tert-Butyl methyl ether → (4R,5R)-3-Methoxyimino-4,5-dimethyl-heptanoic Acid Ethyl Ester

HRID 349835Notes

Reaction equation

HRID 349835 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[CH2:5][C:6](=O)[C@H:7]([CH3:12])[C@H:8]([CH3:11])[CH2:9][CH3:10])[CH3:2].Cl.[O:16]([NH2:18])[CH3:17].C([O-])(=O)C.[Na+].CC(OC)(C)C>CCO.O>[CH2:1]([O:3][C:4](=[O:14])[CH2:5][C:6](=[N:18][O:16][CH3:17])[C@H:7]([CH3:12])[C@H:8]([CH3:11])[CH2:9][CH3:10])[CH3:2]

Participants

7

Reactant 4

HCID 15413tert-Butyl methyl etherHCID 517045Sodium AcetateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 86597962(4R,5R)-4,5-Dimethyl-3-oxo-heptanoic Acid Ethyl Ester

Product 1

HCID 86597963(4R,5R)-3-Methoxyimino-4,5-dimethyl-heptanoic Acid Ethyl EsterYield 87.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

(4R,5R)-4,5-Dimethyl-3-oxo-heptanoic acid ethyl ester (21.23 g, 106 mmol) was dissolved in 200 mL of EtOH and added to 10.6 g (127 mmol) of methoxylamine-HCl and 10.6 g (127 mmol) of sodium acetate solids. The slurry was stirred at room temperature for 48 hours. MTBE (200 mL) and 100 mL of water were added, and the resulting phases were separated. The organic phase was washed with 100 mL of water and was evaporated to yield a two-phase mixture. Hexanes (100 mL) were added and the phases were separated. The aqueous phase was extracted with 50 mL of hexanes and the combined organic phases were washed with 50 mL of water, dried over magnesium sulfate, and evaporated to give 21.24 g (87.4% yield) of the titled compound as a clear yellow oil: 1H NMR (CDCl3, 399.77 MHz) δ 0.84–0.88 (m, 6H), 1.07 (d, J=7.1 Hz, 3H), 1.24 (t, J=7.1 Hz, 3H), 1.4–1.6 (m, 2H), 2.24 (m, 1H), 3.08 (d, J=15.8 Hz, 1H), 3.19 (d, J=15.8 Hz, 1H), 3.80 (s, 3H), 4.10–4.2 (m, 3H). Low resolution mass spec: nominal m/e calc'd for C12H23NO3 (M+H)+: 230. Found: m/e 230.

Workup

  1. customthe resulting phases were separated
  2. washThe organic phase was washed with 100 mL of water
  3. customwas evaporated
  4. customto yield a two-phase mixture
  5. customthe phases were separated
  6. extractionThe aqueous phase was extracted with 50 mL of hexanes
  7. washthe combined organic phases were washed with 50 mL of water
  8. dry with materialdried over magnesium sulfate
  9. customevaporated

Sources & evidence

ORD record
ord-3361310ed0c04231ac827d98fef3ac39
Source dataset
uspto-grants-2007_02
Patent number
US07179934B2

Reaction notes

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