Sodium Hydroxide → HCID 18182446, compound

HRID 1359406Notes

Reaction equation

HRID 1359406 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].CO[C:9]([C:11]1[S:12][CH:13]=[CH:14][C:15]=1[C:16]#[C:17][Si](C)(C)C)=[O:10].[OH-].[Na+].[C:24]1([Li])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.[Cl-].[NH4+]>C(OCC)(=O)C.C(OCC)C.C1CCCCC1.C(OCC)C.O.O1CCCC1>[C:16]([C:15]1[CH:14]=[CH:13][S:12][C:11]=1[CH:9]([OH:10])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)#[CH:17]

Participants

11

Reactant 5

HCID 14798Sodium HydroxideHCID 25517Ammonium ChlorideHCID 18182420HCID 18182420, compoundHCID 21226445Aluminium lithium hydrideHCID 178506676HCID 178506676, compound

Product 1

HCID 18182446HCID 18182446, compoundYield 11.6%

Reagents, catalysts & solvents 5

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 21895417Cyclohexane diethyletherSolvent

Procedure

131 mg of lithium aluminum hydride was added to a mixture of 821 mg of 2-methoxycarbonyl-3-(trimethylsilylethynyl)thiophene and 10 ml of tetrahydrofuran, followed by heating under reflux for 1.5 hours. After cooling as it was, 131 μl of water, 131 μl of an aqueous 1N sodium hydroxide solution and 393 μl of water were successively added thereto, followed by filtering through Celite. After removing the solvent, 5.25 g of manganese dioxide was added to a solution of 10 ml of dichloromethane containing the residue, followed by stirring at room temperature overnight. The mixture was filtered through Celite, and the solvent was removed. 3.5 ml of a cyclohexane-diethyl ether solution containing 1.8 mol of phenyl lithium was added dropwise to a mixture of the residue and 5 ml of diethyl ether at −78° C., followed by stirring at the same temperature for 20 minutes. Aqueous ammonium chloride was added to the reaction solution and the temperature of the system was raised to room temperature. Ethyl acetate was added thereto, and the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate and the solvent was removed. The residue was subjected to silica gel column chromatography using 10% ethyl acetate/hexane, to give 85.7 mg of the target compound.

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 1.5 hours
  3. temperatureAfter cooling as it
  4. filtrationby filtering through Celite
  5. customAfter removing the solvent, 5.25 g of manganese dioxide
  6. additionwas added to a solution of 10 ml of dichloromethane containing the residue
  7. filtrationThe mixture was filtered through Celite
  8. customthe solvent was removed
  9. stirringby stirring at the same temperature for 20 minutes
  10. temperaturethe temperature of the system was raised to room temperature
  11. washthe organic phase was washed with water and brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customthe solvent was removed

Sources & evidence

ORD record
ord-eb1f750a8944408a8a54c8db3ff00976
Source dataset
uspto-grants-2003_07
Patent number
US06599917B1

Reaction notes

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