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

HRID 1274276Notes

Reaction equation

HRID 1274276 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 EtherSolvent2×

Procedure

Ethyl difluoroacetate (24.82 g, 200 mmol) was placed in a 500 mL three-necked round bottom flask, and dissolved in diethyl ester (200 mL). To the stirred solution was added 25% 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 to give 31.96 g (69%) of the dione: mp 65-66.5° C.

Workup

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

Sources & evidence

ORD record
ord-41d67625bd3a4250a349be814f28b135
Source dataset
uspto-grants-2000_12
Patent number
US06156781

Reaction notes

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