Ammonium Chloride → Ethyl-2-hydroxy-4-methyl-2-(trifluoromethyl)pentenoate

HRID 656691Notes

Reaction equation

HRID 656691 reaction equation
Br[CH2:2][C:3]([CH3:5])=[CH2:4].[CH2:6]([O:8][C:9](=[O:16])[C:10]([C:12]([F:15])([F:14])[F:13])=[O:11])[CH3:7].[NH4+].[Cl-]>C1COCC1.[Cl-].[Cl-].[Zn+2]>[CH2:6]([O:8][C:9](=[O:16])[C:10]([OH:11])([C:12]([F:13])([F:15])[F:14])[CH:2]=[C:3]([CH3:5])[CH3:4])[CH3:7]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 3577853-Bromo-2-methyl-1-propeneHCID 2737239Ethyl 3,3,3-trifluoro-2-oxopropanoate

Product 1

HCID 86624389Ethyl-2-hydroxy-4-methyl-2-(trifluoromethyl)pentenoateYield 73%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of 0.27 mol Mn and 0.01 mol ZnCl2 in 105 ml THF is heated to reflux. 0.01 mol 3-bromo-2-methyl-1-propene is added to the boiling mixture and after 30 minutes a solution of 0.11 mmol ethyl-trifluoropyruvate and 0.18 mol 2-bromo-2-methyl-1-propene in 90 ml THF is dropped to the reaction mixture within 2.5 hours. After 3 hours under reflux the mixture is stirred for 19 hours at room temperature. The reaction mixture is poured on 90 ml of a saturated NH4Cl and ice mixture. After vigorous stirring for 30 minutes the mixture is extracted four times with 110 ml of MTBE each. The combined organic extracts are washed with 30 ml of brine, dried over magnesiumsulfate and concentrated in vacuo. The residue is destined under reduced pressure. ethyl-2-hydroxy-4-methyl-2-(trifluoromethyl)pentenoate is obtained in 73% yield.

Workup

  1. temperatureis heated to reflux
  2. additionis dropped to the reaction mixture within 2.5 hours
  3. temperatureAfter 3 hours under reflux the mixture
  4. stirringAfter vigorous stirring for 30 minutes the mixture
  5. extractionis extracted four times with 110 ml of MTBE each
  6. washThe combined organic extracts are washed with 30 ml of brine
  7. dry with materialdried over magnesiumsulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6db0edf68f1b460596a582f6b8778510
Source dataset
uspto-grants-2011_12
Patent number
US08071796B2

Reaction notes

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