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

HRID 126724Notes

Reaction equation

HRID 126724 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 g. 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 g. of n-butyl trimethylsilylethynyl ketone and 3.51 ml. of propargyl bromide in 13 ml. of ether is added, dropwise so that the mixture is very gently boiling during 40 minutes. After addition, the cooling bath is removed and the mixture is stirred at room temperature for 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 g. of a red liquid. This liquid is Kugelrohr-distilled at 60° C./0.25-0.3 mm. The pale yellow liquid distillage which is the desired product weighs 8.5 g.

Workup

  1. additionTo a stirred suspension of 1.29 g
  2. temperatureThe stirred mixture is cooled in an ice-water bath
  3. additionAfter addition
  4. customthe cooling bath is removed
  5. stirringthe mixture is stirred at room temperature for 1.5 hours
  6. customThe mixture is recooled in an ice-bath
  7. additionof saturated ammonium chloride solution is added
  8. filtrationThe resulting white mixture is filtered through diatomaceous earth
  9. washThe clear mother liquor is washed with saturated sodium chloride solution
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customThe solvent is evaporated to dryness
  12. customgiving 10.5 g
  13. distillationThis liquid is Kugelrohr-distilled at 60° C./0.25-0.3 mm

Sources & evidence

ORD record
ord-031aef73628548ba8568335c77e63bc9
Source dataset
uspto-grants-1981_03
Patent number
US04254036

Reaction notes

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