Dibromomethane → HCID 67151026, compound

n-Butyllithium (1.6 molar in hexanes; 33.2 ml; 53 1 mmol) was added dropwise to (2E)-2-methyl-3-(4-methylphenyl)-2-propen-1-ol (8.61 g, 53 1 mmol) in dry diethyl ether (120 ml) at 0° C. under nitrogen. After 10 minutes, dibromomethane (46.6 g; 265 mmol) was added dropwise, followed, after 15 minutes, by t-butyl magnesium chloride (2 molar in diethyl ether; 133 ml; 265 mmol). The reaction was then slowly warmed up to room temperature and stirred overnight. It was then cooled into an ice-water bath and a saturated aqueous ammonium chloride solution (300 ml) was added (initially dropwise, exothermic). After warming to room temperature, diethyl ether (200 ml) was added and the mixture shaken vigorously. The organic phase was washed with water (600 ml) and brine (300 ml). Each aqueous phase was re-extracted with diethyl ether (300 ml). Combined extracts were dried over solid anhydrous sodium sulfate. The product was purified by column chromatography on silica gel (heptane/ethyl acetate 5:1 to 2:1) followed by bulb-to-bulb distillation (120° C./1 mbar). 2.21 g of 90% pure material was obtained as a colorless liquid (11.3 mmol; 21%).

1. temperatureIt was then cooled into an ice-water bath
2. temperatureAfter warming to room temperature
3. stirringthe mixture shaken vigorously
4. washThe organic phase was washed with water (600 ml) and brine (300 ml)
5. extractionEach aqueous phase was re-extracted with diethyl ether (300 ml)
6. dry with materialCombined extracts were dried over solid anhydrous sodium sulfate
7. customThe product was purified by column chromatography on silica gel (heptane/ethyl acetate 5:1 to 2:1)
8. distillationfollowed by bulb-to-bulb distillation (120° C./1 mbar)

ORD record

ord-b4e5c43fe47546c0a263045197bcdb9b

Source dataset

uspto-grants-2013_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08410042B2