4-Fluoroiodobenzene → 6-bromo-1-(4-fluoro-phenyl)-1H-indazole-4-carboxylic acid methyl ester

HRID 1677705ノート

反応式

HRID 1677705 の反応式
[CH3:1][O:2][C:3]([C:5]1[C:6]2[CH:7]=[N:8][NH:9][C:10]=2[CH:11]=[C:12]([Br:14])[CH:13]=1)=[O:4].C(=O)([O-])[O-].[K+].[K+].[F:21][C:22]1[CH:27]=[CH:26][C:25](I)=[CH:24][CH:23]=1.CN[C@@H]1CCCC[C@H]1NC>O.C(OCC)(=O)C.[Cu]I.CN(C=O)C>[CH3:1][O:2][C:3]([C:5]1[C:6]2[CH:7]=[N:8][N:9]([C:25]3[CH:26]=[CH:27][C:22]([F:21])=[CH:23][CH:24]=3)[C:10]=2[CH:11]=[C:12]([Br:14])[CH:13]=1)=[O:4]

参加物

9

反応物 4

HCID 96054-FluoroiodobenzeneHCID 11430Potassium CarbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 24728062methyl 6-bromo-1H-indazole-4-carboxylate

生成物 1

HCID 581387736-bromo-1-(4-fluoro-phenyl)-1H-indazole-4-carboxylic acid methyl ester

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
120 °C

実験手順

A mixture of 6-bromo-4-indazolecarboxylic acid methyl ester (2.0 g, 7.8 mmol), copper(I) iodide (0.4 g, 0.2 mmol), potassium carbonate (1.2 g, 8.5 mmol) and 4-fluoroiodobenzene (1.8 g, 8.5 mmol) was charged in a sealed tube at room temperature. The tube was evacuated and back-filled with argon, and DMF (10 mL) and rac-trans-N,N′-dimethylcyclohexane-1,2-diamine (0.20 g, 1.4 mmol) was added. The solution was stirred at 120° C. for 3 hours, cooled to room temperature, and diluted with water (30 mL) and ethyl acetate (50 mL). The organic layer was separated, washed with brine (10 mL) and dried over sodium sulfate. The solvent was removed in vacuo. The residue was purified by silica gel chromatography eluting with a gradient of 0-30% ethyl acetate in hexanes to afford 6-bromo-1-(4-fluoro-phenyl)-1H-indazole-4-carboxylic acid methyl ester.

後処理

  1. additionwas charged in a sealed tube at room temperature
  2. customThe tube was evacuated
  3. additionwas added
  4. temperaturecooled to room temperature
  5. customThe organic layer was separated
  6. washwashed with brine (10 mL)
  7. dry with materialdried over sodium sulfate
  8. customThe solvent was removed in vacuo
  9. customThe residue was purified by silica gel chromatography
  10. washeluting with a gradient of 0-30% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-8ca364cebcb24a77a6a290ce4b5477df
出典データセット
uspto-grants-2011_08
特許番号
US08008327B2

反応ノート

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