反应详情

Under argon, a suspension of 49.3 g (513 mmol) of potassium tert-butanolate was introduced as initial charge at RT in 360 ml of dioxane, and 82.2 g (513 mmol) of diethyl malonate were added such that the temperature remained below 30° C. The reaction mixture was stirred for 1 h at RT, 3.4 g (11.0 mmol) of bis(2-pyridinecarboxylato)copper(II) complex and 49.7 g (147 mmol) of 3-bromo-1-[2-(methoxymethyl)-4-nitrophenyl]pyridin-2(1H)-one were added and the mixture was stirred for 4.5 h at 95° C. A further 2.0 g (6.5 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were added and the reaction mixture was stirred overnight at 95° C. After cooling to RT, the mixture was diluted with 0.9 l of ethyl acetate, 1.8 l of 3N hydrochloric acid were added and the mixture was stirred for 15 min at RT. The aqueous phase was extracted with 0.9 l of ethyl acetate and the combined organic phases were washed with saturated aqueous sodium chloride solution. After drying over sodium sulphate, filtration and removal of the solvent on a rotary evaporator, the residue was dried in vacuo. This gave 115 g of crude product, which was reacted further without purification.

1. additionwas introduced
2. customremained below 30° C
3. stirringthe mixture was stirred for 4.5 h at 95° C
4. additionA further 2.0 g (6.5 mmol) of bis(2-pyridinecarboxylato)copper(II) complex were added
5. stirringthe reaction mixture was stirred overnight at 95° C
6. temperatureAfter cooling to RT
7. additionwere added
8. stirringthe mixture was stirred for 15 min at RT
9. extractionThe aqueous phase was extracted with 0.9 l of ethyl acetate
10. washthe combined organic phases were washed with saturated aqueous sodium chloride solution
11. dry with materialAfter drying over sodium sulphate, filtration and removal of the solvent on a rotary evaporator
12. customthe residue was dried in vacuo
13. customThis gave 115 g of crude product, which was reacted further without purification