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Hydrochloric Acid → 2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxylic acid

HRID 1282420
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HRID 1282420 반응식
Br[C:2]1[C:7]2[CH:8]=[C:9]([C:12]([F:15])([F:14])[F:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH2:18][F:19])([CH2:16][F:17])[CH:3]=1.[C:20]([O-:23])(=[O:22])C.[K+].[I-].[K+].Cl>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C)C(=O)C>[F:17][CH2:16][C:4]1([CH2:18][F:19])[CH:3]=[C:2]([C:20]([OH:23])=[O:22])[C:7]2[CH:8]=[C:9]([C:12]([F:15])([F:14])[F:13])[CH:10]=[CH:11][C:6]=2[O:5]1
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참가 물질

8

반응물 4

HCID 313Hydrochloric AcidHCID 4875Potassium IodideHCID 517044Potassium AcetateHCID 184244094-bromo-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran

생성물 1

HCID 98796402,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxylic acid수율 80.9%

시약·촉매·용매 3

HCID 11776
Triphenylphosphine
촉매
HCID 167845palladium(II) acetate촉매
HCID 31374Dimethylacetamide용매

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온도
120 °C

실험 절차

A mixture of 4-bromo-2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran (1.72 g), potassium acetate (2.00 g), potassium iodide (0.85 g), triphenylphosphine (27 mg), palladium acetate (11 mg) and N,N-dimethylacetamide (10 ml) was stirred under a CO atmosphere at 120° C. for 9 hours. To the reaction mixture, 2 N HCl was added and the precipitating crystals were recovered by filtration. To the recovered crystals, ethyl acetate was added and the insoluble matter was filtered off; the filtrate was washed with a saturated aqueous solution of sodium thiosulfate and a saturated aqueous solution of sodium chloride, dried with anhydrous sodium sulfate and concentrated under reduced pressure; the resulting residue was dissolved in a saturated aqueous solution of sodium hydrogencarbonate and washed with dichloromethane; to the resulting aqueous layer, concentrated HCl was added to render it acidic and the precipitating crystals were recovered by filtration. The recovered crystals were dissolved in ethyl acetate, dried with anhydrous magnesium sulfate and concentrated under reduced pressure; the resulting residue was recrystallized with an ethyl acetate/hexane mixed solvent to give 2,2-bis(fluoromethyl)-6-trifluoromethyl-2H-1-benzopyran-4-carboxylic acid (1.25 g) having a melting point of 162-163° C.

후처리

  1. filtrationthe precipitating crystals were recovered by filtration
  2. additionTo the recovered crystals, ethyl acetate was added
  3. filtrationthe insoluble matter was filtered off
  4. washthe filtrate was washed with a saturated aqueous solution of sodium thiosulfate
  5. dry with materiala saturated aqueous solution of sodium chloride, dried with anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. dissolutionthe resulting residue was dissolved in a saturated aqueous solution of sodium hydrogencarbonate
  8. washwashed with dichloromethane
  9. additionto the resulting aqueous layer, concentrated HCl was added
  10. filtrationthe precipitating crystals were recovered by filtration
  11. dissolutionThe recovered crystals were dissolved in ethyl acetate
  12. dry with materialdried with anhydrous magnesium sulfate
  13. concentrationconcentrated under reduced pressure
  14. customthe resulting residue was recrystallized with an ethyl acetate/hexane mixed solvent

출처 및 근거

ORD 기록
ord-402579526651490487574261b934a424
출처 데이터셋
uspto-grants-2002_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06455708B1

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