Methyl morpholine oxide → 5-[(2-Methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-carbaldehyde

HRID 2091397Notes

Reaction equation

HRID 2091397 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][N:5]([CH3:20])[C:6]1[CH:7]=[CH:8][C:9]2[O:13][C:12]([C:14](OC)=[O:15])=[C:11]([CH3:18])[C:10]=2[CH:19]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].C[N+]1([O-])CCOCC1>O1CCCC1.C(#N)C.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[CH3:1][O:2][CH2:3][CH2:4][N:5]([CH3:20])[C:6]1[CH:7]=[CH:8][C:9]2[O:13][C:12]([CH:14]=[O:15])=[C:11]([CH3:18])[C:10]=2[CH:19]=1

Participants

7

Reactant 3

HCID 82029Methyl morpholine oxideHCID 21226445Aluminium lithium hydrideHCID 66778759Methyl 5-[(2-methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-carboxylate2×

Product 1

HCID 866627595-[(2-Methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-carbaldehydeYield 3.7%

Reagents, catalysts & solvents 3

HCID 178419074HCID 178419074, compoundCatalystHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution (10 mL) of methyl 5-[(2-methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-carboxylate (2.7 g) synthesized in the above-mentioned (1) in tetrahydrofuran was added to an ice-cooled solution (40 mL) of lithium aluminum hydride (0.38 g) in tetrahydrofuran. The ice bath was removed, and the reaction mixture was stirred at room temperature for 1 hr then ice-cooled again, and water (1.0 mL), 1N aqueous sodium hydroxide solution (5.0 mL) and water (1.0 mL) were successively added dropwise to quench the reaction. The residue was filtered through celite, and the filtrate was concentrated under reduced pressure to give a crude product (0.41 g) of {5-[(2-methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-yl}methanol as a pale-yellow oil. The obtained oil was dissolved in acetonitrile (20 mL), tetrapropylammonium perruthenate (0.07 g) and N-methylmorpholine N-oxide (0.46 g) were added to the solution at room temperature, and the mixture was stirred for 30 min. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:2, volume ratio) to give the title object compound (0.09 g, 3%) as a yellow oil.

Workup

  1. customThe ice bath was removed
  2. temperatureice-cooled again
  3. additionwater (1.0 mL), 1N aqueous sodium hydroxide solution (5.0 mL) and water (1.0 mL) were successively added dropwise
  4. customto quench
  5. customthe reaction
  6. filtrationThe residue was filtered through celite
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customto give a crude product (0.41 g) of {5-[(2-methoxyethyl)(methyl)amino]-3-methyl-1-benzofuran-2-yl}methanol as a pale-yellow oil
  9. stirringthe mixture was stirred for 30 min
  10. customThe solvent was evaporated under reduced pressure
  11. customthe residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:2, volume ratio)

Sources & evidence

ORD record
ord-cb9487ea717b48df8b99c7bcaec297ff
Source dataset
uspto-grants-2013_05
Patent number
US08436043B2

Reaction notes

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