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-Eintrag

ord-d62a07508aec4316b3a3c38cdf23091f

Quelldatensatz

uspto-grants-2012_07

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08212040B2