Sulfuric Acid → HCID 23565261, compound

HRID 1059290Notes

Reaction equation

HRID 1059290 reaction equation
[C:1]([O:3][CH2:4][CH3:5])#[CH:2].C([Li])CCC.[CH3:11][N:12]1[CH2:21][CH2:20][CH2:19][CH:18]2[C:22](=[O:23])[CH:14]([CH2:15][CH2:16][CH2:17]2)[CH2:13]1.[Cl-].[NH4+].S(=O)(=O)(O)[OH:27].C(=O)(O)[O-].[Na+]>C(OCC)C.CCCCCC.C(OCC)(=O)C.O1CCCC1>[CH2:1]([O:3][C:4](=[O:27])[CH2:5][C:22]1([OH:23])[CH:20]2[CH2:21][N:12]([CH3:11])[CH2:13][CH:14]1[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19]2)[CH3:2]

Participants

11

Reactant 6

HCID 1118Sulfuric AcidHCID 25517Ammonium ChlorideHCID 61239Ether, ethyl ethynylHCID 516892Sodium BicarbonateHCID 18670575HCID 18670575, compoundHCID 178418339Butyllithium

Product 1

HCID 23565261HCID 23565261, compoundYield 47.9%

Reagents, catalysts & solvents 4

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×HCID 8857Ethyl AcetateSolvent2×

Procedure

A solution of 2.1 g of ethyl ethynyl ether (a 50% hexane solution) in dry diethyl ether (25 ml) was cooled in a nitrogen atmosphere to −78° C. After dropping 6 ml of a 2.5 M solution of n-butyllithium in hexane, the resulting mixture was stirred for 10 minutes. Next, 10 ml of a solution of 78 g of 3-methyl-3-azabicyclo[5.3.1]undecan-11-one in dry diethyl ether (10 ml) was dropped into the reaction mixture. After stirring for 15 minutes, the mixture was brought back to room temperature and then distributed into an aqueous solution of ammonium chloride and ethyl acetate. The organic layer was extracted and dried over anhydrous sodium sulfate. After distilling off the solvent, an oily component was obtained. Then 100 ml of tetrahydrofuran was added thereto and the resulting mixture was stirred. After dropping 10 mmol of conc. sulfuric acid thereinto, the reaction mixture was distributed into an aqueous solution of sodium bicarbonate and ethyl acetate and the organic layer was extracted. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane) to thereby give 1.29 g of the title compound as a colorless oily substance.

Workup

  1. stirringAfter stirring for 15 minutes
  2. customwas brought back to room temperature
  3. extractionThe organic layer was extracted
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationAfter distilling off the solvent
  6. customan oily component was obtained
  7. stirringthe resulting mixture was stirred
  8. extractionthe organic layer was extracted
  9. distillationAfter distilling off the solvent under reduced pressure
  10. customthe residue was purified by silica gel column chromatography (eluted with ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-e85ceb9c4f474e9da4fb3413d6bb29a4
Source dataset
uspto-grants-2003_02
Patent number
US06518423B1

Reaction notes

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