Allyl bromide → HCID 178490210, compound

Participants

Reaction Conditions

Reaction Steps

A mixture of ammonium phosphinate (1.00 g, 12.0 mmol) and Hexamethyldisilazane (1.94 g, 12.0 mmol) was heated to 110° C. under N2 for approximately 1.5 hours. The reaction mixture was cooled to 0° C., charged with anhydrous DCM (10 mL) followed by Allyl bromide (1.46 g, 12.0 mmol) and allowed to stir at RT for 16 hours. The reaction mixture was then cooled to 0° C. and charged with more hexamethyldisilazane (1.94 g, 12.0 mmol). The reaction mixture was stirred at 0° C. for 2 hours then treated with 4-(bromomethyl)-2-methoxy-1-nitrobenzene (3.00 g, 12.2 mmol). The reaction mixture was allowed to stir for 16 hours at rt after which it was filtered. The filtrate was quenched with 1N HCl (10 mL) and extracted with DCM (20 mL). The organic layer was washed with brine (10 mL), dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to a yellow oil. The material was dissolved in DCM and extracted with aq. NaHCO3. The aqueous layer was cooled to 0° C. and then acidified with 6 M HCl. The aqueous layer was saturated with solid NaCl then extracted with DCM. The organic layer was concentrated under reduced pressure to a yellow oil (1.29 g, 39%). This material was used in successive reactions without any further purification. 1H NMR (CDCl3, 400 MHz): δ=9.81 (br. s., 1H), 7.81 (d, J=8.3 Hz, 1H), 7.01 (s, 1H), 6.89 (td, J=1.8, 8.3 Hz, 1H), 5.79-5.67 (m, 1H), 5.29-5.18 (m, 2H), 3.96 (s, 3H), 3.10 (d, J=15.9 Hz, 2H), 2.53-2.44 (m, 2H). MS (ESI): m/z 270.37 [M−H]+. UPLC: tR=0.76 min (UPLC-SQD: analytical—2 min).

Provenance & Evidence