Potassium Carbonate → HCID 53762825, compound

HRID 484564Notes

Reaction equation

HRID 484564 reaction equation
[CH3:1][C:2]([C:9]#[CH:10])=[CH:3][CH2:4][CH2:5][C:6](=[O:8])[CH3:7].[Cl:11][CH2:12][C:13]([CH2:15]Cl)=[CH2:14].C(=O)([O-])[O-].[K+].[K+]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(#N)C.CCOCC>[Cl:11][CH2:12][C:13](=[CH2:14])[CH2:15][C:10]#[C:9][C:2]([CH3:1])=[CH:3][CH2:4][CH2:5][C:6](=[O:8])[CH3:7]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 158593-Chloro-2-chloromethyl-1-propeneHCID 54188136HCID 54188136, compound

Product 1

HCID 53762825HCID 53762825, compoundYield 74%

Reagents, catalysts & solvents 3

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent

Procedure

A mixture of 120 mg (0.88 mmole) of 6-methyl-5-octen-7-yn-2-one (produced in accordance with Example II), 2.00 mL (19 mmoles, the excess of which can be quantitatively recovered by distillation at reduced pressure after the reaction is complete) of 3-chloro-2-chloromethyl-1-propene (purchased from Aldrich Chemical Co., Milwaukee, Wis.), 193 mg (1.4 mmoles) of anhydrous potassium carbonate, 20 mg (0.20 mmole) of cuprous chloride, and 20 mg (0.087 mmole) of benzyltriethylammonium chloride in 2.00 mL of acetonitrile (HPLC-grade, purchased from Aldrich Chemical Co., Milwaukee, Wis.) was stirred vigorously at room temperature for 22 hours, during which time the mixture was maintained under an atmosphere of nitrogen. The mixture was then diluted with 40 mL of 1:1 (v/v) ether:hexane and filtered through a small pad of Hyflo Super-Cel® filtering aid. The filtrate was washed with 20 mL of 5% aqueous sodium chloride, then dried over anhydrous magnesium sulfate, and re-filtered. Removal of the volatile organic material by evaporation at reduced pressure (50 mm) and recovery of unreacted 3-chloro-2-chloromethyl-1-propene by evaporative fractional distillation at reduced pressure (2.5 mm) afforded 146 mg (74% yield) of the named ketone after distillation in the presence of a small amount of calcium carbonate: boiling point 122°-130° C. (bath temperature, 0.20 mm). Proton NMR analysis indicated the presence of a minor impurity, subsequently found to have been present as a contaminant in 3-chloro-2-chloromethyl-1-propene. The named ketone was characterized by a singlet at δ1.78 (CH3 bonded to C-6), a singlet at δ2.12 (CH3C=O), a singlet at δ3.15 (2 hydrogens bonded to C-9), and a singlet at δ4.05 (CH2Cl).

Workup

  1. distillationthe excess of which can be quantitatively recovered by distillation at reduced pressure after the reaction
  2. temperaturewas maintained under an atmosphere of nitrogen
  3. filtrationhexane and filtered through a small pad of Hyflo Super-Cel®
  4. filtrationfiltering aid
  5. washThe filtrate was washed with 20 mL of 5% aqueous sodium chloride
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationre-filtered
  8. customRemoval of the volatile organic material
  9. customby evaporation at reduced pressure (50 mm) and recovery of unreacted 3-chloro-2-chloromethyl-1-propene
  10. distillationby evaporative fractional distillation at reduced pressure (2.5 mm)

Sources & evidence

ORD record
ord-a810db34364a4434b5eb6bb0467644bf
Source dataset
uspto-grants-1993_07
Patent number
US05231232

Reaction notes

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