Water → tert-Butyl (2E)-3-(4-chloro-3-nitrophenyl)prop-2-enoate

HRID 877218Notes

Reaction equation

HRID 877218 reaction equation
[H-].[Na+].[C:3]([O:7][C:8](=[O:18])[CH2:9]P(OCC)(OCC)=O)([CH3:6])([CH3:5])[CH3:4].[Cl:19][C:20]1[CH:27]=[CH:26][C:23]([CH:24]=O)=[CH:22][C:21]=1[N+:28]([O-:30])=[O:29].O>C1(C)C=CC=CC=1.C1COCC1>[Cl:19][C:20]1[CH:27]=[CH:26][C:23](/[CH:24]=[CH:9]/[C:8]([O:7][C:3]([CH3:4])([CH3:5])[CH3:6])=[O:18])=[CH:22][C:21]=1[N+:28]([O-:30])=[O:29]

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 855054-Chloro-3-nitrobenzaldehydeHCID 2773685tert-Butyl diethylphosphonoacetate

Product 1

HCID 58136394tert-Butyl (2E)-3-(4-chloro-3-nitrophenyl)prop-2-enoate

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Under argon, 1.19 g (29.64 mmol, 60% pure) of sodium hydride were suspended in 25 ml of toluene and 25 ml of THF, and the suspension was cooled to 0° C. 7.28 ml (30.99 mmol) of tert-butyl(diethoxyphosphoryl)acetate were then slowly added dropwise, and the mixture was stirred at 0° C. for 30 min. 5 g (26.94 mmol) of 4-chloro-3-nitrobenzaldehyde were then added to the reaction mixture, and the reaction mixture was then warmed to room temperature. The mixture was stirred at room temperature for 2 hours, and 50 ml of water were then added. After removal of the organic phase, the aqueous phase was extracted three more times with ethyl acetate. The combined organic phases were dried over sodium sulfate. After filtration, the solvent was removed under reduced pressure. The crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 9:1). This gave 6.77 g (23.86 mmol, 77% of theory) of the title compound.

Workup

  1. temperaturethe reaction mixture was then warmed to room temperature
  2. stirringThe mixture was stirred at room temperature for 2 hours
  3. customAfter removal of the organic phase
  4. extractionthe aqueous phase was extracted three more times with ethyl acetate
  5. dry with materialThe combined organic phases were dried over sodium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was removed under reduced pressure
  8. customThe crude product was purified chromatographically on silica gel (mobile phase cyclohexane/ethyl acetate 9:1)

Sources & evidence

ORD record
ord-349a3d7039b64c99ab0816748bde8c9e
Source dataset
uspto-grants-2015_03
Patent number
US08987256B2

Reaction notes

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