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

HRID 708804

反応式

HRID 708804 の反応式
[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

参加物

5

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 23978Copper触媒HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
60 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-43108a86b60045159095cf0762cf1d8c
出典データセット
uspto-grants-2015_11
特許番号
US09174974B2

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