Water → Ethyl 4-(3,5-bis(trifluoromethyl)benzyloxy)-3-phenyl-2-butenoate

HRID 548196Notes

Reaction equation

HRID 548196 reaction equation
C(OP([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])(OCC)=O)C.[H-].[Na+].[F:17][C:18]([F:41])([F:40])[C:19]1[CH:20]=[C:21]([CH:33]=[C:34]([C:36]([F:39])([F:38])[F:37])[CH:35]=1)[CH2:22][O:23][CH2:24][C:25]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=O.O>C1COCC1>[F:17][C:18]([F:40])([F:41])[C:19]1[CH:20]=[C:21]([CH:33]=[C:34]([C:36]([F:39])([F:38])[F:37])[CH:35]=1)[CH2:22][O:23][CH2:24][C:25]([C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)=[CH:9][C:10]([O:12][CH2:13][CH3:14])=[O:11]

Participants

6

Reactant 4

HCID 962WaterHCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 229606442-{[3,5-Bis(trifluoromethyl)phenyl]methoxy}-1-phenylethan-1-one

Product 1

HCID 86624036Ethyl 4-(3,5-bis(trifluoromethyl)benzyloxy)-3-phenyl-2-butenoateYield 69%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Ethyl diethoxyphosphorylacetate (30 mL, 150 mmol) was dropped into a suspension of sodium hydride (60% oily) (6.00 g, 150 mmol) in THF (300 mL) at room temperature during 30 minutes. After the dropping, the mixture was stirred at room temperature for 1 hour more, a solution of 2-(3,5-bis(trifluoromethyl)-benzyloxy)-1-phenylethanone (48.90 g, 135 mmol) in THF (100 mL) was dropped thereinto at room temperature during 30 minutes and the mixture was stirred for 1 hour more. The reaction mixture was added to water (1000 mL) followed by extracting with ethyl acetate. The organic layers were combined, washed with water and a saturated saline solution and dried over anhydrous sodium sulfate and the solvent was evaporated in vacuo. The residual oily product was purified by a silica gel column chromatography (n-hexane:ethyl acetate=9:1) to give ethyl 4-(3,5-bis(trifluoromethyl)-benzyloxy)-3-phenyl-2-butenoate (40.00 g, 69%) as an oily product. 1H-NMR (DMSO-d6) δ: 1.23 (t, J=7.1 Hz, 3H), 4.15 (q, J=7.1 Hz, 2H), 4.63 (s, 2H), 5.08 (s, 2H), 6.24 (s, 1H), 7.39-7.43 (m, 3H), 7.57-7.61 (m, 2H), 7.79 (s, 2H), 7.96 (s, 1H).

Workup

  1. waitat room temperature during 30 minutes
  2. stirringthe mixture was stirred for 1 hour more
  3. extractionby extracting with ethyl acetate
  4. washwashed with water
  5. dry with materiala saturated saline solution and dried over anhydrous sodium sulfate
  6. customthe solvent was evaporated in vacuo
  7. customThe residual oily product was purified by a silica gel column chromatography (n-hexane:ethyl acetate=9:1)

Sources & evidence

ORD record
ord-9ff3e59774bd48b6bdc5445b6c18ac1e
Source dataset
uspto-grants-2011_05
Patent number
US07939552B2

Reaction notes

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