Methyl vinyl ketone → 5-Nonyn-2-one, 9-chloro-

HRID 427091Notes

Reaction equation

HRID 427091 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][C:5]#[CH:6].C([Li])CCC.B(F)(F)F.CCOCC.[CH:21]([C:23]([CH3:25])=[O:24])=[CH2:22]>C1(C)C=CC=CC=1>[Cl:1][CH2:2][CH2:3][CH2:4][C:5]#[C:6][CH2:22][CH2:21][C:23](=[O:24])[CH3:25]

Participants

6

Reactant 4

HCID 6570Methyl vinyl ketoneHCID 8000Boron trifluoride etherateHCID 843081-Pentyne, 5-chloro-HCID 178418339Butyllithium

Product 1

HCID 114352145-Nonyn-2-one, 9-chloro-

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

14.85 Parts of 5-chloropent-1-yne is dissolved in 250 parts by volume of toluene and the resulting solution is cooled to approximately -40°. To that solution is then added 62.8 parts by volume of 2.31 M ethereal butyl lithium and stirring is continued for approximately 15 minutes. 6.87 Parts of boron trifluoride etherate is added and the reaction mixture is stirred for about 2 hours, then allowed to stand for about 16 hours at -5° to -10°. At the end of that time 10.14 parts of methyl vinyl ketone is added at -40° and the reaction mixture is stirred for about 4 hours, then is quenched with water. 50 Parts by volume of 3 N hydro=chloric acid is added and the mixture is kept at room temperature for about 16 hours, at the end of which time the aqueous and organic layers are separated. The aqueous layer is extracted with toluene and the organic layer with water. The organic solutions are combined, washed successively with aqueous sodium hydroxide and water, then dried over anhydrous sodium sulfate and stripped to dryness under reduced pressure, thus affording the crude product. This material is purified by distillation under reduced pressure to afford 9-chloro-5-nonyn-2-one, boiling at about 80°-92° at a pressure of 0.11-0.06 mm.

Workup

  1. temperaturethe resulting solution is cooled to approximately -40°
  2. stirringthe reaction mixture is stirred for about 2 hours
  3. waitto stand for about 16 hours at -5° to -10°
  4. stirringthe reaction mixture is stirred for about 4 hours
  5. customis quenched with water
  6. addition50 Parts by volume of 3 N hydro=chloric acid is added
  7. waitthe mixture is kept at room temperature for about 16 hours, at the end of which time
  8. customthe aqueous and organic layers are separated
  9. extractionThe aqueous layer is extracted with toluene
  10. washwashed successively with aqueous sodium hydroxide and water
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthus affording the crude product
  13. distillationThis material is purified by distillation under reduced pressure

Sources & evidence

ORD record
ord-5eb8593aa9e146d6938a9e0cb00ba8a6
Source dataset
uspto-grants-1979_10
Patent number
US04172953

Reaction notes

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