Diethyl chlorophosphate → 1-Bromo-4-[(E)-2-ethoxysulfonylethenyl]benzene

Temperature

0 °C

n-Butyllithium (59.0 mL, 1.6M solution in hexanes) was added dropwise during 25 min to a solution of ethylmethanesulfonate (9.1 mL, 86 mmol) in THF (200 mL) at −78° C. The reaction mixture was stirred for 15 min then diethyl chlorophosphate (7.2 ml, 50 mmol) was added dropwise. The solution was stirred at −78° C. for 30 min, allowed to warm to 0° C. and then cooled to −78° C. again. 4-Bromobenzaldehyde (9.2 g, 50 mmol) in THF (50 mL) was then added dropwise during 15 minutes and the resulting mixture was then allowed to slowly reach RT and stirred overnight. Water (20 mL) was added to the mixture and the reaction was concentrated in vacuo. The residue was extracted with diethyl ether and the combined organic extracts were washed with aqueous saturated sodium chloride, dried over magnesium sulfate, filtered and the solvent was evaporated in vacuo. Purification by column chromatography, using 15% ethyl acetate/hexanes as the eluent, afforded the title compound (9.3 g, 64%).

1. stirringThe solution was stirred at −78° C. for 30 min
2. temperaturecooled to −78° C. again
3. customwas then allowed to slowly reach RT
4. stirringstirred overnight
5. concentrationthe reaction was concentrated in vacuo
6. extractionThe residue was extracted with diethyl ether
7. washthe combined organic extracts were washed with aqueous saturated sodium chloride
8. dry with materialdried over magnesium sulfate
9. filtrationfiltered
10. customthe solvent was evaporated in vacuo
11. customPurification by column chromatography

ORD record

ord-e6e13d12bb50468b8e062189a5b6d9dd

Source dataset

uspto-grants-2015_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09145380B2