Sulfuric Acid → ethyl 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylate

HRID 264853Notes

Reaction equation

HRID 264853 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:11]2[CH:12]=[C:13](N)[CH:14]=[CH:15][C:10]=2[O:9][C:8]([CH2:19][F:20])([CH2:17][F:18])[CH:7]=1)=[O:5])[CH3:2].S(=O)(=O)(O)O.N([O-])=O.[Na+].[I-:30].[K+]>O.C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[C:11]2[CH:12]=[C:13]([I:30])[CH:14]=[CH:15][C:10]=2[O:9][C:8]([CH2:19][F:20])([CH2:17][F:18])[CH:7]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 4875Potassium IodideHCID 19037020ethyl 6-amino-2,2-bisfluoromethyl-2H-1-benzopyran-4-carboxylateHCID 23668193Sodium Nitrite

Product 1

HCID 19037016ethyl 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylateYield 65.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent4×HCID 6344DichloromethaneSolvent

Procedure

To a mixture of 4.0 g of 6-amino-2,2-bis(fluoromethyl)-2H-1-benzopyran-4-carboxylic acid ethyl ester, 1.66 g of sulfuric acid and 40 ml of water was added a mixture of 1.09 g of sodium nitrite, 10 ml of methylene chloride and 10 ml of water under ice-cooling. The mixture was stirred under ice-cooling for 10 minutes. Further, to the reaction mixture was added a mixture of 2.85 g of potassium iodide and 5 ml of water, and the mixture was stirred at room temperature for 1.5 hours. To the reaction mixture solution was added water and the resultant solution was extracted with methylene chloride. An organic layer was washed with a 20% aqueous sodium sulfite solution and a saturated saline solution, dried over sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (developing solution, ethyl acetate:hexane=10:1) to obtain 3.67 g of 2,2-bis(fluoromethyl)-6-iodo-2H-1-benzopyran-4-carboxylic acid ethyl ester with a melting point of 89°-90° C.

Workup

  1. additionwas added
  2. temperaturecooling
  3. temperaturecooling for 10 minutes
  4. additionFurther, to the reaction mixture was added
  5. stirringthe mixture was stirred at room temperature for 1.5 hours
  6. extractionthe resultant solution was extracted with methylene chloride
  7. washAn organic layer was washed with a 20% aqueous sodium sulfite solution
  8. dry with materiala saturated saline solution, dried over sodium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9337ac98e8924c4daa56ef20bfa5bb73
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

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