Acetylene → 4,4-Dimethyl-1-octyn-3-ol

HRID 1580298Notes

Reaction equation

HRID 1580298 reaction equation
C#C.[CH2:3]([Mg]Br)[CH3:4].[CH3:7][C:8]([CH3:15])([CH2:11][CH2:12][CH2:13][CH3:14])[CH:9]=[O:10].[Cl-].[NH4+]>O1CCCC1>[CH3:7][C:8]([CH3:15])([CH2:11][CH2:12][CH2:13][CH3:14])[CH:9]([OH:10])[C:3]#[CH:4]

Participants

6

Reactant 4

HCID 6326Acetylene2×HCID 25517Ammonium ChlorideHCID 523230Hexanal, 2,2-dimethyl-HCID 178418443HCID 178418443, compound

Product 1

HCID 145163694,4-Dimethyl-1-octyn-3-ol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution containing 90 parts of acetylene dissolved in 600 parts by volume of tetrahydrofuran is added, over a period of about 50 minutes at -70°, 600 parts by volume of tetrahydrofuran containing 133 parts of ethyl magnesium bromide. Acetylene gas is continuously passed through the mixture during the addition period. Following that addition, the mixture is stirred at approximately -40° for about 45 minutes. To that mixture is then added, with stirring under nitrogen over a period of about 1 hour, 80 parts by volume of 2,2-dimethyl-n-hexaldehyde dissolved in 350 parts by volume of tetra=hydrofuran. Stirring at room temperature is continued for about 16 hours, at the end of which time approximately 125 parts by volume of saturated aqueous ammonium chloride is added slowly with stirring. The precipitate which forms is removed by filtration and the filtrate is partially concentrated, then diluted with ether and again filtered. The filtrate is stripped of solvent, then is distilled under reduced pressure to afford 4,4-dimethyl-1-octyn-3-ol, boiling at about 55°-65° at a pressure of about 3 mm.

Workup

  1. additionis added, over a period of about 50 minutes at -70°
  2. additionFollowing that addition
  3. additionTo that mixture is then added
  4. stirringwith stirring under nitrogen over a period of about 1 hour
  5. stirringStirring at room temperature
  6. additionis added slowly
  7. stirringwith stirring
  8. customThe precipitate which forms is removed by filtration
  9. concentrationthe filtrate is partially concentrated
  10. additiondiluted with ether
  11. filtrationagain filtered
  12. distillationis distilled under reduced pressure

Sources & evidence

ORD record
ord-6624af278b184bb0949808cd6afd2acc
Source dataset
uspto-grants-1976_01
Patent number
US03932496

Reaction notes

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