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

HRID 257573

반응식

HRID 257573 반응식
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]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 311Citric Acid용매

반응 조건

온도
110 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-9226506e77cd4c338434ebf0c8e1403d
출처 데이터셋
uspto-grants-1993_11
특허 번호
US05262412

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