Sodium hydride → HCID 21883655, compound

HRID 2214868Notes

Reaction equation

HRID 2214868 reaction equation
[F:1][C:2]([F:12])([F:11])[C:3](=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[H-].[Na+].F[C:16]1[CH:24]=[CH:23][C:22]([C:25]([F:28])([F:27])[F:26])=[CH:21][C:17]=1[C:18](Cl)=[O:19]>C1(C)C=CC=CC=1.C(OCC)C>[F:1][C:2]([F:11])([F:12])[C:3]1[O:10][C:16]2[CH:24]=[CH:23][C:22]([C:25]([F:26])([F:28])[F:27])=[CH:21][C:17]=2[C:18](=[O:19])[C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 67793Ethyl 4,4,4-trifluoroacetoacetateHCID 27348802-Fluoro-5-(trifluoromethyl)benzoyl Chloride

Product 1

HCID 21883655HCID 21883655, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

To a stirred solution of ethyl 4,4,4-trifluoroacetoacetate (3.22 mL, 4.06 g, 22.07 mmol) in toluene (100 mL) was added portion-wise sodium hydride (0.971 g, of 60% oil dispersion reagent, 22.07 mmol) causing gas evolution. After gas evolution has subsided, 2-fluoro-5-(trifluoromethyl)benzoyl chloride (5.00 g, 22.07 mmol) was added. The reaction was stirred at room temperature for 24 hours, then heated to 105° C. for 24 hours. After cooling to room temperature, the reaction was diluted with diethyl ether and the resulting solution was washed with H2O and brine, dried over MgSO4, filtered and concentrated in vacuo yielding a slightly sticky white solid. This solid was triturated with hexanes yielding the desired ester(3.05 g, 39%) as a white powder: mp 116–120.1° C. 1H NMR (CDCl3/300 MHz) 8.52 (d, 2H, J=1.6 Hz), 8.03 (dd, 1H, J=8.9, 2.2 Hz), 7.71 (d, 1H, J=8.9 Hz), 4.48 (q, 2H, J=7.3 Hz), 1.39 (t, 3H, J=7.3 Hz). FABLRMS m/z 355 (M+H). Anal. Calc'd for C14H8F6O4: C, 47.45; H, 2.28. Found: C, 47.59; H, 2.43.

Workup

  1. temperatureheated to 105° C. for 24 hours
  2. temperatureAfter cooling to room temperature
  3. washthe resulting solution was washed with H2O and brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customyielding a slightly sticky white solid
  8. customThis solid was triturated with hexanes yielding the desired ester(3.05 g, 39%) as a white powder

Sources & evidence

ORD record
ord-56987b4af49d4c208a1e7feae33a1c64
Source dataset
uspto-grants-2006_09
Patent number
US07109211B2

Reaction notes

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