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DOI: 10.1055/s-2003-43350
Highly Efficient Mechanochemical Reactions of 1,3-Dicarbonyl Compounds with Chalcones and Azachalcones Catalyzed by Potassium Carbonate
Publikationsverlauf
Publikationsdatum:
26. November 2003 (online)
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Abstract
Under the high-speed vibration milling conditions, K2CO3 was found to be a very efficient catalyst for the solvent-free Michael reactions of 1,3-dicarbonyl compounds with chalcones and azachalcones. In most cases, conventional side reactions were avoided and thus excellent yields were achieved. The influences of other catalysts and the vibration frequency on the Michael reaction were investigated.
Key words
Michael addition - chalcone - azachalcone - potassium carbonate - mechanochemical reaction
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References
General Procedure for the Synthesis of Compounds 3:
A mixture of compound 1 (0.1 mmol), diethyl malonate 2 (15.2 µL, 0.1 mmol) and K2CO3 (1.4 mg, 0.01 mmol) was vigorously shaken by HSVM for a designated time. The reaction mixture was collected and washed with water to remove the small amount of K2CO3, and then dried to give the crude product 3. The obtained product is essentially pure and can be further purified by crystallization from petroleum ether-EtOAc (10:1) at -20 ºC. Products 3c, 3i and 3m were purified by column chromatography on silica gel with petroleum ether-EtOAc (5:1) as an eluent.
Selected analytical data:3f: Mp 93-94 ºC. IR (KBr): 2224, 1752, 1731, 1686 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.87 (d, J = 7.6 Hz, 2 H), 7.54 (d, J = 8.0 Hz, 2 H), 7.53 (m, 1 H), 7.43 (d, J = 7.6 Hz, 2 H), 7.41 (d, J = 8.0 Hz, 2 H), 4.26-4.14 (m, 3 H), 3.98 (q, J = 7.1 Hz, 2 H), 3.81 (d, J = 9.5 Hz, 1 H), 3.57 (dd, J = 17.3, 4.6 Hz, 1 H), 3.48 (dd, J = 17.3, 9.2 Hz, 1 H), 1.23 (t, J = 7.1 Hz, 3 H), 1.04 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3) δ = 196.90, 167.92, 167.42, 146.41, 136.51, 133.50, 132.26 (2 × C), 129.39 (2 × C), 128.78 (2 × C), 128.10 (2 × C), 118.74, 111.15, 62.02, 61.74, 56.91, 42.08, 40.68, 14.10, 13.90. HRMS (EI-TOF): m/z [M+] calcd for C23H23NO5: 393.1576; found: 393.1577.
3h: Mp 114-115 ºC. IR (KBr): 1743, 1721, 1684 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.90 (dd, J = 7.8, 1.3 Hz, 2 H), 7.56 (t, J = 7.3 Hz, 1 H), 7.44 (t, J = 7.5 Hz, 2 H), 7.38 (d,
J = 2.0 Hz, 1 H), 7.32 (d, J = 8.3 Hz, 1 H), 7.16 (dd, J = 8.3, 2.0 Hz, 1 H), 4.26-4.11 (m, 3 H), 4.02 (q, J = 7.1 Hz, 2 H), 3.77 (d, J = 9.3 Hz, 1 H), 3.55 (dd, J = 17.2, 4.6 Hz, 1 H), 3.44 (dd, J = 17.2, 9.2 Hz, 1 H),1.25 (t, J = 7.1 Hz, 3 H), 1.09 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 197.04, 168.07, 167.55, 141.13, 136.62, 133.48, 132.47, 131.30, 130.45 (2 × C), 128.81 (2 C), 128.18 (2 × C), 128.06, 62.01, 61.79, 57.15, 42.18, 39.87, 14.15, 13.97. HRMS (EI-TOF): m/z [M+] calcd for C22H22O5
35Cl2: 436.0844; found: 436.0847.
