Methyl acetoacetate → HCID 2727782, compound

HRID 734660Notes

Reaction equation

HRID 734660 reaction equation
[F: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].[OH-].[Na+]>C(O)(=O)C.CCOC(C)=O.O>[F: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 7757Methyl acetoacetateHCID 14798Sodium HydroxideHCID 162492,2-Dimethyl-1,3-dioxane-4,6-dioneHCID 680234-FluorobenzaldehydeHCID 517165Ammonium Acetate

Product 1

HCID 2727782HCID 2727782, compoundYield 20%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

4-Fluorobenzaldehyde (0.997 mL, 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 3.5 hours. The reaction mixture was diluted with EtOAc and water, and neutralized with 2N NaOH. The phases were separated, and the organic phase was washed with satd. NaHCO3, then NaCl. The organic phase was dried over Na2SO4, filtered and concentrated to a yellow residue. Recrystallization (CH2Cl2/hexanes) provided 480 mg (20%) of the product as a pale yellow solid. MS (ES+) m/e 264 [M+H]+.

Workup

  1. temperatureheated
  2. temperatureto reflux for 3.5 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 to a yellow residue
  8. customRecrystallization (CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-8acc7bdce7e04c37acc80633012a556a
Source dataset
uspto-grants-2009_09
Patent number
US07592357B2

Reaction notes

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