Highly Efficient Mechanochemical Reactions of 1,3-Dicarbonyl Compounds with Chalcones and Azachalcones Catalyzed by Potassium Carbonate

Ze Zhang; Ya-Wei Dong; Guan-Wu Wang; Koichi Komatsu

doi:10.1055/s-2003-43350

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Synlett 2004(1): 61-64
DOI: 10.1055/s-2003-43350

LETTER

Highly Efficient Mechanochemical Reactions of 1,3-Dicarbonyl Compounds with Chalcones and Azachalcones Catalyzed by Potassium Carbonate

Ze Zhang^a, Ya-Wei Dong^a, Guan-Wu Wang*^a, Koichi Komatsu^b
^a Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
Fax: +86(551)3607864; e-Mail: gwang@ustc.edu.cn;
^b Institute for Chemical Research, Kyoto University, Uji, Kyoto 611, Japan

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Publication History

Received 19 September 2003
Publication Date:
26 November 2003 (online)

Abstract
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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

References

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16

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.