3i: Mp 58-60 ºC. IR (KBr): 1748, 1728, 1682 cm-1. 1H NMR (300 MHz, CDCl3) δ = 7.90 (dd, J = 7.4, 1.2 Hz, 2 H), 7.54 (t, J = 7.3 Hz, 1 H), 7.43 (t, J = 7.6 Hz, 2 H), 6.76 (d, J = 1.1 Hz, 1 H), 6.71 (dd, J = 8.0, 1.1 Hz, 2 H), 6.66 (d, J = 8.0 Hz, 1 H), 5.88 (s, 2 H), 4.20 (qd, J = 7.1, 2.6 Hz, 2 H), 4.10 (td, J = 9.4, 4.7 Hz, 1 H), 4.01 (q, J = 7.1 Hz, 2 H), 3.75 (d, J = 9.8 Hz, 1 H), 3.50 (dd, J = 16.5, 4.6 Hz, 1 H), 3.39 (dd, J = 16.5, 9.3 Hz, 1 H), 1.25 (t, J = 7.1 Hz, 3 H), 1.08 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 197.70, 168.45, 167.83, 147.67, 146.65, 136.95, 134.32, 133.20, 128.71 (2 × C), 128.26 (2 × C), 121.65, 108.78, 108.27, 101.06, 61.81, 61.53, 57.90, 42.88, 40.75, 14.18, 14.01. HRMS (EI-TOF): m/z [M+] calcd for C23H24O7: 412.1522; found: 412.1527.
3j: Mp 66-67 ºC. IR (KBr): 1749, 1730, 1699, 1521, 1348 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.64 (d, J = 4.2 Hz, 1 H), 8.11 (d, J = 8.6 Hz, 2 H), 7.90 (d, J = 7.8 Hz, 1 H), 7.78 (td, J = 7.6, 1.6 Hz, 1 H), 7.53 (d, J = 8.6 Hz, 2 H), 7.45 (dd, J = 7.0, 4.6 Hz, 1 H), 4.32 (td, J = 10.0, 4.0Hz, 1 H), 4.21 (qd, J = 7.1, 2.5 Hz, 2 H), 3.97 (q, J = 7.1 Hz, 2 H), 3.97 (dd, J = 18.2, 9.9 Hz, 1 H), 3.85 (d, J = 10.2 Hz, 1 H), 3.64 (dd, J = 18.2, 4.1 Hz, 1 H), 1.26 (t, J = 7.1 Hz, 3 H), 1.04 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.52, 167.80, 167.45, 152.88, 149.08, 148.93, 147.05, 137.13, 129.69 (2 × C), 127.62, 123.64 (2 × C), 121.96, 62.09, 61.76, 57.22, 41.67, 40.24, 14.17, 13.98. HRMS (EI-TOF): m/z [M+] calcd for C21H22N2O7: 414.1427; found: 414.1424.
3k: Mp 72-74 ºC. IR (KBr): 1748, 1729, 1691, 1531, 1352 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.65 (d, J = 4.3 Hz, 1 H), 8.22 (s, 1 H), 8.03 (dd, J = 7.7, 1.7 Hz, 1 H), 7.90 (d,
J = 7.9 Hz, 1 H), 7.79 (dd, J = 7.4, 1.2 Hz, 1 H), 7.73 (d, J = 8.7 Hz, 1 H), 7.46 (d, J = 5.0 Hz, 1 H), 7.41 (d, J = 8.1 Hz, 1 H), 4.3 2 (td, J = 9.8, 4.1 Hz, 1 H), 4.21 (q, J = 7.1 Hz, 2 H), 3.97 (dd, J = 18.2, 9.9 Hz, 1 H), 3.97 (q, J = 7.1 Hz, 2 H), 3.85 (d, J = 10.1 Hz, 1 H), 3.66 (dd, J = 18.2, 4.0 Hz, 1 H), 1.25 (t, J = 7.1 Hz, 3 H), 1.03 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.61, 167.84, 167.49, 152.92, 149.10, 148.28, 143.36, 137.07, 135.44, 129.29, 127.56, 123.43, 122.29, 121.91, 62.04, 61.71, 57.34, 41.61, 40.11, 14.15, 13.94. HRMS (EI-TOF): m/z [M+] calcd for C21H22N2O7: 414.1427; found: 414.1428.
3l: Mp 42-44 ºC. IR (KBr): 2228, 1750, 1732, 1700 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.64 (d, J = 4.6 Hz, 1 H), 7.91 (d, J = 7.8 Hz, 1 H), 7.78 (td, J = 7.6, 1.6 Hz, 1 H), 7.55 (d, J = 8.3 Hz, 2 H), 7.47 (d, J = 8.3 Hz, 2 H), 7.46 (m, 1 H), 4.29-4.16 (m, 3 H), 3.96 (q, J = 7.1 Hz, 2 H), 3.96 (dd, J = 18.2, 9.9 Hz, 1 H), 3.82 (d, J = 10.3 Hz, 1 H), 3.62 (dd, J = 18.2, 4.0 Hz, 1 H), 1.25 (t, J = 7.1 Hz, 3 H), 1.03 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.57, 167.82, 167.47, 153.00, 149.04, 146.84, 137.06, 132.18 (2 × C), 129.59 (2 × C), 127.50, 121.91, 118.81, 111.07, 61.98, 61.64, 57.24, 41.56, 40.53, 14.13, 13.92. HRMS (EI-TOF): m/z [M+] calcd for C22H22N2O5: 394.1529; found: 394.1528.
