Methyl iodide → Methyl 3-methyl-4-oxooxane-3-carboxylate

HRID 736779Notes

Reaction equation

HRID 736779 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][O:5][CH2:4][CH:3]1[C:8]([O:10][CH3:11])=[O:9].O[C:13]1CCOCC=1C(OC)=O.[H-].[Na+].IC>CN(C=O)C.C(OCC)(=O)C>[CH3:13][C:3]1([C:8]([O:10][CH3:11])=[O:9])[C:2](=[O:1])[CH2:7][CH2:6][O:5][CH2:4]1

Participants

7

Reactant 4

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 14666555Methyl 4-oxooxane-3-carboxylateHCID 68541653methyl 4-hydroxy-5,6-dihydro-2H-pyran-3-carboxylate

Product 1

HCID 68819284Methyl 3-methyl-4-oxooxane-3-carboxylateYield 61%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 4-oxo-tetrahydro-2H-pyran-3-carboxylate and methyl 4-hydroxy-5,6-dihydro-2H-pyran-3-carboxylate (13.5 g, 85.5 mmol) were dissolved in DMF (70 mL). Sodium hydride (60%, 3.6 g, 1.05 eq) was added at 0° C. After 10 min, iodomethane (6.7 mL, 1.25 eq) was added. The reaction was stirred overnight, diluted with ethyl acetate (200 mL), and washed with water (5×100 mL). The aqueous layer was re-extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, and concentrated. The residue was purified by chromatography on silica gel eluting with 20% ethyl acetate/hexane to yield 8.2 g (61%) of methyl 3-methyl-4-oxo-tetrahydro-2H-pyran-3-carboxylate.

Workup

  1. washwashed with water (5×100 mL)
  2. extractionThe aqueous layer was re-extracted with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography on silica gel eluting with 20% ethyl acetate/hexane

Sources & evidence

ORD record
ord-4436b5a6cbe04081ab88f5302356c23f
Source dataset
uspto-grants-2009_09
Patent number
US07595327B2

Reaction notes

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