Potassium Carbonate → HCID 86599454, compound

HRID 854899Notes

Reaction equation

HRID 854899 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([OH:21])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2.C([O-])([O-])=O.[K+].[K+].[F:28][C:29]([F:33])([F:32])[CH2:30]I.C([O-])(O)=O.[Na+]>CN(C=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([O:21][CH2:30][C:29]([F:33])([F:32])[F:28])[CH:5]=[C:6]2[C:11]=1[O:10][CH:9]([C:12]([F:15])([F:14])[F:13])[C:8]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:7]2

Participants

6

Reactant 4

HCID 11430Potassium Carbonate2×HCID 677091,1,1-Trifluoro-2-iodoethane3×HCID 516892Sodium BicarbonateHCID 69517568HCID 69517568, compound

Product 1

HCID 86599454HCID 86599454, compoundYield 41%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of ethyl 8-chloro-6-hydroxy-2-(trifluoromethyl)-2H-chromene-3-carboxylate prepared as in Example 17a, Step 3 (0.500 g, 1.55 mmole) in anhydrous DMF (5.0 mL) under a dry N2 atmosphere was added KI (26 mg, 0.155 mmole), K2CO3 (0.321 g, 2.33 mmole) and 2,2,2-trifluoroethyl iodide (0.458 mL, 4.65 mmole) and the mixture was stirred at room temperature for 1 h, and then at 40° C. for 1 h. Additional K2CO3 (0.647 g, 4.65 mmole) and 2,2,2-trifluoroethyl iodide (0.458 mL, 4.65 mmole) were added to the mixture and the temperature was raised to 50° C. overnight. Additional 2,2,2-trifluoroethyl iodide (0.458 mL (4.65 mmole) was added and the temperature was raised to 85° C. for 18.5 h. The mixture was then poured into sat. NaHCO3 (100 mL) and extracted with EtOAc (2×200 mL). The combined extracts were then washed with brine (2×200 mL), dried over MgSO4, filtered and concentrated in vacuo to give a brown oil. Purification of the crude product by silica chromatography (6:1 hexanes:EtOAc) gave 0.237 g (41% yield) of the product as a light yellow crystalline solid: EIHRMS m/z 404.0246 (M+, C15H11ClF6O4, Calc'd 404.0250).

Workup

  1. waitat 40° C. for 1 h
  2. temperaturethe temperature was raised to 50° C. overnight
  3. temperaturethe temperature was raised to 85° C. for 18.5 h
  4. extractionextracted with EtOAc (2×200 mL)
  5. washThe combined extracts were then washed with brine (2×200 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give a brown oil
  10. customPurification of the crude product by silica chromatography (6:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-0c255c60f3374208abd75c4432697355
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

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