Iodine → 3-(Methylthio)benzeneboronic acid

A solution of 3-bromothioanisole (10.3 g, 50.9 mmol) in anhydrous tetrahydrofuran (15 ml) was added dropwise to a stirred mixture of magnesium turnings (1.86 g, 75 mmol) and a crystal of iodine under nitrogen. Once the reaction was initiated, the remainder of the solution was added at such a rate as to keep the reaction mixture under reflux. When the addition was complete, the mixture was stirred under reflux for a further 1 hour, allowed to cool to room temperature and then added to a solution of trimethyl borate (5.8 ml, 51 mmol) in anhydrous tetrahydrofuran (25 ml), whilst keeping the internal temperature at about −10° C. The reaction mixture was allowed to warm to about 0° C., stirred for 30 minutes and then quenched with 2M hydrochloric acid. The resulting mixture was extracted with ether, then the combined extracts extracted, in turn, with 2M aqueous sodium hydroxide solution. The combined aqueous extracts were acidified with concentrated hydrochloric acid and extracted with ether. The combined ether extracts were dried (MgSO4) and evaporated under reduced pressure to provide the title compound (7.8 g, 100%) as a white solid. δ(DMSOd6): 2.45 (s,3H), 7.27 (m,2H), 7.54 (m,1H), 7.67 (s,1H), 8.05 (brs,2H),

1. additionthe remainder of the solution was added at such a rate as
2. temperatureunder reflux
3. additionWhen the addition
4. temperatureunder reflux for a further 1 hour
5. customat about −10° C
6. temperatureto warm to about 0° C.
7. stirringstirred for 30 minutes
8. customquenched with 2M hydrochloric acid
9. extractionThe resulting mixture was extracted with ether
10. extractionthe combined extracts extracted, in turn, with 2M aqueous sodium hydroxide solution
11. extractionextracted with ether
12. dry with materialThe combined ether extracts were dried (MgSO4)
13. customevaporated under reduced pressure

ORD record

ord-eb1dee2c431443ae838ea330bc06bc85

Source dataset

uspto-grants-2002_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06495568B1