Sodium Iodide → 1-(4,4-Difluorobut-3-enyloxy)-3-((4-(difluoromethoxy)phenyl)ethynyl)benzene

HRID 30592

反応式

HRID 30592 の反応式
[F:1][CH:2]([F:19])[O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]#[C:11][C:12]2[CH:13]=[C:14]([OH:18])[CH:15]=[CH:16][CH:17]=2)=[CH:6][CH:5]=1.C(=O)([O-])[O-].[K+].[K+].[I-].[Na+].Br[CH2:29][CH2:30][CH:31]=[C:32]([F:34])[F:33]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].C(C(C)=O)C.ClCCl>[F:33][C:32]([F:34])=[CH:31][CH2:30][CH2:29][O:18][C:14]1[CH:15]=[CH:16][CH:17]=[C:12]([C:11]#[C:10][C:7]2[CH:6]=[CH:5][C:4]([O:3][CH:2]([F:19])[F:1])=[CH:9][CH:8]=2)[CH:13]=1

参加物

8

反応物 4

HCID 5238Sodium IodideHCID 11430Potassium CarbonateHCID 27822404-Bromo-1,1-difluorobut-1-eneHCID 597903213-((4-(Difluoromethoxy)phenyl)ethynyl)phenol

生成物 1

HCID 597903171-(4,4-Difluorobut-3-enyloxy)-3-((4-(difluoromethoxy)phenyl)ethynyl)benzene収率 46.2%

試薬・触媒・溶媒 3

HCID 21218Trioctylmethylammonium chloride触媒HCID 6344Dichloromethane溶媒HCID 6569Methyl Ethyl Ketone溶媒

反応条件

温度
80 °C

実験手順

A mixture of 3-((4-(difluoromethoxy)phenyl)ethynyl)phenol (900 mg), potassium carbonate (636 mg), Aliquat 336 (4 drops), sodium iodide (catalytic) and 4-bromo-1,1-difluoro-1-butene (591 μL) in methyl ethyl ketone was placed in a pressure vessel, heated at 80° C. for 15 h, cooled to room temperature, diluted with dichloromethane and filtered. The filtrate was concentrated in vacuo. The resultant residue was purified by flash chromatography (silica gel, eluant: 2.5% ethyl acetate/hexane to afford 1-(4,4-difluorobut-3-enyloxy)-3-((4-(difluoromethoxy)phenyl)ethynyl)benzene, 560 mg (46.2% yield); 1H NMR (chloroform-d1): δ 7.51 (d, J=8.8 Hz, 2H), 7.24 (m, 1H), 7.10 (m, 1H), 7.08 (d, J=8.8 Hz, 2H), 7.03 (m, 1H), 6.87 (m, 1H), 6.52 (t, J=73.5 Hz, 1H), 4.32 (m, 1H), 3.97 (t, J=6.4 Hz, 2H) and 2.47 (m, J=6.4 Hz, 2H); MS (ES pos) m/z 350.

後処理

  1. customwas placed in a pressure vessel
  2. temperaturecooled to room temperature
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated in vacuo
  5. customThe resultant residue was purified by flash chromatography (silica gel, eluant

出典と根拠

ORDレコード
ord-04f34b7d441e4224abcdfc90649b95ba
出典データセット
uspto-grants-2008_09
特許番号
US07423158B2

関連ノート

読み込み中…