Azobisisobutyronitrile → 1-(Bromomethyl)-3-(1,1,2,2-tetrafluoroethoxy)benzene

To a solution of 3-(1,1,2,2-tetrafluoroethoxy)toluene (2.84 ml, 16.8 mmol) in ethyl acetate (30 ml) were added N-bromosuccinimide (3.0 g, 16.8 mmol) and 2,2′-azobisisobutyronitrile (0.1 g) and the mixture was heated under reflux for 2 hrs. The reaction solution was concentrated under reduced pressure and diethyl ether and hexane were added. Insoluble material was removed and washed with diethyl ether. The filtrate was evaporated under reduced pressure to give 3-(1,1,2,2-tetrafluoroethoxy)-1-bromomethylbenzene. To a solution of ethyl 3-[4-(methylsulfonyl)phenyl]-3-oxopropanoate (3.5 g, 13.0 mmol) in 1,2-dimethoxyethane (30 ml) was added sodium hydride (0.52 g, 60% in oil, 13.0 mmol) under ice-cooling and the mixture was stirred for 10 min. A solution of 3-(1,1,2,2-tetrafluoroethoxy)-1-bromomethylbenzene obtained above in 1,2-dimethoxyethane (5 ml) was dropwise added, and the mixture was stirred at room temperature for 4 hrs. To the reaction solution was added water (100 ml) and the mixture was extracted with ethyl acetate (100 ml). The extract was washed with water, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography (hexane:ethyl acetate=3:1-2:1) to give the objective substance (3.03 g, 49%) as an oil.

1. temperaturethe mixture was heated
2. temperatureunder reflux for 2 hrs
3. concentrationThe reaction solution was concentrated under reduced pressure and diethyl ether and hexane
4. additionwere added
5. customInsoluble material was removed
6. washwashed with diethyl ether
7. customThe filtrate was evaporated under reduced pressure

ORD record

ord-f13f68880fd846f68f73e5ebd87f699e

Source dataset

uspto-grants-2006_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06982348B2