Dimethylformamide → 4-Methyl-2-nitro-1-(trifluoromethyl)benzene

HRID 257573

反応式

HRID 257573 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].Cl[C:13]([F:19])([F:18])C(OC)=O.[F-:20].[K+].CN(C=O)C>C(O)(=O)CC(CC(O)=O)(C(O)=O)O>[N+:9]([C:3]1[CH:4]=[C:5]([CH3:8])[CH:6]=[CH:7][C:2]=1[C:13]([F:19])([F:20])[F:18])([O-:11])=[O:10]

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 73935Methyl chlorodifluoroacetateHCID 792244-Bromo-3-nitrotolueneHCID 522689Potassium Fluoride

生成物 1

HCID 197831564-Methyl-2-nitro-1-(trifluoromethyl)benzene収率 57%

試薬・触媒・溶媒 1

HCID 311Citric Acid溶媒

反応条件

温度
110 °C

実験手順

A mixture of 6.00 g (27.8 mmol) of 4-bromo-3-nitrotoluene, 5.86 mL (8.03 g, 55.6 mmol) of methyl chlorodifluoroacetate, 1.93 g (33.4 mmol) of potassium fluoride, 5.31 g (27.8 mmol) of cuprous iodide, and 25 mL of dry DMF was stirred at 110° C. for 2 days. The cooled material was diluted with aqueous citric acid and extracted 3× with ethyl acetate. The combined organic extracts were washed with H2O, then with brine, and dried over anhydrous Na2SO4. The residue obtained upon concentration of the filtered solution was flash chromatographed 3× on silica gel (elution with 100:1 and 25:1 hexane-EtOAc) to give 3.25 g (57%) of the title compound as a yellow liquid; homogeneous by TLC in 4:1 hexane-EtOAc; mass spectrum (EI) m/e 205 (M+). 400 MHz 1H NMR (CDCl3) δ2.48 (s, 3H), 7.49 (d, J=8 Hz, 1H), 7.67 (s, 1H) overlapping 7.68 (d, J=8 Hz, 1H).

後処理

  1. extractionextracted 3× with ethyl acetate
  2. washThe combined organic extracts were washed with H2O
  3. dry with materialwith brine, and dried over anhydrous Na2SO4
  4. customThe residue obtained upon concentration of the filtered solution
  5. customchromatographed 3× on silica gel (elution with 100:1 and 25:1 hexane-EtOAc)

出典と根拠

ORDレコード
ord-9226506e77cd4c338434ebf0c8e1403d
出典データセット
uspto-grants-1993_11
特許番号
US05262412

関連ノート

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