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

HRID 256614Notes

Reaction equation

HRID 256614 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.Cl[Si:25]([CH3:28])([CH3:27])[CH3:26].Cl>CCCCCC.O1CCCC1.C1CCCCC1>[CH3:26][Si:25]([CH3:28])([CH3:27])[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-carbaldehydeYield 68%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 8078CyclohexaneSolvent

Procedure

n-Butyl lithium (a 2.5 m 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 min., 3-furaldehyde (7.0 g, 72 mmol) was added. After another 20 min., sec-butyl lithium (a 1.3 m solution in cyclohexane; 55.4 ml, 72 mmol) was added dropwise and stirring continued at -780 for 7h before chlorotrimethylsilane (27 ml, 216 mmol) was added. Stirring continued overnight (14h) 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 min., the layers were separated. The aqueous phase was extracted with diethyl 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 8.22 g (68%) of the title aldehyde as a light yellow oil, bp 48°-50°/0.25 torr.

Workup

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

Sources & evidence

ORD record
ord-9470ad66ebf444ada3e04f9ce8a034df
Source dataset
uspto-grants-1993_11
Patent number
US05258400

Reaction notes

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