Ethyl 3,3,3-trifluoro-2-oxopropanoate → 4-Bromo-2-hydroxy-2-trifluoromethylpent-4-enoic acid ethyl ester

To a chilled (−78° C.) solution of 5.2 mL (30.18 mmol) of 2-bromoallyltrimethylsilane and 5.3 g (31.16 mmol) of ethyl trifluoropyruvate in 75 mL of dichloromethane was added 30 mL (30 mmol) of a 1 M solution of titanium tetrachloride in dichloromethane over a 10 minute period. The cold bath was then removed and the mixture was warmed to room temperature. After 3 hours, the mixture was cautiously added to 100 mL of saturated aqueous ammonium chloride and filtered through diatomaceous earth, washing with dichloromethane. The dichloromethane was separated and the aqueous layer was extracted with three 50 mL portions of dichloromethane. The combined organic layers were washed with two 50 mL portions of saturated aqueous sodium bicarbonate, 50 mL of brine, dried over magnesium sulfate, filtered, and concentrated to afford 6.7 g (76%) of 4-bromo-2-hydroxy-2-trifluoromethylpent-4-enoic acid ethyl ester as a yellow oil which was used without further purification.

1. customThe cold bath was then removed
2. additionthe mixture was cautiously added to 100 mL of saturated aqueous ammonium chloride
3. filtrationfiltered through diatomaceous earth
4. washwashing with dichloromethane
5. customThe dichloromethane was separated
6. extractionthe aqueous layer was extracted with three 50 mL portions of dichloromethane
7. washThe combined organic layers were washed with two 50 mL portions of saturated aqueous sodium bicarbonate, 50 mL of brine
8. dry with materialdried over magnesium sulfate
9. filtrationfiltered
10. concentrationconcentrated

ORD record

ord-9b44d19130cc40f0869286f70ea3228a

Source dataset

uspto-grants-2005_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06903215B2