Sulfuryl chloride → 4-Amino-3,6-dichloro-5-fluoropicolinonitrile

Participants

Reaction Steps

To a suspension of 4-amino-3-chloro-5-fluoro-6-hydrazinylpicolinonitrile (9.04 g, 44.8 mmol) in CH2Cl2 (150 mL) was added sulfuryl chloride (7.20 mL, 89 mmol). The mixture was stirred at room temperature for 40 h. The solvent was removed under reduced pressure, and the residue was partitioned with saturated aqueous sodium bicarbonate (NaHCO3) and EtOAc. The organic phase was separated, dried over Na2SO4, and filtered. The solution was concentrated and the residue was purified by silica gel chromatography to give the product (7.01 g, 76%) as an off-white solid: 1H NMR (300 MHz, DMSO-d6) δ 7.55 (s, 2H); 13C NMR (101 MHz, DMSO-d6) δ 143.26 (d, J=259.2 Hz, C5), 142.69 (d, J=14.0 Hz, C4), 135.53 (d, J=17.6 Hz. C6), 126.07 (d, J=4.4 Hz, C2), 120.14 (d, J=4.3 Hz, C3), 114.36 (s, CN); 19F NMR (376 MHz, DMSO-d6) δ −132.30 (s); ESIMS m/z 203 ([M+H]+), 206.

Provenance & Evidence