Ethanol → HCID 10290795, compound

HRID 568208Notes

Reaction equation

HRID 568208 reaction equation
[CH3:1][C:2]([O:9]C1CCCO1)([C:4]#[C:5][CH:6]1[CH2:8][CH2:7]1)[CH3:3].C(O)C.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C[O-].[Na+]>O>[CH3:1][C:2]([OH:9])([C:4]#[C:5][CH:6]1[CH2:8][CH2:7]1)[CH3:3]

Participants

6

Reactant 4

HCID 702Ethanol2×HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 10313514HCID 10313514, compoundHCID 10942334Sodium Methoxide

Product 1

HCID 10290795HCID 10290795, compoundYield 93.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

In a dried flask (300 ml volume), the inside of which had been flushed with nitrogen, were placed 2-methyl-2-tetrahydrofuranoxy-4-cyclopropyl-3-butyne (13.4 g, purity 97.5%, 67.3 mmol.) prepared in Example 4, ethanol (120 ml) and pyridinium p-toluenesulfonate (6.7 mg), and the resulting mixture was heated at 50° C. to 60° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, 10 mg of sodium methoxide (25% methanol solution) was added to the cooled mixture and ethanol was distilled through a rotary evaporator. To the concentrate obtained was added 100 ml of water, and the mixture was subjected to extraction with two 100 ml portions of ethyl acetate. The extract was washed with an aqueous saturated sodium bicarbonate solution and a saturated saline solution, dried over anhydrous sodium sulfate and concentrated by distillation of the solvent through a rotary evaporator to give 10.8 g of a crude product. The crude product was purified by silica gel column chromatography to give 2-methyl-2-hydroxy-4-cyclopropyl-3-butyne (7.84 g, purity 98.6%, yield 92.6%) having the following physical data:

Workup

  1. customIn a dried flask (300 ml volume), the inside of which had been flushed with nitrogen
  2. temperaturethe resulting mixture was heated at 50° C. to 60° C. for 1 hour
  3. customAfter completion of the reaction
  4. distillationwas distilled through a rotary evaporator
  5. customTo the concentrate obtained
  6. extractionthe mixture was subjected to extraction with two 100 ml portions of ethyl acetate
  7. washThe extract was washed with an aqueous saturated sodium bicarbonate solution
  8. dry with materiala saturated saline solution, dried over anhydrous sodium sulfate
  9. concentrationconcentrated by distillation of the solvent through a rotary evaporator
  10. customto give 10.8 g of a crude product
  11. customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-86fbe8a96d4840d5823d262617789820
Source dataset
uspto-grants-2001_01
Patent number
US06180835B2

Reaction notes

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