Sodium Hydroxide → Hydrazine, [4-bromo-2-(phenylmethoxy)phenyl]-, hydrochloride (1:1)

Temperature

0 °C

To a stirred slurry of 2-(benzyloxy)-4-bromoaniline (12.60 g, 45.3 mmol) in concentrated HCl (150 mL) was added a solution of sodium nitrite (3.44 g, 49.9 mmol) in water (20 mL). The reaction mixture was stirred at 0° C. for 30 min before adding a slurry of tin dichloride (25.8 g, 136.0 mmol) in concentrated HCl (35 mL). The reaction mixture was stirred at 0° C. overnight, warmed to ambient temperature, made basic to pH 10 by addition of sodium hydroxide and extracted with diethyl ether. The organic layer was washed with brine, dried over sodium sulfate and treated with 1.25M HCl in methanol (10 mL). The solution was concentrated in vacuo to give (2-(benzyloxy)-4-bromophenyl)hydrazine hydrochloride (5.64 g, 38%) as a brown solid: 1H NMR (CD3OD, 300 MHz) δ 7.31-7.47 (m, 5H), 7.06 (dd, J=8.4, 2.1 Hz, 1H), 6.96 (d, J=2.1 Hz, 1H), 6.86 (d, J=8.4 Hz, 1H), 5.01 (s, 2H).

1. stirringThe reaction mixture was stirred at 0° C. overnight
2. temperaturewarmed to ambient temperature
3. extractionextracted with diethyl ether
4. washThe organic layer was washed with brine
5. dry with materialdried over sodium sulfate
6. additiontreated with 1.25M HCl in methanol (10 mL)
7. concentrationThe solution was concentrated in vacuo

ORD record

ord-e6eb02599404499aacc685f49f67b07d

Source dataset

uspto-grants-2013_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08575186B2