
hexahydroquinoline-3-carboxylate (4o). Melting point: 246–
Ethyl (E)-2-cyano-3-(4-hydroxy-3-methoxyphenyl)acrylate
(d, J ¼ 8.2 Hz, 2H), 7.33 (d, J ¼ 8.1 Hz, 2H), 4.40 (q, J ¼ 7.1 Hz,
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47 C; H NMR (300 MHz, DMSO) d 9.16 (s, 1H), 7.36 (dd, J ¼ (5h). Melting point: 108–110 C; FT-IR (KBr, cm ): 3273,
1
.8, 0.9 Hz, 1H), 6.23 (dd, J ¼ 3.1, 1.8 Hz, 1H), 5.83 (d, J ¼ 3.1 Hz, 2982, 2942, 2229, 1721, 1577, 1510, 1276, 1217, 1096, 855; H
H), 5.02 (s, 1H), 4.14–3.96 (m, 2H), 2.45–1.97 (m, 7H), 1.18 (t, J NMR (400 MHz, CDCl
3
) d 8.16 (s, 1H), 7.87 (d, J ¼ 2.0 Hz, 1H),
¼
7.1 Hz, 3H), 1.02 (s, 3H), 0.93 (s, 3H).
Ethyl
2,7,7-trimethyl-5-oxo-4-propyl-1,4,5,6,7,8- 1H), 4.39 (q, J ¼ 7.1 Hz, 2H), 4.00 (s, 3H), 1.41 (t, J ¼ 7.1 Hz, 3H).
hexahydroquinoline-3-carboxylate (4p). Melting point: 178–
Ethyl (E)-2-cyano-3-(furan-2-yl)acrylate (5i). Melting point:
7.41 (dd, J ¼ 8.3, 2.0 Hz, 1H), 7.02 (d, J ¼ 8.3 Hz, 1H), 6.30 (s,
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80 C; H NMR (300 MHz, CDCl ) d 5.64 (s, 1H), 4.24–4.09 (m, 86–88 C; FT-IR (KBr, cm ): 3040, 2926, 2224, 1716, 1621, 1262,
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1
H), 4.02 (t, J ¼ 5.3 Hz, 1H), 2.41–2.05 (m, 7H), 1.39–1.18 (m, 1212, 1025, 761; H NMR (400 MHz, CDCl
) d 8.04 (s, 1H), 7.77
3
H), 1.09 (s, 6H), 0.83 (t, J ¼ 7.1 Hz, 3H).
(d, J ¼ 1.4 Hz, 1H), 7.42 (d, J ¼ 3.6 Hz, 1H), 6.68 (dd, J ¼ 3.6,
1
.6 Hz, 1H), 4.38 (q, J ¼ 7.1 Hz, 2H), 1.40 (t, J ¼ 7.1 Hz, 3H).
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-Benzylidenemalononitrile (5j). Melting point: 79–80 C;
General procedure for Knoevenagel condensation
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FT-IR (KBr, cm ): 3033, 2985, 2223, 1591, 1568, 1450, 1218,
3
A mixture of aromatic aldehyde (1 mmol), activated methy- 1157, 958, 755; H NMR (300 MHz, CDCl ) d 7.90–7.81 (m, 2H),
lene compounds (1.1 mmol), and BIL@MNP (70 mg) was 7.72 (s, 1H), 7.61–7.54 (m, 1H), 7.48 (t, J ¼ 7.5 Hz, 2H).
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stirred at 70 C in an oil bath for a certain time, as indicated
2-(3-Nitrobenzylidene)malononitrile (5k). Melting point:
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by TLC for a complete reaction. Ethyl acetate was added and 101–102 C; H NMR (300 MHz, CDCl ) d 8.59 (t, J ¼ 1.9 Hz, 1H),
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the catalyst was separated magnetically from the product 8.41 (ddd, J ¼ 8.3, 2.1, 0.9 Hz, 1H), 8.27 (d, J ¼ 7.9 Hz, 1H), 7.83
solution, washed with ethyl acetate, and dried under (s, 1H), 7.73 (t, J ¼ 8.1 Hz, 1H).
53868 | RSC Adv., 2017, 7, 53861–53870
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