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

HRID 1067650Notes

Reaction equation

HRID 1067650 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:11]2[CH:12]=[C:13](I)[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].[F:21][C:22]([F:27])([F:26])C([O-])=O.[K+].C1(C)C=CC=CC=1>CN(C)C=O>[CH2:1]([O:3][C:4]([C:6]1[C:11]2[CH:12]=[C:13]([C:22]([F:27])([F:26])[F:21])[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

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 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylic acid ethyl ester, 0.84 g of potassium trifluoroacetate, 1.18 g of cuprous iodide, 4 ml of toluene and 10 ml of N,N-dimethylformamide was stirred with heating at 150° C. for 5.5 hours under a nitrogen gas atmosphere while removing toluene. The reaction mixture was combined with a mixture of 2N hydrochloric acid and ethyl acetate, and unsoluble matters were filtered out with Celite. Organic layers were collected from the filtrate and the aqueous layer was extracted with ethyl acetate. The organic layers were combined and washed with saturated saline, dried over sodium sulfate, then concentrated under reduced pressure, and the resulting residue was subjected to silica gel chromatography (eluent: ethyl acetate:hexane=10:1) to give 0.51 g of 2,2-bisfluoromethyl-6-trifluoromethyl-2H-1-benzopyran-4-carboxylic acid ethyl ester as an oil;

Workup

  1. customwhile removing toluene
  2. additionThe reaction mixture was combined with a mixture of 2N hydrochloric acid and ethyl acetate, and unsoluble matters
  3. filtrationwere filtered out with Celite
  4. customOrganic layers were collected from the filtrate
  5. extractionthe aqueous layer was extracted with ethyl acetate
  6. washwashed with saturated saline
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4c1635100aa648e097b5e149dff334af
Source dataset
uspto-grants-2001_06
Patent number
US06248777B1

Reaction notes

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