2-Methyl-3-butyn-2-ol → 1-Methoxy-2,5-dimethylhex-3-yne-2,5-diol

HRID 1191578Notes

Reaction equation

HRID 1191578 reaction equation
C([Mg]Br)C.[CH3:5][C:6]([OH:10])([C:8]#[CH:9])[CH3:7].[CH3:11][O:12][CH2:13][C:14](=[O:16])[CH3:15].[Cl-].[NH4+]>C(OCC)C>[CH3:11][O:12][CH2:13][C:14]([CH3:15])([OH:16])[C:9]#[C:8][C:6]([CH3:7])([OH:10])[CH3:5]

Participants

6

Reactant 4

HCID 82582-Methyl-3-butyn-2-olHCID 22172MethoxyacetoneHCID 25517Ammonium ChlorideHCID 178418443HCID 178418443, compound

Product 1

HCID 594459121-Methoxy-2,5-dimethylhex-3-yne-2,5-diolYield 94.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of anhydrous diethyl ether at 0-5° C. is added ethyl magnesium bromide (37.33 ml, 112 mmol, 3M solution in diethyl ether), then 2-methyl-3-butyn-2-ol (4.70 g, 55.87 mmol) dropwise. The mixture is allowed to warm to room temperature, followed by stirring at this temperature for 30 minutes, then at 40° C. until gas evolution ceases (approximately 1 hour). The viscous mixture is next cooled to room temperature and methoxyacetone (3.78 g, 42.90 mmol) is added dropwise, followed by heating to 40° C. for 1 hour. After cooling to room temperature the suspension is poured into a mixture of ice and saturated aqueous ammonium chloride, and the product is extracted with diethyl ether (2×50 ml) then dichloromethane (2×50 ml, 2×100 ml). The organic extracts are combined, washed with brine, dried over anhydrous magnesium sulfate then concentrated in vacuo to afford 1-methoxy-2,5-dimethylhex-3-yne-2,5-diol (6.98 g) as a clear oil.

Workup

  1. customat 40° C.
  2. customuntil gas evolution ceases (approximately 1 hour)
  3. temperatureThe viscous mixture is next cooled to room temperature
  4. temperatureby heating to 40° C. for 1 hour
  5. temperatureAfter cooling to room temperature the suspension
  6. extractionthe product is extracted with diethyl ether (2×50 ml)
  7. washwashed with brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationthen concentrated in vacuo

Sources & evidence

ORD record
ord-a0d0958a19ca4118b7cf028df8320348
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

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