Allyl bromide → HCID 178490210, compound

Temperature

110 °C

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).

1. temperatureThe reaction mixture was cooled to 0° C.
2. temperatureThe reaction mixture was then cooled to 0° C.
3. stirringThe reaction mixture was stirred at 0° C. for 2 hours
4. stirringto stir for 16 hours at rt after which it
5. filtrationwas filtered
6. customThe filtrate was quenched with 1N HCl (10 mL)
7. extractionextracted with DCM (20 mL)
8. washThe organic layer was washed with brine (10 mL)
9. dry with materialdried over anhydrous Na2SO4
10. filtrationfiltered
11. concentrationconcentrated under reduced pressure to a yellow oil
12. dissolutionThe material was dissolved in DCM
13. extractionextracted with aq. NaHCO3
14. temperatureThe aqueous layer was cooled to 0° C.
15. extractionthen extracted with DCM
16. concentrationThe organic layer was concentrated under reduced pressure to a yellow oil (1.29 g, 39%)
17. customThis material was used in successive reactions without any further purification
18. customtR=0.76 min (UPLC-SQD: analytical—2 min)

ORD record

ord-ec46b9c991084f2788ad32008eabd74a

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09133224B2