Ethyl bromodifluoroacetate → HCID 66913596, compound

HRID 2405154Notes

Reaction equation

HRID 2405154 reaction equation
I[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[CH2:10]([O:12][C:13](=[O:18])[C:14](Br)([F:16])[F:15])[CH3:11]>[Cu].CS(C)=O>[CH2:10]([O:12][C:13](=[O:18])[C:14]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1)([F:16])[F:15])[CH3:11]

Participants

5

Reactant 2

HCID 69585Ethyl bromodifluoroacetateHCID 764674-Iodobenzonitrile2×

Product 1

HCID 66913596HCID 66913596, compound

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
55 °C

Procedure

According to the Kumadaki method (K. Sato et al., Chem. Pharm. Bull., vol. 47 p. 1013 (1999)) and the above-described scheme, 4-iodobenzonitrile (Compound 1a; 343.5 mg, 1.5 mmol), bromodifluoroacetic acid ethyl ester (304.5 mg, 1.5 mmol), copper powder (190.5 mg, 3.0 mmol) and DMSO (3.0 mL) were put into a two-neck reaction tube, and the mixture was stirred under argon atmosphere at 55° C. for 24 hours. The reaction mixture was extracted with ethyl acetate and washed with water, and an organic layer was dried with anhydrous sodium sulfate. Ethyl acetate was distilled away under reduced pressure, and by carrying out purification by silica gel column chromatography, 2-(4-cyanophenyl)-2,2-difluoroacetic acid ethyl ester (Compound 2a) was obtained with a yield of 60%.

Workup

  1. extractionThe reaction mixture was extracted with ethyl acetate
  2. washwashed with water
  3. dry with materialan organic layer was dried with anhydrous sodium sulfate
  4. distillationEthyl acetate was distilled away under reduced pressure
  5. custompurification by silica gel column chromatography

Sources & evidence

ORD record
ord-341fdb4e03b64c9aaf96015356658de3
Source dataset
uspto-grants-2014_08
Patent number
US08802886B2

Reaction notes

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