| 86% |
With bis-triphenylphosphine-palladium(II) chloride In 1,4-dioxane at 90℃; for 4 h; |
The dichlorobis (triphenylphosphine) palladium (II) (1.6g, 2.28mmol, 0.05equiv) was added to the two dioxanyl (100 mL) of 1-bromo-2-fluoro-3-nitrobenzene (10.0g, 45.6mmol, 1equiv) and tri-n-butyl (1-ethoxy-vinyl) stannane (15.4 mL, 45.6mmol, 1equiv) solution.The resulting cloudy solution was heated 4 hours at 90 , during which the formation of a dark brown solution.In TLC (30percent MTBE / heptane) to confirm complete conversion, the reaction was cooled to room temperature.Was added KF (100mL) and ethyl acetate (100 mL), saturated solution, and the biphasic mixture stirred for 1 hour and filtered through celite, washed with ethyl acetate.The organic layer was separated over Na2SO4Sulfate, filtered, and evaporated to give a brown oil of the crude enol ether form.The crude product was dissolved in THF (50mL) and added 2NHCl (50mL).The reaction was stirred at room temperature for 1.5 hours.The reaction was then saturated with NaCl, and extracted with MTBE (2x150mL).Washed with brine (1x300mL) and the organic layer was washed over Na2SO4Sulfate, filtered, and evaporated to give the crude material was eluted through silica gel column chromatography crude material was purified with 0-40percent ethyl acetate / heptane gradient solutions.Compound under reduced pressure, the product-containing fractions evaporated to give a yellow oil of 1- (2-fluoro-3-nitrophenyl) ethanone (7.1g, 86percent yield) |
| 82% |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In 1,4-dioxane at 10 - 95℃; for 4 h; Inert atmosphere; Large scale |
Pd(dppf)C12 (0.13 kg, 0.19 mol) was added to a solution of 1-bromo-2-fluoro-3-nitrobenzene (0.827 kg, 3.6 mol) and tributyl(1-ethoxyvinyl)tin (1.36 kg, 3.6 mol) in 1,4-dioxane (8.27 kg) at 10-30°C under N2. The solution was heated to 85-95°C and thetemperature was maintained at 85-95°C for 4 h under N2. The mixture was cooled to 10- 30°C, then ethyl acetate (8.27 L) and saturated aqueous KF solution (4 L) were added.The mixture was stirred for 1 h, then the solution was filtered through a pad of celite and washed with ethyl acetate (2 L). The organic layer was separated and dried over Na2SO4,then concentrated. The resulting crude material was combined with two similar batches, then treated with THF (12.5 L) and 2N HC1 (12.5 L). The mixture was stirred at 10-25°C for 3 h, then extracted with ethyl acetate (3 x 20 L). The organic phase was separated and washed with saturated aqueous NaHCO3 solution (10 L) and brine (10 L), then the solvent was concentrated. The crude residue was purified by chromatography (silica, 100-200mesh, 4percent EtOAc in petroleum ether) to give the title compound (1.70 kg, 82percent). oH (400MHz, CDC13) 8.21-8.13 (m, 2H), 7.42-7.38 (m, 1H), 2.71-2.69 (d, J5.2 Hz, 3H). |
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