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Methyl p-toluenesulfonate → 3-Methoxy-4,4,4-trifluoro-2-butenoic acid ethyl ester

HRID 6971
Notes
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Reaction equation

HRID 6971 reaction equation
[F:1][C:2]([F:12])([F:11])[C:3](=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[C:13](=O)([O-])[O-].[Cs+].[Cs+].C1(C)C=CC(S(OC)(=O)=O)=CC=1>CN(C=O)C.O>[CH2:8]([O:7][C:5](=[O:6])[CH:4]=[C:3]([O:10][CH3:13])[C:2]([F:11])([F:12])[F:1])[CH3:9]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 6645Methyl p-toluenesulfonateHCID 10796Cesium carbonateHCID 67793Ethyl 4,4,4-trifluoroacetoacetate

Product 1

HCID 27588673-Methoxy-4,4,4-trifluoro-2-butenoic acid ethyl esterYield 56%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent
HCID 6228
Dimethylformamide
Solvent
2×

Conditions

Temperature
70 °C

Procedure

To a solution of ethyl 4,4,4-trifluoroacetoacetate (12 mL, 82 mmol) in DMF (80 mL) is added cesium carbonate (26.4 g, 82 mmol). The reaction mixture is heated to 70° C. A solution of methyl p-toluenesulfonate (13.5 mL, 90 mmol) in DMF (30 mL) is then added dropwise during 30 min and the reaction mixture is stirred for an additional 1 hr. After cooling to room temperature, the reaction mixture is diluted with H2O (150 mL) and extracted with Et2O (2×150 mL). The organic extracts are combined and washed with H2O and brine, then dried (Na2SO4), filtered and concentrated to afford the title compound (9.0 g, 56%) as an oil which is used without further purification.

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionextracted with Et2O (2×150 mL)
  3. washwashed with H2O and brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-d146ffc4743f46cfb9a96289a70a2846
Source dataset
uspto-grants-2006_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07084170B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes