Acetic Acid → Dimethyl [4-(furan-2-yl)-2-oxobutyl]phosphonate

HRID 614042Notes

Reaction equation

HRID 614042 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].[CH2:12]([Li])[CH2:13][CH2:14][CH3:15].C(O)(=[O:19])C.[O:21]1C[CH2:24][CH2:23][CH2:22]1>CCCCCC>[O:19]=[C:12]([CH2:13][CH2:14][C:15]1[O:21][CH:22]=[CH:23][CH:24]=1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 406CID 406HCID 8028TetrahydrofuranHCID 12958Dimethyl methylphosphonateHCID 178418339Butyllithium

Product 1

HCID 13941306Dimethyl [4-(furan-2-yl)-2-oxobutyl]phosphonate

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

A solution of 25 g (0.21 mole) dimethyl methylphosphonate (Aldrich) in 300 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 80 ml of 2.67 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 18 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 16.0 g (0.104 mole) methyl 3-(2-furyl) propionate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 3.5 hours at -78° the reaction mixture was allowed to warm to ambient temperature, neutralized with 6 ml acetic acid and rotary evaporated to a white gel. The gelatinous material was taken up in 75 ml water, the aqueous phase extracted with 100 ml portions of chloroform (3×), the combined organic extracts were backwashed (50 cc H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 148°-50° (0.5 mm) to give 8.4 g dimethyl 2-oxo-4-(2-furyl)butylphosphonate (2C).

Workup

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 3.5 hours at -78° the reaction mixture was allowed
  3. customrotary evaporated to a white gel
  4. extractionthe aqueous phase extracted with 100 ml portions of chloroform (3×)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled

Sources & evidence

ORD record
ord-cdf68825294943e19cd34b5926fb0a31
Source dataset
uspto-grants-1979_03
Patent number
US04143051

Reaction notes

Loading…