Toluene → ethyl 2,2-bisfluoromethyl-6-trifluoromethyl-2H-1-benzopyran-4-carboxylate

HRID 264824

Reaction equation

HRID 264824 reaction equation
[F:1][CH2:2][C:3]1([CH2:19][F:20])[CH:8]=[C:7]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:6]2[CH:14]=[C:15](I)[CH:16]=[CH:17][C:5]=2[O:4]1.[F:21][C:22]([F:27])([F:26])C([O-])=O.[K+].C1(C)C=CC=CC=1>CN(C)C=O>[F:1][CH2:2][C:3]1([CH2:19][F:20])[CH:8]=[C:7]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:6]2[CH:14]=[C:15]([C:22]([F:27])([F:26])[F:21])[CH:16]=[CH:17][C:5]=2[O:4]1

Participants

5

Reactant 3

HCID 1140TolueneHCID 19037016ethyl 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylateHCID 23662811Potassium trifluoroacetate

Product 1

HCID 19037095ethyl 2,2-bisfluoromethyl-6-trifluoromethyl-2H-1-benzopyran-4-carboxylateYield 59.8%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 1.00 g of ethyl 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylate, 0.84 g of potassium trifluoroacetate, 1.18 g of cuprous iodide, 4 ml of toluene and 10 ml of N,N-dimethylformamide was heated with stirring at 150° C. for 5.5 hours in a nitrogen gas atmosphere while removing toluene. The reaction mixture was added to a mixed solution of 2N hydrochloric acid and ethyl acetate, and an insoluble material was separated by filtration using celite. The organic layer was separated from the filtrate, and the aqueous layer was extracted with ethyl acetate. The resulting organic layers were combined, washed with a brine, dried over sodium sulfate and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography (an eluting solvent, ethyl acetate:hexane =10:1) to obtain 0.51 g of ethyl 2,2-bisfluoromethyl-6-trifluoromethyl-2H-1-benzopyran-4-carboxylate as an oily substance.

Workup

  1. temperaturewas heated
  2. customwhile removing toluene
  3. additionThe reaction mixture was added to a mixed solution of 2N hydrochloric acid and ethyl acetate
  4. customan insoluble material was separated by filtration
  5. customThe organic layer was separated from the filtrate
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. washwashed with a brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-2e1e4b4c1fbe43408df122cb91c8598a
Source dataset
uspto-grants-1997_07
Patent number
US05646310

Linked notes

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