Potassium Iodide → 3-((3-Fluoro-4-nitrophenoxy)methyl)-1-methyl-1H-pyrazole

HRID 1527738ノート

反応式

HRID 1527738 の反応式
[F:1][C:2]1[CH:3]=[C:4]([OH:11])[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].Cl.Cl[CH2:14][C:15]1[CH:19]=[CH:18][N:17]([CH3:20])[N:16]=1.C(=O)([O-])[O-].[K+].[K+].[I-].[K+]>C(#N)C>[F:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9])[O:11][CH2:14][C:15]1[CH:19]=[CH:18][N:17]([CH3:20])[N:16]=1

参加物

6

反応物 4

HCID 4875Potassium IodideHCID 11430Potassium CarbonateHCID 5209483-Fluoro-4-nitrophenolHCID 128450493-(Chloromethyl)-1-methyl-1H-pyrazole--hydrogen chloride (1/1)

生成物 1

HCID 828819703-((3-Fluoro-4-nitrophenoxy)methyl)-1-methyl-1H-pyrazole収率 90.8%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

A solution of 3-fluoro-4-nitrophenol (50.0 g, 0.31 mol), 3-(chloromethyl)-1-methyl-1H-pyrazole hydrochloride (52.1 g, 0.31 mol), powdered potassium carbonate (53.3 g, 0.38 mol), potassium iodide (52.8 g, 0.32 mol), and acetonitrile (900 mL) was stirred at 60° Celsius for 8 h. The reaction was cooled to RT and concentrated to dryness. The residue was partitioned between H2O (500 mL), sat. NaHCO3 (200 mL), and ethyl acetate (900 mL). The organic layer was separated, dried with MgSO4, filtered and concentrated to dryness. The resulting residue was recrystallized from ethanol (250 mL) and H2O (250 mL). The solid was collected by filtration and rinsed with a H2O/ethanol (2:1, 225 mL) followed by hexanes (250 mL) yielding the title compound as a tan solid (70.7 g, 90.2%). MS (ESI): mass calcd. for C11H10FN3O3, 251.1; m/z found, 252.0 [M+H]+. 1H NMR (400 MHz, CDCl3) δ 8.13-8.03 (m, 1H), 7.42-7.32 (d, J=2.2, 1H), 6.93-6.87 (m, 1H), 6.87-6.84 (d, J=1.6, 1H), 6.36-6.29 (d, J=2.2, 1H), 5.18-5.10 (s, 2H), 4.00-3.87 (s, 3H).

後処理

  1. concentrationconcentrated to dryness
  2. customThe residue was partitioned between H2O (500 mL), sat. NaHCO3 (200 mL), and ethyl acetate (900 mL)
  3. customThe organic layer was separated
  4. dry with materialdried with MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated to dryness
  7. customThe resulting residue was recrystallized from ethanol (250 mL) and H2O (250 mL)
  8. filtrationThe solid was collected by filtration
  9. washrinsed with a H2O/ethanol (2:1, 225 mL)

出典と根拠

ORDレコード
ord-2154b4b5690645e9819e3d546d087e0b
出典データセット
uspto-grants-2015_07
特許番号
US09089569B2

反応ノート

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