Potassium Iodide → HCID 46896511、化合物

HRID 241986ノート

反応式

HRID 241986 の反応式
[N+:1](=[C:3]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[F:14])=[N:6][N:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[F:21])[C:4]1=[O:22])=[N-:2].C(P(CCCC)CCCC)CCC.Cl[CH2:37][C:38]1[CH:43]=[CH:42][C:41]([N:44]2[CH:48]=[CH:47][N:46]=[CH:45]2)=[CH:40][CH:39]=1.[I-].[K+].C(=O)([O-])[O-].[K+].[K+]>C(#N)C.O>[F:14][C:9]1[C:8]2[C:7]3[C:3]([C:4](=[O:22])[N:5]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=4[F:21])[N:6]=3)=[N:1][N:2]([CH2:37][C:38]3[CH:39]=[CH:40][C:41]([N:44]4[CH:48]=[CH:47][N:46]=[CH:45]4)=[CH:42][CH:43]=3)[C:13]=2[CH:12]=[CH:11][CH:10]=1

参加物

8

反応物 5

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 13831TributylphosphineHCID 70638591-(4-(Chloromethyl)phenyl)-1H-imidazoleHCID 178514319HCID 178514319、化合物

生成物 1

HCID 46896511HCID 46896511、化合物

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6342Acetonitrile溶媒

実験手順

4-Diazo-2,5-bis(2-fluorophenyl)-2,4-dihydro-3H-pyrazol-3-one (0.17 g, 0.56 mmol) was dissolved in acetonitrile (5 mL) and treated with tri-n-butylphosphine (0.11 g, 0.56 mmol, 1.0 equiv). After stirring for 30 minutes at ambient temperature, 1-[4-(chloromethyl)phenyl]-1H-imidazole (0.11 g, 0.56 mmol, 1.0 equiv), potassium iodide (47 mg, 0.28 mmol, 0.5 equiv) and potassium carbonate (97 mg, 0.70 mmol, 1.25 equiv) were added at ambient temperature. After 45 minutes, the reaction mixture was warmed to 85° C., stirred for 2.5 hours and then cooled to ambient temperature. The mixture was poured into water (100 mL), extracted with ethyl acetate (2×75 mL) and the combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified twice by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 10% methanol; and then 100:0 to 90:10; dichloromethane:methanol containing 10% ammonium hydroxide), providing the titled compound as a deep red solid: 1H-NMR (400 MHz, CDCl3) δ 8.33 (1H, dd, J=7.6, 1.8 Hz), 7.85 (1H, br s), 7.67-7.53 (4H, m), 7.46 (2H, d, J=8.5 Hz), 7.40 (2H, d, J=8.5 Hz), 7.42-7.37 (1H, m), 7.31-7.20 (4H, m), 5.88 (2H, s) ppm; high resolution mass spectrometry (ES+) m/z 437.1526 [(M+H)+; calculated for C25H18FN6O: 437.1521].

後処理

  1. waitAfter 45 minutes
  2. temperaturethe reaction mixture was warmed to 85° C.
  3. stirringstirred for 2.5 hours
  4. temperaturecooled to ambient temperature
  5. extractionextracted with ethyl acetate (2×75 mL)
  6. dry with materialthe combined organic extracts were dried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified twice by silica gel gradient chromatography (100:0 to 0:100

出典と根拠

ORDレコード
ord-7f12b7f3609f415dab3821db2a863fff
出典データセット
uspto-grants-2014_02
特許番号
US08653079B2

反応ノート

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