Pyridine → HCID 13317598, Verbindung

In a round bottom flask 4 (1 g, 4.63 mmol, 1 eq) was dissolved in dry DCM (10 mL) and dry pyridine (0.47 mL, 5.78 mmol, 1.25 eq) was added. Thionyl bromide (0.45 mL, 5.78 mmol, 1.25 eq) was then added to the round bottom flask under inert atmosphere. The round bottom flask was sealed with a septum, cooled in an ice bath and slowly allowed to come to room temperature overnight. The solvent was then evaporated and the crude product was dissolved in ethyl acetate. The organic layer was washed with 1 M HCl, saturated NaHCO3, water, brine, then dried over Na2SO4 and filtered. The solvent was evaporated and the crude product was purified on a silica plug 1:4 (hexanes:ethyl acetate) followed by 3:7 (hexanes:ethyl acetate) to give 5 as a viscous oil (1.14 g, 88%). The product was dried under high vacuum over P2O5. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J=7.8 Hz, 2H), 7.34 (d, J=7.5 Hz, 3H), 7.26 (s, 1H), 4.88 (d, J=13.1 Hz, 1H), 3.85 (d, J=10.8 Hz, 3H), 3.60 (d, J=10.7 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 134.56 (d, JC-P=3.3 Hz), 129.70 (d, JC-P=6.7 Hz), 129.40 (d, JC-P=2.2 Hz), 129.04 (d, JC-P=1.3 Hz), 54.87 (dd, JC-P=22.1, 7.0 Hz), 41.11 (d, JC-P=159.9 Hz). 31P NMR (162 MHz, CDCl3) δ 20.55 (s). ESIMS calculated for C9H12BrO3PNa [M+Na]+300.96, found: 300.96.