Acetic Acid → 5-BROMO-N1-METHYLBENZENE-1,2-DIAMINE

To a stirred solution of 5-bromo-N-methyl-2-nitroaniline (1-1) (12.4 g, 53.7 mmol) in 1,4 Dioxane (100 mL) at 0° C. was added powdered zinc (17.6 g, 269 mmol), followed by dropwise addition of glacial acetic acid (15.0 mL, 262 mmol). The reaction mixture was then permitted to warm to room temperature, sonicated for a few minutes, then permitted to stir at room temperature overnight, then heated to 90° C. in a hot oil bath for four hours. The crude reaction mixture was then cooled to room temperature, then suspended in ethyl acetate, cooled to 0° C. and neutralized with 6N NaOH while stirring until slightly basic. Crude mixture was then filtered. Filtrate organics were separated, then washed with a saturated solution of sodium bicarbonate, followed by water, then brine, dried over sodium sulfate, filtered, and concentrated to give 4-bromo-N2-methylbenzene-1,2-diamine (1-2) as a black oil. MS (M)+: observed=200.9, calculated=201.06.

1. customsonicated for a few minutes
2. temperatureheated to 90° C. in a hot oil bath for four hours
3. customThe crude reaction mixture
4. temperaturewas then cooled to room temperature
5. stirringwhile stirring until slightly basic
6. filtrationCrude mixture was then filtered
7. customFiltrate organics were separated
8. washwashed with a saturated solution of sodium bicarbonate
9. dry with materialbrine, dried over sodium sulfate
10. filtrationfiltered
11. concentrationconcentrated

ORD record

ord-3ba135bfbe5b49e799f2f377867a17fd

Source dataset

uspto-grants-2015_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09108937B2