Reaktion #729436

Reaktionsgleichung

4-fluoroaniline

3,3-dimethyl-1-nitro-but-1-ene

ethyl acetoacetate

sodium

→

title product

4-tert-Butyl-1-(4-fluoro-phenyl)-2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester

Lösungsmittel

toluene

ether

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigethen the reaction was quenched with saturated ammonium chloride aqueous solution
2. 2
   Waschenthe ether layer was washed with saturated NaCl aqueous solution
3. 3
   Trocknendried over anhydrous sodium sulfate
4. 4
   Filtrationfiltered
5. 5
   Einengenconcentrated
6. 6
   Sonstigeto give a mixture, which
7. 7
   Sonstigereaction
8. 8
   Sonstigewithout further purification and characterization
9. 9
   Temperaturwas refluxed overnight
10. 10
    workup.DISTILLATIONthe generated water was collected with a Dean-Stark distillation apparatus
11. 11
    Temperaturthen the reaction was cooled to room temperature
12. 12
    workup.ADDITIONdiluted with EtOAc
13. 13
    Waschenwashed with diluted HCl aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated NaCl aqueous solution respectively
14. 14
    Trocknendried over anhydrous sodium sulfate
15. 15
    Filtrationfiltered
16. 16
    Einengenconcentrated
17. 17
    Sonstigethe residue was purified with column
18. 18
    Sonstigeto give a slightly brown oil

Vorschrift

A mixture of 3,3-dimethyl-1-nitro-but-1-ene (6.2 g, 36 mmol) and ethyl acetoacetate, sodium salt (5.76 g, 36 mmol) in ether (50 mL) was stirred at 0° C. for 30 min; then the reaction was quenched with saturated ammonium chloride aqueous solution, the ether layer was washed with saturated NaCl aqueous solution dried over anhydrous sodium sulfate, filtered, concentrated, to give a mixture, which was used next reaction without further purification and characterization. The above mixture was refluxed with 4-fluoroaniline (4.09 mL, 43.2 mmol), and TsOH monohydrate (343 mg, 1.8 mmol) in toluene (100 mL) was refluxed overnight, the generated water was collected with a Dean-Stark distillation apparatus; then the reaction was cooled to room temperature, diluted with EtOAc, washed with diluted HCl aqueous solution, saturated sodium bicarbonate aqueous solution, and saturated NaCl aqueous solution respectively, then dried over anhydrous sodium sulfate filtered, concentrated, the residue was purified with column to give a slightly brown oil, the title product (1.904 g); The title compound, ESI MS (m/z): 304 (M+H+).

Quelle