Convenient synthesis of 3,4-dihydro-2(1h)-quinolinones from malonate derivatives

Heterocyclic Communications

Volumn 15, Issue 1, 2009, Pages 79-83

  Tsubusaki, Takuma ^a   Nishino, Hiroshi ^a  

^a KUMAMOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 70350145048     PISSN: 07930283     EISSN: None     Source Type: Journal    
DOI: 10.1515/HC.2009.15.1.79     Document Type: Article

References (34)

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30. Diethyl 2-[2-(N-methyl-N-phenylamino)-2-oxoethyl]malonate (1): Rf = 0.45 (diethyl ether-hexane, 8:2 v/v); colorless oil; IR (CHC13) □ 1744, 1724, 1651 (C=0); 1H NMR (300 MHz, CDC13) □ 7.48-7.22 (5H, m, arom. H), 4.26-4.08 (4H, m, O-CH2CH3), 3.96 (1H, t, J = 7.3 Hz, H-2), 3.26 (3H, s, N-CH3), 2.66 (2H, d,J=7.3 Hz, CH2), 1.24 (6H, t, J=7.3 Hz, O-CH2CH3J; 13C NMR (75 MHz, CDCI3) □ 169.6 (C=0), 169.0 (2C, C=0), 143.2 (arom. C), 129.8, 127.9, 127.2 (5C, arom. CH), 61.4 (2C, 0-CH2CH3), 48.1 (N-CH3), 37.3 (C-2), 33.3 (CH2), 13.8 (2C, O-CH2CH3). FAB HRMS (acetone-NBA) calcd for C16H22N05 308.1498 (M+l). Found 308.1499.
31. 4,4-Bis(ethoxycarbonyl)-3,4-dihydro-2(lH)-quinolinone (2): Rf=0.47 (diethyl ether-hexane, 8:2 v/v); colorless prisms (from chlorofrom-hexane); mp 86-87 °C; IR (KBr) □ 1757, 1734, 1688 (C=0); 1H NMR (300 MHz, CDCI3) □ 7.40-7.29 (2H, m, arom. H), 7.13-7.02 (2H, m, arom. H), 4.35-4.19 (4H, m, O-CH2CH3), 3.33 (3H, s, N-CH3), 3.23 (2H, s, CH2), 1.27 (6H, t, J=7.3 Hz, O-CH2CH3); 13C NMR (75 MHz, CDC13) □ 168.8 (2C, C=O), 166.5 (C=O), 139.6 (arom. C), 129.2, 127.6, 122.9 (arom. CH), 122.4 (arom. C), 115.1 (arom. CH), 62.2 (2C, O-CH2CH3), 56.7 (C-4), 37.8 (CH2), 29.4 (N-CH3), 13.7 (2C, O-CH2CH3). Anal, calcd for C16H19N05: C, 62.94; H, 6.27; N, 4.59. Found: C, 62.90; H, 6.35; N, 4.62.
32. The typical oxidation was as follows. To a mixture of malonate 1 (0.5 mmol) and glacial acetic acid (30 mL) was added manganese(III) acetate dihydrate (1.5 rnmol). The mixture was heated under reflux for 30 min in air. The solvent was removed in vacuo, and the residue was triturated with water followed by extraction with dichloromethane (10 mL x 3). The combined extract was dried over anhydrous magnesium sulfate, and then concentrated to dryness. The obtained product 2 was purified by silicagel TLC while eluting with diethyl ether-hexane (80:20 v/v).
33. Diethyl 2-[2-{N-(2,4-dimethoxyphenyl)-N-methylamino}-2-oxoethyl]malonate: Rf=0.41 (ethyl acetate-hexane, 5:5 v/v); yellow oil; IR (CHCI3) □ 1744, 1728,1651 (C=0); 1H NMR (300 MHz, CDCI3) □ 7.17-7.08 (1H, m, arom. H), 6.58-6.46 (2H, m, arom. H), 4.28-4.06 (4H, m, O-CH2CH3), 3.92 (1H, t, J = 7.3 Hz, H-2), 3.83 (6H, s, O-CH3), 3.13 (3H, s, N-CH3), 2.75 (1H, dd, J=17.2, 8.4 Hz, CH2), 2.48 (1H, dd, J=17.2, 6.2 Hz, CH2), 1.32-1.19 (6H, m, O-CH2CH3); 13C NMR (75 MHz, CDCI3) □ 170.6 (C=O), 169.1 (2C, C=O), 160.4, 155.7 (arom. C), 129.3 (arom. CH), 124.6 (arom. C), 104.5, 99.4 (arom. CH), 61.2 (2C, O-CH2CH3), 55.3 (2C, O-CH3), 48.0 (N-CH3), 36.1 (C-2), 32.6 (CH2), 13.8 (2C, O-CH2CH3). FAB HRMS (acetone-NBA) calcd for C18 H26NO7 368.1709 (M+l). Found 368.1707.
34. 4,4-Bis(ethoxycarbonyl)-6-methoxy-l-methyl-l-azaspiro[4,5]deca-6, 9-diene-2,8-dione: Rf = 0.18 (diethyl ether); colorless prisms (from chloroform-hexane); mp 119 °C; IR (KBr) □ 1740, 1719, 1670, 1603 (CO); 1H NMR (300 MHz, CDCI3) □ 6.66 (1H, d, J=10.3 Hz, H-10), 6.43 (1H, dd, J=10.3,1.5 Hz, H-9), 5.71 (1H, d, J=1.5 Hz, H-7), 4.36-4.05 (4H, m, 0-CH2CH3), 3.70 (3H, s, O-CH3), 3.31 (1H, d, J=17.2 Hz, CH2), 2.84 (1H, d, J=17.2 Hz, CH2), 2.62 (3H, s, N-CH3), 1.29 (3H, t, J=7.3 Hz, O-C2CH3, 1.20 (3H, t, J=7.3 Hz, 0-CH2CH3); 13C NMR (75 MHz, CDCI3) □ 185.6 (C=O), 173.0, 170.9, 168.5, 166.8 (C=O, C-6), 140.3, 132.8, 104.8 (C-7, C-9, C-10), 66.4 (C-5), 62.9, 62.3 (0-CH2CH3), 61.3 (C-4), 56.3 (O-CH3), 38.5 (CH2), 26.2 (N-CH3), 13.9, 13.7 (0-CH2CH3). Anal, calcd for C17H21NO7: C, 58.11; H, 6.02; N, 3.99. Found: C, 58.12; H, 5.94; N, 4.09.