Citric Acid → 4-[(Di-tert-butoxyphosphoryl)oxy]-3,3-dimethylbutanoic acid

HRID 2238329Notes

Reaction equation

HRID 2238329 reaction equation
[P:1]([O:13][CH2:14][C:15]([CH3:20])([CH3:19])[CH2:16][CH2:17][OH:18])([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=[O:22].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CN(C=O)C>[C:9]([O:8][P:1]([O:13][CH2:14][C:15]([CH3:20])([CH3:19])[CH2:16][C:17]([OH:22])=[O:18])([O:3][C:4]([CH3:5])([CH3:6])[CH3:7])=[O:2])([CH3:10])([CH3:11])[CH3:12]

Participants

5

Reactant 3

HCID 311Citric AcidHCID 2724130Cornforth reagentHCID 86616511Di-tert-butyl 4-hydroxy-2,2-dimethylbutyl phosphate

Product 1

HCID 860938834-[(Di-tert-butoxyphosphoryl)oxy]-3,3-dimethylbutanoic acidYield 60%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of the product from Example 10C (0.235 g, 0.76 mmol) in DMF (7.6 mL) at room temperature was added pyridinium dichromate (1.71 g), and the mixture was stirred for 16 hours. 10% citric acid was added and the reaction mixture was extracted twice with ethyl acetate. The combined organic layer was washed with brine, dried over MgSO4, filtered and evaporated. The residue was purified by chromatography on silica gel, eluting with a gradient starting with chloroform and ending with 5% methanol in chloroform, to give the title compound (0.144 g, 60%).

Workup

  1. extractionthe reaction mixture was extracted twice with ethyl acetate
  2. washThe combined organic layer was washed with brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue was purified by chromatography on silica gel
  7. washeluting with

Sources & evidence

ORD record
ord-2a2d6e44d9ed435ea8d5e181f4cfbbfa
Source dataset
uspto-grants-2010_05
Patent number
US07718633B2

Reaction notes

Loading…