Ethyl bromodifluoroacetate → Ethyl 2-(5-(4-cyanophenoxy)pyridin-2-yl)-2,2-difluoroacetate

HRID 63253

反応式

HRID 63253 の反応式
Br[C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4].Br[C:11]1[N:16]=[CH:15][C:14]([O:17][C:18]2[CH:25]=[CH:24][C:21]([C:22]#[N:23])=[CH:20][CH:19]=2)=[CH:13][CH:12]=1>CS(C)=O.C(OCC)(=O)C.[Cu]>[C:22]([C:21]1[CH:20]=[CH:19][C:18]([O:17][C:14]2[CH:13]=[CH:12][C:11]([C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4])=[N:16][CH:15]=2)=[CH:25][CH:24]=1)#[N:23]

参加物

6

反応物 2

HCID 69585Ethyl bromodifluoroacetateHCID 451422674-((6-Bromopyridin-3-yl)oxy)benzonitrile

生成物 1

HCID 90052223Ethyl 2-(5-(4-cyanophenoxy)pyridin-2-yl)-2,2-difluoroacetate収率 56.5%

試薬・触媒・溶媒 3

HCID 23978Copper触媒HCID 679Dimethyl Sulfoxide溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A mixture of ethyl 2-bromo-2,2-difluoroacetate (22.13 mL, 109.05 mmol) and copper (13.85 g, 218.1 mmol) in dry dimethylsulfoxide (DMSO) (80 mL) was stirred at room temperature (rt) for 4 h. 4-((6-Bromopyridin-3-yl)oxy)benzonitrile (10 g, 36.35 mmol) was added and the mixture heated at 50° C. for 16 h. The reaction mixture was cooled to room temperature, diluted with 200 mL of ethyl acetate (EtOAc) and stirred for 10 min. The mixture was filtered through a plug of Celite® and the filtrate was washed with saturated NH4Cl solution to remove any remaining copper. The solution was dried (Na2SO4) and solvent was removed under reduced pressure to give the title compound as brown oil (6.5 g, 56.5%): IR (thin film) 2229, 1767 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.44 (d, J=2.7 Hz, 1H), 7.78 (d, J=8.7 Hz, 1H), 7.73-7.64 (m, 2H), 7.49 (dd, J=8.6, 2.7 Hz, 1H), 7.16-7.07 (m, 2H), 4.39 (q, J=7.1 Hz, 2H), 1.35 (t, J=7.2 Hz, 3H); ESIMS m/z 319 ([M+H]+).

後処理

  1. temperaturethe mixture heated at 50° C. for 16 h
  2. temperatureThe reaction mixture was cooled to room temperature
  3. stirringstirred for 10 min
  4. filtrationThe mixture was filtered through a plug of Celite®
  5. washthe filtrate was washed with saturated NH4Cl solution
  6. customto remove any remaining copper
  7. dry with materialThe solution was dried (Na2SO4) and solvent
  8. customwas removed under reduced pressure

出典と根拠

ORDレコード
ord-02423e094bc241c49175ffd10b6637c0
出典データセット
uspto-grants-2016_09
特許番号
US09447073B2

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