Triphenylphosphine → 1-[(E)-3-bromo-1-methyl-1-propenyl]-3-nitrobenzene

To a solution of triphenylphosphine (5.15 g, 19.7 mmol) in acetonitrile (140 ml) was added dropwise over 5 minutes a solution of bromine (3.15 g, 19.7 mmol) in acetonitrile (5 ml) at a rate such that the temperature did not exceed −10° C. The mixture was allowed to warm to room temperature, then to this was added a solution of (E)-3-(3-nitrophenyl)-2-buten-1-ol (Preparation 2, 4 g, 20.7 mmol) in acetonitrile (5 ml). The mixture was warmed gently to 65° C. for 1 h, cooled to room temperature and then poured onto diethyl ether (50 ml). The mixture was concentrated in vacuo, then diethyl ether (200 ml) was added. The mixture was filtered, concentrated again in vacuo and the residue purified by silica column (300 g) chromatography, eluting with 3:1 hexane/dichloromethane then 1:1 hexane/dichloromethane. Appropriate fractions were combined and concentrated in vacuo to give the title compound as a very pale yellow oil (4 g, 75%).

1. customdid not exceed −10° C
2. temperatureThe mixture was warmed gently to 65° C. for 1 h
3. temperaturecooled to room temperature
4. additionpoured onto diethyl ether (50 ml)
5. concentrationThe mixture was concentrated in vacuo
6. additiondiethyl ether (200 ml) was added
7. filtrationThe mixture was filtered
8. concentrationconcentrated again in vacuo
9. customthe residue purified by silica column (300 g) chromatography
10. washeluting with 3:1 hexane/dichloromethane
11. concentrationconcentrated in vacuo

ORD record

ord-09856ba663cd48cc9d2fd6f51612900e

Source dataset

uspto-grants-2006_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07049444B2