Hydrochloric Acid → [3-(Methylamino)phenyl]boronic acid

Temperature

-70 °C

37.6 g (202 mmol, 1 eq) of (3-bromophenyl)methylamine (obtained as in 1c) are dissolved in 300 ml of tetrahydrofuran. The reaction mixture is cooled to −70° C., and 166 mL (242 mmol, 1.2 eq) of 1.5 M methyllithium are then added slowly while maintaining the temperature at −70° C. The reaction mixture is stirred for 1 hour at −70° C. 306 mL (444 mmol, 2.2 eq) of 1.46 M tert-butyllithium are added while maintaining the temperature at −70° C. The reaction mixture is stirred for 45 minutes at −70° C. 103.5 mL (808 mmol, 4 eq) of trimethyl borate are added at −65° C., and the reaction mixture is then warmed to room temperature. The reaction is stopped by addition of 1 L of 1N hydrochloric acid. The pH is adjusted to 5 and the reaction medium is then extracted with n-butanol. The organic phases are combined and dried over sodium sulfate. The solvents are evaporated off and the residue is then chromatographed on silica gel (70/30 heptane/ethyl acetate). 11.3 g of N-methyl-3-aminophenylboronic acid are obtained. Yield=40%

1. temperaturewhile maintaining the temperature at −70° C
2. temperaturewhile maintaining the temperature at −70° C
3. stirringThe reaction mixture is stirred for 45 minutes at −70° C
4. temperaturethe reaction mixture is then warmed to room temperature
5. extractionthe reaction medium is then extracted with n-butanol
6. dry with materialdried over sodium sulfate
7. customThe solvents are evaporated off
8. customthe residue is then chromatographed on silica gel (70/30 heptane/ethyl acetate)

ORD record

ord-904ec88a0acb4c2f8c2b9d0e09a8b7f9

Source dataset

uspto-grants-2011_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07863332B2