Hydrochloric Acid → (2-Bromo-6-fluorophenyl)hydrazine hydrochloride

2-Bromo-6-fluoroaniline (2.0 g, 10 mmol) was dissolved in hydrochloric acid (7.0 mL, 12 N aqueous, 8.0 equiv) and cooled to 0° C. An aqueous solution (10 mL) of sodium nitrite (0.80 g, 11 mmol, 1.1 equiv) was added dropwise over 30 minutes via addition funnel and the mixture was stirred for an additional 30 minutes at 0° C. A hydrochloric acid solution (10 mL, 12 N aqueous) of stannous chloride (7.1 g, 31 mmol, 3.0 equiv) was then added to the mixture over 45 minutes via addition funnel and the mixture was stirred for an additional 1 hour at 0° C. To the mixture, sodium hydroxide (30 mL, 1 N aqueous) was added slowly until basic (pH>8). The mixture was warmed to ambient temperature, poured into sodium hydroxide (50 mL, 25% aqueous) and the aqueous layer was extracted with diethyl ether (3×250 mL). The combined organic extracts were dried with sodium sulfate, filtered and partially concentrated in vacuo. The mixture was diluted with diethyl ether (200 mL) and treated with gaseous hydrochloric acid until saturated, resulting in a white precipitate, which was filtered and washed with diethyl ether (2×50 mL), providing the titled compound as a white solid.

1. stirringthe mixture was stirred for an additional 1 hour at 0° C
2. temperatureThe mixture was warmed to ambient temperature
3. extractionthe aqueous layer was extracted with diethyl ether (3×250 mL)
4. dry with materialThe combined organic extracts were dried with sodium sulfate
5. filtrationfiltered
6. concentrationpartially concentrated in vacuo
7. additionThe mixture was diluted with diethyl ether (200 mL)
8. additiontreated with gaseous hydrochloric acid until saturated,
9. customresulting in a white precipitate, which
10. filtrationwas filtered
11. washwashed with diethyl ether (2×50 mL)

ORD-Eintrag

ord-981c138a835c45fbb52eff1087f33f5f

Quelldatensatz

uspto-grants-2014_02

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08653079B2