Hydrochloric Acid → 3-Acetyl-2-methoxyimino-5-methyl-hexanoic acid ethyl ester

HRID 2261728Notes

Reaction equation

HRID 2261728 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[C:5](=[N:10][O:11][CH3:12])[CH2:6][C:7](=[O:9])[CH3:8])[CH3:2].C(=O)([O-])[O-].[K+].[K+].I[CH2:21][CH:22]([CH3:24])[CH3:23].Cl>CN(C=O)C.CCOC(C)=O>[CH2:1]([O:3][C:4](=[O:13])[C:5](=[N:10][O:11][CH3:12])[CH:6]([C:7](=[O:9])[CH3:8])[CH2:21][CH:22]([CH3:24])[CH3:23])[CH3:2]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 10556Isobutyl iodide2×HCID 11430Potassium CarbonateHCID 589173Ethyl 2-(methoxyimino)-4-oxopentanoate

Product 1

HCID 765400763-Acetyl-2-methoxyimino-5-methyl-hexanoic acid ethyl esterYield 29.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 2-methoxyimino-4-oxo-pentanoic acid ethyl ester (2.62 g, 14 mmol) in DMF (30 mL) is added potassium carbonate (2.5 g, 18.2 mmol) followed by 1-iodo-2-methyl-propane (1.62 mL, 14 mmol) and the mixture is stirred at ambient temperature overnight. Additional 1-iodo-2-methyl-propane (0.8 mL, 7 mmol) is added and the mixture is stirred at 60° C. for 1 hour. The reaction mixture is diluted with EtOAc and is adjusted to pH 3 with 1N HCl. The organic layer is washed with brine, dried (MgSO4), filtered, and concentrated under reduced pressure. The residue is purified by column chromatography (0 to 20% EtOAc in hexanes) to give the title compound as a colorless oil (1 g, 29%). 1H NMR (400 MHz, CDCl3) δ 4.33 (q, 2H), 4.06 (s, 3H), 4.03 (dd, 1H), 2.07 (s, 3H), 1.88 (m, 1H), 1.58 (m, 1H), 1.43 (m, 1H), 1.37 (t, 3H), 0.89 (d, 6H).

Workup

  1. stirringthe mixture is stirred at 60° C. for 1 hour
  2. washThe organic layer is washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue is purified by column chromatography (0 to 20% EtOAc in hexanes)

Sources & evidence

ORD record
ord-83f7b6a6cfc84cdeb6d1a0b0560ad9f0
Source dataset
uspto-grants-2010_12
Patent number
US07846960B2

Reaction notes

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