Water → 6-Fluoro-2,5-dimethylquinoline

HRID 1199124

反応式

HRID 1199124 の反応式
Br[C:2]1[C:11]([F:12])=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][C:6]([CH3:13])=[N:7]2.[CH3:14][Mg]Cl.O>[Ni+2].ClC(Cl)(CP(C1C=CC=CC=1)C1C=CC=CC=1)CP(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1.O1CCCC1>[CH3:13][C:6]1[CH:5]=[CH:4][C:3]2[C:8](=[CH:9][CH:10]=[C:11]([F:12])[C:2]=2[CH3:14])[N:7]=1

参加物

7

反応物 3

HCID 962WaterHCID 130353135-Bromo-6-fluoro-2-methylquinolineHCID 178418332HCID 178418332、化合物

生成物 1

HCID 198681766-Fluoro-2,5-dimethylquinoline収率 44%

試薬・触媒・溶媒 3

HCID 131716311dichloro[1,3-bisdiphenylphosphinopropane] nickel (II)触媒HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

Under a nitrogen atmosphere, 28.0 g (0.05 mole) of dichloro[1,3-bis(diphenylphosphino)propane] nickel (II) catalyst (prepared by the method of G. R. Van Hecke and W. DeW. Horrocks, Inorganic Chemistry, 5, 1968 (1966), incorporated herein by reference) was added to a solution of 240 g (1.0 mole) of 5-bromo-6-fluoro-2-methylquinoline in 3.8 liters of toluene. 440 ml (1.4 mole) of 3.17 molar methylmagnesium chloride in tetrahydrofuran was added rapidly to the above mixture, the resulting exotherm being controlled with an ice bath. The reaction was allowed to stir at room temperature overnight. The reaction was treated with 1 liter of water to destroy the excess Grignard reagent, and the organic layer and aqueous layers were then separated. The organic layer was extracted twice with 1 liter portions of 3N hydrochloric acid. The acid extracts were combined, extracted twice with 1 liter portions of methylene chloride, and made basic (pH>9) with ammonium hydroxide and ice. The product was collected as a tan solid (156.4 g, 0.894 mole). This material was recrystallized from 1 liter of hexane to give 77.1 g (0.44 mole) of 2,5-dimethyl-6-fluoroquinoline which was 98.7% pure as determined by gas chromatography analysis.

後処理

  1. customthe resulting exotherm being controlled with an ice bath
  2. customto destroy the excess Grignard reagent
  3. customthe organic layer and aqueous layers were then separated
  4. extractionThe organic layer was extracted twice with 1 liter portions of 3N hydrochloric acid
  5. extractionextracted twice with 1 liter portions of methylene chloride
  6. customThis material was recrystallized from 1 liter of hexane

出典と根拠

ORDレコード
ord-f13e41b20f364585b8923927ccdf70f4
出典データセット
uspto-grants-1990_02
特許番号
US04898945

関連ノート

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