Methyl chlorodifluoroacetate → 1-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene

HRID 74008

反応式

HRID 74008 の反応式
[C:1]([C:5]1[CH:10]=[C:9](Br)[C:8]([N+:12]([O-:14])=[O:13])=[CH:7][C:6]=1[O:15][CH3:16])([CH3:4])([CH3:3])[CH3:2].[F-:17].[K+].[K+].[Br-].Cl[C:22]([F:28])([F:27])C(OC)=O>CN(C=O)C.O.[Cu]I>[C:1]([C:5]1[CH:10]=[C:9]([C:22]([F:28])([F:17])[F:27])[C:8]([N+:12]([O-:14])=[O:13])=[CH:7][C:6]=1[O:15][CH3:16])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 4

HCID 73935Methyl chlorodifluoroacetateHCID 253877Potassium BromideHCID 522689Potassium FluorideHCID 574702451-Bromo-5-(tert-butyl)-4-methoxy-2-nitrobenzene

生成物 1

HCID 574702461-Tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene収率 61.6%

試薬・触媒・溶媒 3

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

反応条件

温度
125 °C

実験手順

A mixture of 1-tert-butyl-2-methoxy-5-bromo-4-nitrobenzene (867 mg, 3.0 mmol), KF (348 mg, 6 mmol), KBr (714 mg, 6 mmol), CuI (684 mg, 3.6 mmol), methyl chlorodifluoroacetate (2.2 mL, 21.0 mmol) in DMF (5 mL) was stirred at 125° C. in a sealed tube overnight, cooled to room temperature, diluted with water and extracted three times with EtOAc. The combined organic layers were washed with brine and dried over anhydrous MgSO4. After removal of the solvent, the residue was purified by column chromatography (0-5% EtOAc-Hexane) to yield 1-tert-butyl-2-methoxy-5-(trifluoromethyl)-4-nitrobenzene (512 mg, 61%). 1H NMR (400 MHz, CDCl3) δ 7.60 (s, 1H), 7.29 (s, 1H), 3.90 (s, 3H), 1.33 (s, 9H).

後処理

  1. temperaturecooled to room temperature
  2. extractionextracted three times with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over anhydrous MgSO4
  5. customAfter removal of the solvent
  6. customthe residue was purified by column chromatography (0-5% EtOAc-Hexane)

出典と根拠

ORDレコード
ord-e77fe0383fc346d59ce7a71dd0be2d9e
出典データセット
uspto-grants-2014_09
特許番号
US08829204B2

関連ノート

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