4-Chlorobenzaldehyde → Methyl 4-(4-chlorophenyl)-2-methyl-6-oxo-1,4,5,6-tetrahydropyridine-3-carboxylate

HRID 734666Notes

Reaction equation

HRID 734666 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[CH3:10][C:11]1(C)[O:16]C(=O)CC(=O)O1.[C:20]([O:26][CH3:27])(=[O:25])[CH2:21][C:22]([CH3:24])=O.C([O-])(=O)C.[NH4+:32].C([O-])([O-])=O.[K+].[K+]>C(O)(=O)C.CCOC(C)=O.O>[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]2[CH2:10][C:11](=[O:16])[NH:32][C:22]([CH3:24])=[C:21]2[C:20]([O:26][CH3:27])=[O:25])=[CH:4][CH:3]=1

Participants

9

Reactant 5

HCID 77264-ChlorobenzaldehydeHCID 7757Methyl acetoacetateHCID 11430Potassium CarbonateHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 517165Ammonium Acetate

Product 1

HCID 2849828Methyl 4-(4-chlorophenyl)-2-methyl-6-oxo-1,4,5,6-tetrahydropyridine-3-carboxylateYield 28.3%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

4-Chlorobenzaldehyde (1.30 g, 9.30 mmol, 1.00 equiv), 2,2-dimethyl-1,3-dioxane-4,6-dione (1.34 g, 9.30 mmol, 1.00 equiv), methyl acetoacetate (1.00 mL, 9.30 mmol, 1.00 equiv), and ammonium acetate (0.752 g, 9.77 mmol, 1.05 equiv) were dissolved in acetic acid (10 mL) and heated to reflux for 2 hours. The reaction mixture was cooled to room temperature, neutralized with solid K2CO3, and diluted with EtOAc and water. The phases were separated, and the organic phase was washed with satd. NaCl. The organic phase was dried over Na2SO4, filtered and concentrated en vacuo to a yellow residue. Recrystallization (CH2Cl2/hexanes) provided 735 mg (28%) of the product as a pale yellow solid. MS (ES+) m/e 280 [M+H]+.

Workup

  1. temperatureheated
  2. temperatureto reflux for 2 hours
  3. customThe phases were separated
  4. washthe organic phase was washed with satd
  5. dry with materialThe organic phase was dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated en vacuo to a yellow residue
  8. customRecrystallization (CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-aadf442793f448b2b104c75b573591ad
Source dataset
uspto-grants-2009_09
Patent number
US07592357B2

Reaction notes

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