Hydrochloric Acid → 5-(Trimethylsilyl)furan-3-carbaldehyde

HRID 1492930Notes

Reaction equation

HRID 1492930 reaction equation
C([Li])CCC.N1CCOCC1.[O:12]1[CH:16]=[CH:15][C:14]([CH:17]=[O:18])=[CH:13]1.C([Li])(CC)C.[CH3:24][Si:25](Cl)([CH3:27])[CH3:26].Cl>CCCCCC.O1CCCC1.C1CCCCC1>[CH3:24][Si:25]([CH3:27])([CH3:26])[C:16]1[O:12][CH:13]=[C:14]([CH:17]=[O:18])[CH:15]=1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 8083MorpholineHCID 103513-FuraldehydeHCID 178418339ButyllithiumHCID 178418400CID 53628100

Product 1

HCID 156632515-(Trimethylsilyl)furan-3-carbaldehyde

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 8078CyclohexaneSolvent

Procedure

n-Butyl lithium (a 2.5M solution in hexane; 28.8 ml, 72 mmol) was added to a solution of morpholine (6.28 ml, 72 mmol) in tetrahydrofuran (700 ml) at -78° under argon. After 20 minutes, 3-furaldehyde (7.0 g, 72 mmol) was added. After another 20 minutes, sec-butyl lithium (a 1.3M solution in cyclohexane; 55.4 ml, 72 mmol) was added dropwise and stirring continued at -78° for 7 hours before trimethylsilyl chloride (27 ml, 2.6 mmol) was added. Stirring was continued overnight (14 hours) while the cooling bath was allowed to attain room temperature. The solution was poured into ice cold 10% (v/v) hydrochloric acid (200 ml) and after stirring at 0° for 10 minutes, the layers were separated. The aqueous phase was extracted with ethyl ether. All the organic phases were combined, dried (magnesium sulfate) and evaporated down to give a light brown oil, which was purified by flash chromatography on silica using 2% ethyl ether/hexane. Fractions with Rf of about 0.30 (silica, 10% ethyl ether/hexane) on evaporation gave the title aldehyde as a light yellow oil, b.p. 48°-50°/0.25 torr.

Workup

  1. waitAfter another 20 minutes
  2. addition55.4 ml, 72 mmol) was added dropwise
  3. additionwas added
  4. stirringStirring
  5. waitwas continued overnight
  6. custom(14 hours)
  7. customto attain room temperature
  8. stirringafter stirring at 0° for 10 minutes
  9. customthe layers were separated
  10. extractionThe aqueous phase was extracted with ethyl ether
  11. dry with materialdried (magnesium sulfate)
  12. customevaporated down
  13. customto give a light brown oil, which
  14. customwas purified by flash chromatography on silica using 2% ethyl ether/hexane
  15. customFractions with Rf of about 0.30 (silica, 10% ethyl ether/hexane) on evaporation

Sources & evidence

ORD record
ord-1bcef093eae84c9eb3e37c7d5c81f179
Source dataset
uspto-grants-1994_12
Patent number
US05376676

Reaction notes

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