Triethyl phosphonoacetate → HCID 67314943, compound

HRID 408487Notes

Reaction equation

HRID 408487 reaction equation
[CH2:1]([O:3][C:4](=[O:14])[CH2:5]P(OCC)(OCC)=O)[CH3:2].[H-].[Na+].[Cl:17][C:18]1[CH:25]=[CH:24][CH:23]=[C:22]([F:26])[C:19]=1[CH:20]=O>O1CCCC1>[CH2:1]([O:3][C:4](=[O:14])[CH:5]=[CH:20][C:19]1[C:22]([F:26])=[CH:23][CH:24]=[CH:25][C:18]=1[Cl:17])[CH3:2]

Participants

5

Reactant 3

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 678472-Chloro-6-fluorobenzaldehyde

Product 1

HCID 67314943HCID 67314943, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
50 °C

Procedure

A solution of (diethoxyphosphoryl)-acetic acid ethyl ester (87 g, 0.39 mol) in tetrahydrofuran (100 mL) was slowly added to a suspension of sodium hydride (60% in mineral oil, 15 g, 0.39 mol) in tetrahydrofuran (200 mL) at 0° C. After stirring for 20 minutes, a solution of 2-chloro-6-fluoro-benzaldehyde (40 g, 0.26 mol) in tetrahydrofuran (100 mL) while maintaining the temperature at 0° C. The mixture was heated to 50° C. for 1 hour and then cooled to room temperature. The reaction was quenched by addition of a saturated aqueous solution of ammonium chloride (300 mL). The layers were separated and the aqueous layer was extracted with ether. The combined organic layers were washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, and evaporated to dryness to give 3-(2-chloro-6-fluoro-phenyl)-acrylic acid ethyl ester, which was used directly in the next step. 1H NMR (CDCl3) δ: 7.89 (d, 1H, J=16.4 Hz), 7.26-7.06 (m, 2H), 7.06-7.02 (m, 1H), 6.72 (d, 1H, J=16.4 Hz), 4.28 (q, 2H, J=7.6 Hz), 1.34 (t, 3H, J=7.6 Hz).

Workup

  1. temperaturecooled to room temperature
  2. customThe reaction was quenched by addition of a saturated aqueous solution of ammonium chloride (300 mL)
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ether
  5. washThe combined organic layers were washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over sodium sulfate
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-94f3c08cb4564312b571bec0ae23ceb2
Source dataset
uspto-grants-2014_06
Patent number
US08759335B2

Reaction notes

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