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

HRID 257573

Reaktionsgleichung

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]

Komponenten

Reaktionsbedingungen

Temperatur: 110 °C

Versuchsvorschrift

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).

Aufarbeitung

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

Quellen und Nachweise

ORD-Eintrag: ord-9226506e77cd4c338434ebf0c8e1403d
Quelldatensatz: uspto-grants-1993_11
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US05262412

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