Phosphorus oxychloride → 2,5-dichloro-4-nitropyridine

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Reaction Steps

To a solution of phosphorus oxychloride (6.40 μL, 73.21 mmol) in chloroform (61.2 mL) was added 2,5-dichloro-4-nitropyridine 1-oxide (3.06 g, 14.64 mmol), and the mixture was stirred under reflux overnight. The reaction solution was poured into ice, adjusted by saturated aqueous sodium hydrogen carbonate solution to pH7 to 8, and extracted with chloroform three times. The organic layer was combined, filtered through Phase-separator (Varian Inc.), and then concentrated under reduced pressure to give a crude 2,5-dichloro-4-nitropyridine (2.98 g, quant.) as a yellow oil. (2) To a solution of vinylmagnesium bromide (54.04 mmol) in tetrahydrofuran (104 mL) was added a solution of the above crude compound (2.98 g, 15.44 mmol) in tetrahydrofuran (100 mL) at 0° C. over 40 minutes, and the mixture was stirred at room temperature for 1 hour. To the reaction solution was added saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted with ethyl acetate three times. The organic layer was combined, filtered through Phase-separator (Varian Inc.), and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=80:20→50:50) to give 4,7-dichloro-1H-pyrrolo[3,2-c]pyridine (0.74 g, 27%) as a pale yellow powder.

Provenance & Evidence