3m: Mp 50-52 ºC. IR (KBr): 1750, 1730, 1697 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.64 (d, J = 4.4 Hz, 1 H), 7.91 (d, J = 7.7 Hz, 1 H), 7.77 (t, J = 7.6 Hz, 1 H), 7.44 (dd, J = 7.0, 5.2 Hz, 1 H), 7.27 (d, J = 8.3 Hz, 2 H), 7.20 (d, J = 8.3 Hz, 2 H), 4.23-4.15 (m, 3 H), 3.95 (q, J = 7.1 Hz, 2 H), 3.90 (dd, J = 17.9, 9.8 Hz, 1 H), 3.78 (d, J = 10.3 Hz, 1 H), 3.57 (dd, J = 17.9, 4.0 Hz, 1 H), 1.25 (t, J = 7.1 Hz, 3 H), 1.03 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.84, 168.14, 167.73, 153.16, 148.99, 139.59, 137.01, 132.84, 130.02 (2 × C), 128.55 (2 × C), 127.37, 121.93, 61.84, 61.52, 57.73, 41.87, 39.92, 14.16, 13.93. HRMS (EI-TOF): m/z [M+] calcd for C21H22NO5
35Cl: 403.1187; found: 403.1184. HRMS (EI-TOF): m/z [M+] calcd for C21H22NO5
37Cl: 405.1157; found: 405.1147.
3n: Mp 72-73 ºC. IR (KBr): 1755, 1731, 1695 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.65 (d, J = 4.4 Hz, 1 H), 7.93 (d, J = 7.4 Hz, 1 H), 7.79 (td, J = 7.6, 1.6 Hz, 1 H), 7.45 (m, 1 H), 7.43 (d, J = 2.0 Hz, 1 H), 7.30 (t, J = 8.3 Hz, 1 H), 7.20 (dd, J = 8.3, 2.0 Hz, 1 H), 4.25-4.13 (m, 3 H), 4.00 (q, J = 7.1 Hz, 1 H), 3.90 (dd, J = 18.2, 9.7 Hz, 1 H), 3.77 (d, J = 10.2 Hz, 1 H), 3.58 (dd, J = 18.2, 4.1 Hz, 1 H), 1.25 (t, J = 7.1 Hz, 3 H), 1.06 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 198.61, 167.92, 167.54, 152.98, 149.02, 141.43, 137.06, 132.31, 131.09, 130.66, 130.31, 128.19, 127.49, 121.94, 61.94, 61.66, 57.42, 41.62, 39.63, 14.14, 13.94. HRMS (EI-TOF): m/z [M+] calcd for C21H21NO5
35Cl2: 437.0797; found: 437.0791. HRMS (EI-TOF): m/z [M+] calcd C21H21NO5
35Cl37Cl: 439.0767; found: 439.0744.
3o: Mp 104-105 ºC. IR (KBr): 1743, 1726, 1697 cm-1. 1H NMR (300 MHz, CDCl3): δ = 8.65 (d, J = 4.3 Hz, 1 H), 7.92 (d, J = 7.8 Hz, 1 H), 7.77 (td, J = 7.6, 1.4 Hz, 1 H), 7.42 (m, 1 H), 6.81 (d, J = 1.3 Hz, 1 H), 6.77 (dd, J = 7.9, 1.6 Hz, 1 H), 6.66 (d, J = 7.9 Hz, 1 H), 5.87 (s, 2 H), 4.23-4.10 (m, 3 H), 3.98 (q, J = 7.2 Hz, 2 H), 3.87 (dd, J = 17.7, 9.7 Hz, 1 H), 3.74 (d, J = 10.4 Hz, 1 H), 3.53 (dd, J = 17.7, 4.2 Hz, 1 H), 1.24 (t, J = 7.2 Hz, 1 H), 1.06 (t, J = 7.2 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 199.02, 168.31, 167.87, 153.27, 148.97, 147.53, 146.48, 136.96, 134.75, 127.27, 121.94, 121.82, 108.96, 108.17, 100.98, 61.74, 61.42, 58.16, 42.09, 40.25, 14.17, 14.00. HRMS (EI-TOF): m/z [M+] calcd for C22H23NO7: 413.1475; found: 413.1477.