Ethyl bromodifluoroacetate → Ethyl 2-(4-bromo-2,6-dimethylphenyl)-2,2-difluoroacetate

HRID 708804

반응식

HRID 708804 반응식
[Br:1][C:2]1[CH:3]=[C:4]([CH3:10])[C:5](I)=[C:6]([CH3:8])[CH:7]=1.Br[C:12]([F:19])([F:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14]>CS(C)=O.[Cu]>[Br:1][C:2]1[CH:3]=[C:4]([CH3:10])[C:5]([C:12]([F:19])([F:18])[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:6]([CH3:8])[CH:7]=1

참가 물질

5

반응물 2

HCID 69585Ethyl bromodifluoroacetateHCID 27355735-Bromo-2-iodo-1,3-dimethylbenzene

생성물 1

HCID 118098676Ethyl 2-(4-bromo-2,6-dimethylphenyl)-2,2-difluoroacetate수율 88.3%

시약·촉매·용매 2

HCID 23978Copper촉매HCID 679Dimethyl Sulfoxide용매

반응 조건

온도
60 °C

실험 절차

To a degassed solution of 5-bromo-2-iodo-1,3-dimethylbenzene (3.9 g, 12.54 mmol) and ethyl 2-bromo-2,2-difluoroacetate (3.22 ml, 25.08 mmol) in DMSO (30 ml) was added copper (3.19 g, 50.2 mmol). The reaction mixture was stirred at 60° C. for 3 h, then cooled to r.t. and filtered. The filtrate was diluted with EtOAc and water, extracted with EtOAc (3×). The combined organic layer was washed with brine, dried with MgSO4, filtered and concentrated. The crude product was purified by flash chromatography to give Intermediate 7A (3.4 g, 11.07 mmol, 88% yield) as a colorless oil. 1H NMR (400 MHz, chloroform-d) δ ppm 1.32 (t, J=7.03 Hz, 3H) 2.44 (t, J=4.17 Hz, 6H) 4.32 (q, J=7.18 Hz, 2H) 7.23 (s, 2H). 19F NMR (376 MHz, chloroform-d) δ ppm −95.28 (br. s., 2F).

후처리

  1. temperaturecooled to r.t.
  2. filtrationfiltered
  3. additionThe filtrate was diluted with EtOAc and water
  4. extractionextracted with EtOAc (3×)
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried with MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by flash chromatography

출처 및 근거

ORD 기록
ord-43108a86b60045159095cf0762cf1d8c
출처 데이터셋
uspto-grants-2015_11
특허 번호
US09174974B2

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