Methanesulfonic Acid → Dimethyl (3-oxo-1,3-dihydro-2-benzofuran-1-yl)phosphonate

HRID 1473892Notes

Reaction equation

HRID 1473892 reaction equation
C[O-].[Na+].[P:4]([O-:11])([O:8][CH2:9]C)[O:5][CH2:6]C.[CH:12]([C:14]1[CH:22]=[CH:21][CH:20]=[CH:19][C:15]=1[C:16]([OH:18])=[O:17])=O.CS(O)(=O)=O>CO>[O:17]=[C:16]1[C:15]2[C:14](=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:12]([P:4](=[O:11])([O:8][CH3:9])[O:5][CH3:6])[O:18]1

Participants

6

Reactant 4

HCID 6395Methanesulfonic AcidHCID 8406Phthalaldehydic acidHCID 3780918DiethylphosphiteHCID 10942334Sodium Methoxide

Product 1

HCID 11118213Dimethyl (3-oxo-1,3-dihydro-2-benzofuran-1-yl)phosphonateYield 95%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of sodium methoxide (5.4 M, 4.8 mL) in MeOH (20 mL) was added diethyl phosphite (3.31 g, 24 mmol) at 0° C. followed by addition of 2-formylbenzoic acid (3.0 g, 20 mmol) portion-wise over a period of 20 min. The resulting mixture was warmed up to rt and continued to stir for 2 h. Methanesulphonic acid (2.69 g, 28 mmol, 1.4 equiv.) was added to the above mixture over a period of 30 min. The reaction mixture was stirred for 30 min and concentrated to remove most of the MeOH. The residue was partitioned between DCM (100 mL) and water (50 mL). The aqueous layer was extracted DCM twice. The combined organic layer was dried over Na2SO4 and concentrated to give dimethyl 3-oxo-1,3-dihydroisobenzofuran-1-ylphosphonate (4.6 g, 90%). LRMS (M+H+) m/z 257.1.

Workup

  1. stirringThe reaction mixture was stirred for 30 min
  2. concentrationconcentrated
  3. customto remove most of the MeOH
  4. customThe residue was partitioned between DCM (100 mL) and water (50 mL)
  5. extractionThe aqueous layer was extracted DCM twice
  6. dry with materialThe combined organic layer was dried over Na2SO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-a73c5c825ecf42618003b6b8a8c8a918
Source dataset
uspto-grants-2015_04
Patent number
US09018210B2

Reaction notes

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