Ethyl Acetoacetate → Ethyl 2-chloro-6-methoxy-2'-methyl-5'-oxo-1',4',5',6',7',8'-hexahydro-3,4'-biquinoline-3'-carboxylate

HRID 1020283Notes

Reaction equation

HRID 1020283 reaction equation
[C:1]1(=[O:8])[CH2:6][CH2:5][CH2:4][C:3](=O)[CH2:2]1.[Cl:9][C:10]1[C:19]([CH:20]=O)=[CH:18][C:17]2[C:12](=[CH:13][CH:14]=[C:15]([O:22][CH3:23])[CH:16]=2)[N:11]=1.[C:24]([O:30][CH2:31][CH3:32])(=[O:29])[CH2:25][C:26]([CH3:28])=O.C([O-])(=O)C.[NH4+:37]>C(O)C>[Cl:9][C:10]1[C:19]([CH:20]2[C:2]3[C:1](=[O:8])[CH2:6][CH2:5][CH2:4][C:3]=3[NH:37][C:26]([CH3:28])=[C:25]2[C:24]([O:30][CH2:31][CH3:32])=[O:29])=[CH:18][C:17]2[C:12](=[CH:13][CH:14]=[C:15]([O:22][CH3:23])[CH:16]=2)[N:11]=1

Participants

6

Reactant 4

HCID 8868Ethyl AcetoacetateHCID 104341,3-CyclohexanedioneHCID 517165Ammonium AcetateHCID 6890792-Chloro-6-methoxyquinoline-3-carbaldehyde

Product 1

HCID 57542096Ethyl 2-chloro-6-methoxy-2'-methyl-5'-oxo-1',4',5',6',7',8'-hexahydro-3,4'-biquinoline-3'-carboxylateYield 64%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 1,3-cyclohexanedione (0.56 g, 5.0 mmole) in hot ethanol (10 ml) was added 2-chloro-6-methoxy-3-quinolinecarboxaldehyde (1.1 g, 5.0 mmole) followed by ethyl acetoacetate (0.64 ml, 5.0 mmole) and finally ammonium acetate (0.77 g, 10.0 mmole). The mixture was refluxed for 12 h at which time a precipitate was observed. The reaction was cooled to room temperature, filtered and washed with ethanol then ethyl ether to provide the desired product (1.36 g, 64%) as a golden powder. 1H NMR (400 MHz; CDCl3) d 8.14 (s, 1H); 7.81 (d, 1H, J=8.9 Hz); 7.28 (dd, 1H, J=8.9, 2.7 Hz); 7.06 (d, 1H, J=2.7 Hz); 6.58 (bs, 1H); 5.48 (s, 1H); 4.10-3.95 (m, 2H); 3.89 (s, 3H); 2.42 (at, 2H, J=6.5 Hz); 2.35 (s, 3H); 2.28 (at, 2H, J=6.5 Hz); 2.0-1.80 (m, 2H); 1.13 (t, 3H, J=7.0 Hz). LC MS shows MH+ at 427 and 2M+Na at 875.

Workup

  1. temperatureThe mixture was refluxed for 12 h at which time a precipitate
  2. filtrationfiltered
  3. washwashed with ethanol

Sources & evidence

ORD record
ord-1f92602d4e0e41469ce18e63c86a00bb
Source dataset
uspto-grants-2014_05
Patent number
US08716319B2

Reaction notes

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