Propargyl bromide → 4-Trimethylsilylethynyl-1-octyn-4-ol

HRID 1413570Notes

Reaction equation

HRID 1413570 reaction equation
[Mg].[CH2:2](Br)[C:3]#[CH:4].[CH3:6][Si:7]([C:10]#[C:11][C:12]([CH2:14][CH2:15][CH2:16][CH3:17])=[O:13])([CH3:9])[CH3:8]>CCOCC>[CH3:9][Si:7]([C:10]#[C:11][C:12]([OH:13])([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:4][C:3]#[CH:2])([CH3:8])[CH3:6]

Participants

5

Reactant 3

HCID 7842Propargyl bromide2×HCID 5462224MagnesiumHCID 110195111-Heptyn-3-one, 1-(trimethylsilyl)-

Product 1

HCID 127861934-Trimethylsilylethynyl-1-octyn-4-ol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a stirred suspension of 1.29 grams of magnesium and 10 mg of mercuric chloride in 12 ml of ether is added 0.4 ml of propargyl bromide. The reaction is initiated after stirring at room temperature for a few minutes. The stirred mixture is cooled in an ice-water bath and a solution of 9.64 grams of n-butyl trimethylsilylethynyl ketone and 3.51 ml of propargyl bromide in 13 ml of ether added dropwise so that the mixture is very gently boiling during a period of about 40 minutes. After addition is complete, the cooling bath is removed and the mixture is stirred at room temperature for about 1.5 hours. The mixture is recooled in an ice bath and 10 ml of saturated ammonium chloride solution is added. The resulting white mixture is filtered through diatomaceous earth. The clear mother liquor is washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent is evaporated to dryness giving 10.5 grams of a red liquid. The liquid is Kugelrohr-distilled at 60° C./0.25-0.3 mm. The pale yellow liquid distillate which is the desired product weighed 8.5 grams.

Workup

  1. temperatureThe stirred mixture is cooled in an ice-water bath
  2. additionAfter addition
  3. customthe cooling bath is removed
  4. stirringthe mixture is stirred at room temperature for about 1.5 hours
  5. customThe mixture is recooled in an ice bath
  6. addition10 ml of saturated ammonium chloride solution is added
  7. filtrationThe resulting white mixture is filtered through diatomaceous earth
  8. washThe clear mother liquor is washed with saturated sodium chloride solution
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customThe solvent is evaporated to dryness

Sources & evidence

ORD record
ord-ed7d8ee6fe104aa3beedd5453cdff17e
Source dataset
uspto-grants-1981_02
Patent number
US04250325

Reaction notes

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