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

HRID 459754

Reaktionsgleichung

Reaktionsgleichung von HRID 459754
[P:1]([O-:6])([O:4][CH3:5])[O:2][CH3:3].C[O-].[Na+].[C:10]([C:13]1[CH:20]=[CH:19][CH:18]=[CH:17][C:14]=1[CH:15]=[O:16])(O)=[O:11].CS(O)(=O)=O>CO>[O:11]=[C:10]1[C:13]2[C:14](=[CH:17][CH:18]=[CH:19][CH:20]=2)[CH:15]([P:1](=[O:6])([O:4][CH3:5])[O:2][CH3:3])[O:16]1

Komponenten

6

Edukt 4

HCID 6395Methanesulfonic AcidHCID 8406Phthalaldehydic acidHCID 10942334Sodium MethoxideHCID 21884954Dimethylphosphite

Produkt 1

HCID 11118213Dimethyl (3-oxo-1,3-dihydro-2-benzofuran-1-yl)phosphonateAusbeute 90,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

Dimethyl phosphite (100 g, 0.909 mol) was added dropwise at 0° C. under nitrogen to a stirred solution of sodium methoxide [from sodium (20.9 g, 0.909 gatom)] in methanol (730 ml), the mixture was stirred for 5 minutes, and 2-carboxybenzaldehyde (95.45 g, 0.64 mol) was added in portions. The stirred mixture was allowed to warm to ambient temperature, then it was stirred for 30 minutes and cooled in ice. Methanesulfonic acid (96 g, 1 mol) was added in portions at 5–10° C., then the solvent was removed in vacuo. The residue was partitioned between dichloromethane (1800 ml) and water (450 ml), and the organic layer was separated, washed with water (2×450 ml) and dried (MgSO4) The solvent was removed in vacuo, the residue was triturated with ether (150 ml), and the resulting solid was collected by filtration, washed with ether (30 ml) and dried in vacuo to give dimethyl 3-oxo-1,3-dihydroisobenzofuran-1-ylphosphonate (139.94 g) as a white crystalline solid, m.pt 95–96.5° C.; 250 MHz 1H-nmr (d6-DMSO) δ (ppm): 3.65 (d, 3H) (—OCH3), 3.85 (d, 3H) (—OCH3), 6.4 (d, 1H) (—CH—P), 7.75 (m, 2H) (2×ArH), 7.85–8.05 (m, 2H) (2×ArH); m/z (M+H)+. 243, 100% purity.

Aufarbeitung

  1. stirringit was stirred for 30 minutes
  2. temperaturecooled in ice
  3. customthe solvent was removed in vacuo
  4. customThe residue was partitioned between dichloromethane (1800 ml) and water (450 ml)
  5. customthe organic layer was separated
  6. washwashed with water (2×450 ml)
  7. dry with materialdried (MgSO4) The solvent
  8. customwas removed in vacuo
  9. customthe residue was triturated with ether (150 ml)
  10. filtrationthe resulting solid was collected by filtration
  11. washwashed with ether (30 ml)
  12. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-6f6f8d0085474818a20bb04433cdd128
Quelldatensatz
uspto-grants-2007_03
Patentnummer
US07196085B2

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