Hydrochloric Acid → 1-(4-Chlorophenyl)-4,4-difluorobutane-1,3-dione

HRID 440060Notes

Reaction equation

HRID 440060 reaction equation
[F:1][CH:2]([F:8])[C:3]([O:5]CC)=O.C[O-].[Na+].CO.[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([C:21](=[O:23])[CH3:22])=[CH:17][CH:16]=1.Cl>C(OCC)C>[F:8][CH:2]([F:1])[C:3](=[O:5])[CH2:22][C:21]([C:18]1[CH:19]=[CH:20][C:15]([Cl:14])=[CH:16][CH:17]=1)=[O:23]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 887MethanolHCID 7467P-ChloroacetophenoneHCID 9961Ethyl difluoroacetateHCID 10942334Sodium Methoxide

Product 1

HCID 153380131-(4-Chlorophenyl)-4,4-difluorobutane-1,3-dioneYield 99.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

Ethyl difluoroacetate (24.82 g, 200 mmol) was placed in a 500 mL three-necked round bottom flask, and dissolved in diethyl ether (200 mL). To the stirred solution was added 25 weight % sodium methoxide in methanol (48 mL, 210 mmol) via an addition funnel over a 2 minute period. Next, 4'-chloroacetophenone (25.94 g, 200 mmol) was dissolved in diethyl ether (50 mL), and added to the reaction dropwise over 5 minutes. After stirring overnight (18 hours), 1N HCl (250 mL) and ether (250 mL) were added. The organic layer was collected, washed with brine (250 mL), dried over MgSO4, filtered, and concentrated in vacuo to give 46.3 g of a yellow solid. The solid was recrystallized from methylene chloride and iso-octane no give 31.96 g, 69% of dione, mp 65°-66.5° C.

Workup

  1. additionadded to the reaction dropwise over 5 minutes
  2. additionwere added
  3. customThe organic layer was collected
  4. washwashed with brine (250 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-2572ff2c433c4770baf683ee4f88bad3
Source dataset
uspto-grants-1996_05
Patent number
US05516907

Reaction notes

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