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

HRID 371781Notes

Reaction equation

HRID 371781 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

Conditions

Temperature
-40 °C

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° C. To that solution is then added 62.8 parts by volume of 2.31 M ethereal n-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 two hours, then is allowed to stand for about 16 hours at -5° to -10° C. At the end of that time, 10.14 parts of methyl vinyl ketone is added at -40° C. and the reaction mixture is stirred for about 4 hours, then is quenched with water. 50 Parts by volume of 3 N hydrochloric 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 and 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 to afford the crude product. This material is purified by distillation under reduced pressure to give 9-chloro-5-nonyn-2-one, boiling at about 80° - 92° C. at a pressure of 0.11 - 0.06 mm.

Workup

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

Sources & evidence

ORD record
ord-04a9d3e43d2742edb8c1e46cbdc7dd93
Source dataset
uspto-grants-1978_05
Patent number
US04087621

Reaction notes

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