N,N-二甲基甲酰胺 → 4-甲基-2-硝基三氟甲基苯

HRID 257573笔记

反应方程式

HRID 257573 反应方程式
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]

参与物

6

反应物 4

HCID 6228N,N-二甲基甲酰胺HCID 739352-氯-2,2-二氟乙酸甲酯HCID 792244-溴-3-硝基甲苯HCID 522689Potassium Fluoride

产物 1

HCID 197831564-甲基-2-硝基三氟甲基苯收率 57%

试剂、催化剂与溶剂 1

HCID 311ubiquitin cross-reactive protein溶剂

反应条件

温度
110 °C

实验过程

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).

后处理

  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)

来源与证据

ORD记录
ord-9226506e77cd4c338434ebf0c8e1403d
来源数据集
uspto-grants-1993_11
专利号
US05262412

反应笔记

加载中…