HCID 11481114, compound → HCID 178468385, compound

HRID 397308Notes

Reaction equation

HRID 397308 reaction equation
[C:1]([O:7][CH2:8][CH2:9][Si:10]([CH3:13])([CH3:12])[CH3:11])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[N:14]([O-])=[O:15].[Na+]>C(O)(=O)C.O.C(OCC)(=O)C>[N:14](=[C:2]([C:3]([CH3:5])=[O:4])[C:1]([O:7][CH2:8][CH2:9][Si:10]([CH3:11])([CH3:13])[CH3:12])=[O:6])[OH:15]

Participants

6

Reactant 2

HCID 11481114HCID 11481114, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 178468385HCID 178468385, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 18.24 gm (90.3 mMol) 2-(trimethylsilyl)ethyl acetoacetate in 10 mL acetic acid at −4° C. was added a solution of 6.85 gm (99.3 mMol) sodium nitrite in 30 mL of water dropwise over 15 minutes. The reaction mixture was allowed to warm to room temperature while stirring. After 2 hours the reaction mixture was diluted with 100 mL ethyl acetate and washed twice with 50 mL portions of saturated aqueous sodium chloride. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The residual was dissolved in toluene and concentrated under reduced pressure twice to azeotropically remove any remaining acetic acid. The residual oil was finally subjected to flash silica gel chromatography, eluting with hexane containing 30% ethyl acetate. Fractions shown to contain product were combined and concentrated under reduced pressure to provide 12.04 gm (58%) of the desired compound as a colorless oil.

Workup

  1. washwashed twice with 50 mL portions of saturated aqueous sodium chloride
  2. dry with materialThe organic phase was dried over sodium sulfate
  3. concentrationconcentrated under reduced pressure
  4. dissolutionThe residual was dissolved in toluene
  5. concentrationconcentrated under reduced pressure twice
  6. customto azeotropically remove any remaining acetic acid
  7. washeluting with hexane containing 30% ethyl acetate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-5cb3f65ac2514e679b1c7d206c3efe77
Source dataset
uspto-grants-2003_08
Patent number
US06610680B1

Reaction notes

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