Acetic Acid → HCID 178471403, compound

HRID 1464353Notes

Reaction equation

HRID 1464353 reaction equation
[C:1]([NH:4][CH:5]([PH:17]([OH:19])=[O:18])[CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:3])[CH3:2].[H-].[Na+].[CH2:22](I)[CH:23]([CH3:25])[CH3:24].C(O)(=O)C>CS(C)=O>[C:1]([NH:4][CH:5]([PH:17]([OH:19])=[O:18])[C:6]([CH2:22][CH:23]([CH3:25])[CH3:24])([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 10556Isobutyl iodideHCID 24758Sodium hydrideHCID 178472265HCID 178472265, compound

Product 1

HCID 178471403HCID 178471403, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
10 °C

Procedure

12.0 g of diethyl 2-[(acetamido)(hydroxyphosphinyl)methyl]malonate were dissolved in 100 ml of dry dimethyl sulphoxide and the solution was cooled to 10° C. while stirring under a nitrogen atmosphere. 3.2 g of 60% sodium hydride in mineral oil were added, the mixture was stirred at room temperature for 2 hours and then 8 g of isobutyl iodide were added. The mixture was stirred at room temperature in the dark for 20 hours and 20 ml of glacial acetic acid were added. The volatiles were removed by evaporation in a high vacuum and the resulting semi-solid residue was dissolved in 100 ml of water containing 15 ml of 50% hypophosphorous acid. The solution was extracted eight times with ethyl acetate and the combined extracts were dried over sodium sulfate and evaporated. The residue was dissolved in dichloromethane and the solution was washed in sequence with water and saturated sodium chloride solution. The dichloromethane solution was dried over sodium sulfate and evaporated, and the residue was crystallized from diethyl ether/n-hexane to give 6.28 g of diethyl 2-[(acetamido)-(hydroxyphosphinyl)methyl]-2-isobutylmalonate in the form of a white solid; MS: 352 (M+H)+.

Workup

  1. stirringthe mixture was stirred at room temperature for 2 hours
  2. stirringThe mixture was stirred at room temperature in the dark for 20 hours
  3. customThe volatiles were removed by evaporation in a high vacuum
  4. dissolutionthe resulting semi-solid residue was dissolved in 100 ml of water containing 15 ml of 50% hypophosphorous acid
  5. extractionThe solution was extracted eight times with ethyl acetate
  6. dry with materialthe combined extracts were dried over sodium sulfate
  7. customevaporated
  8. dissolutionThe residue was dissolved in dichloromethane
  9. washthe solution was washed in sequence with water and saturated sodium chloride solution
  10. dry with materialThe dichloromethane solution was dried over sodium sulfate
  11. customevaporated
  12. customthe residue was crystallized from diethyl ether/n-hexane

Sources & evidence

ORD record
ord-bf6b2388142f42f9bfe4eedeabb014b8
Source dataset
uspto-grants-1994_04
Patent number
US05304549

Reaction notes

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