Hydrochloric Acid → 1-[3,5-Difluoro-4-(methylthio)phenyl]-4,4,4-trifluorobutane-1,3-dione
Reaction equation
[F:1][C:2]1[CH:3]=[C:4]([C:11](=[O:13])[CH3:12])[CH:5]=[C:6]([F:10])[C:7]=1[S:8][CH3:9].C[O-].[Na+].[F:17][C:18]([F:25])([F:24])[C:19](OCC)=[O:20].Cl>C(OCC)C.C(OCC)(=O)C>[F:10][C:6]1[CH:5]=[C:4]([C:11](=[O:13])[CH2:12][C:19](=[O:20])[C:18]([F:25])([F:24])[F:17])[CH:3]=[C:2]([F:1])[C:7]=1[S:8][CH3:9]Participants
Reactant 4
Product 1
Reagents, catalysts & solvents 2
Procedure
1-[3,5-difluoro-4-(methylthio)phenyl]ethanone (4.84 g, 23.9 mmol) was dissolved in diethyl ether (200 mL). Sodium methoxide (24 mL of 25% in methanol, 30 mmol) was added and stirred 10 min at ambient temperature. Ethyl trifluoroacetate (3.79 g, 23.9 mmol) was added. The solution was stirred for 1 hour then aqueous hydrochloric acid was added (100 mL, 1 M). The layers were separated and the organic layer collected. The organic layer was washed with water (2×100 mL), saturated ammonium chloride (2×200 mL) and dried over sodium sulfate. The solvent was removed in vacuo to afford a yellow oil. The 1-[3,5-difluoro-4-(methylthio)phenyl]-4,4,4-trifluorobutane-1,3-dione was isolated by crystallization from ethyl acetate and hexanes (5.50 g, 77%). 1H NMR (CDCl3/300 MHz) 7.49 (m, 2H), 6.50 (s, 1H), 2.62 (s, 3H). ESHRMS m/z 297.0012 (M+H+, Calcd 297.0009). Anal. Calcd for C11H7F5O2S: C, 44.30; H, 2.37. Found: C, 44.36; H, 2.26.
Workup
- stirringThe solution was stirred for 1 hour
- customThe layers were separated
- customthe organic layer collected
- washThe organic layer was washed with water (2×100 mL), saturated ammonium chloride (2×200 mL)
- dry with materialdried over sodium sulfate
- customThe solvent was removed in vacuo
- customto afford a yellow oil
Sources & evidence
- ORD record
- ord-d521ec084fe74074ac1bfd56019dfc30
- Source dataset
- uspto-grants-2004_03
- Patent number
- US06699884B2
Reaction notes
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