tert-Butyl hydroperoxide → 4-Chloro-5-nitropyridin-2(1H)-one

Temperature

35 °C

Anhydrous THF (50 mL) in a 500-mL round-bottom flask was cooled to −78° C. and anhydrous NH3 (gas) was bubbled into until saturated (about 20 minutes). Potassium t-butoxide (6.5 g, 57.9 mmol) was added portion wise and the mixture was allowed to warm to ˜35° C. To a solution of 4-chloro-3-nitropyridine (3.498 g, 22 mmol) in dry THF (20 mL) at 0° C. was added tBOOH (4.4 mL, 22 mmol) (5M in decane) over 10 minutes. This solution was then added dropwise to the prepared KOtBu solution over a period of 15 minutes, then stirred for 2 hours at ˜35° C., followed by quenching the reaction with 5 mL of saturated aqueous NH4Cl solution. The reaction was allowed to stir at room temperature overnight. Volatiles were removed under reduced pressure and the residue was made weakly acidic with saturated aqueous NH4Cl solution. The solid was filtered and washed with cold water. The title compound was obtained as a tan-powder, dried under high vacuum overnight, and used for the next reaction without further purification. (1.36 g, 35% yield).

1. customanhydrous NH3 (gas) was bubbled into until saturated (about 20 minutes)
2. customby quenching
3. customthe reaction with 5 mL of saturated aqueous NH4Cl solution
4. stirringto stir at room temperature overnight
5. customVolatiles were removed under reduced pressure
6. filtrationThe solid was filtered
7. washwashed with cold water

ORD record

ord-8a83a85118f04ec3b5ca266648793afb

Source dataset

uspto-grants-2014_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08716318B2