Tert-Butylamine → HCID 57700291, compound

Temperature

-78 °C

To a solution of tert-butylamine (1.6 mL, 15 mmol) in dichloromethane (100 mL) at −78° C. was added drop-wise over 30 minutes a solution of bromine (773 μl, 15 mmol in 15 mL of dichloromethane). The solution was stirred at −78° C. for 30 minutes. While maintaining the temperature at −78° C., a solution of methyl 3-hydroxy-2-methylbenzoate (2.5 g, 15 mmol in 15 mL of dichloromethane) was added to the reaction mixture drop-wise over 30 minutes. The mixture was allowed to warm to room temperature and was stirred for 15 hours. The mixture was washed with 20% aqueous citric acid then brine and dried over anhydrous sodium sulfate. Filtration and concentration afforded a brown residue that was purified by silica gel column chromatography. Eluting with 10% diethyl ether in hexane, purified fractions were pooled and concentrated to afford 612 mg, 2.5 mmol (17%) of methyl 4-bromo-3-hydroxy-2-methylbenzoate as a colorless oil. 1H NMR (400 MHz, CDCl3): 7.37-7.29 (m, 2H), 5.71 (s, 1H), 3.81 (s, 3H), 2.53 (s, 3H). MS (EI) for C9H9BrO3: 245 (MH+).

1. temperatureWhile maintaining the temperature at −78° C.
2. temperatureto warm to room temperature
3. stirringwas stirred for 15 hours
4. washThe mixture was washed with 20% aqueous citric acid
5. dry with materialbrine and dried over anhydrous sodium sulfate
6. filtrationFiltration and concentration
7. customafforded a brown residue that
8. customwas purified by silica gel column chromatography
9. washEluting with 10% diethyl ether in hexane
10. custompurified fractions
11. concentrationconcentrated

ORD record

ord-48cccff9db644cfcbfb4d6cbfd53db3d

Source dataset

uspto-grants-2011_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08012956B2