Acetic Acid → Ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate

HRID 1165316Notes

Reaction equation

HRID 1165316 reaction equation
[CH2:1]([O:3][CH:4]([P:8]([O-:12])[O:9][CH2:10][CH3:11])[O:5][CH2:6][CH3:7])[CH3:2].[Cl:13][C:14]1[CH:23]=[CH:22][C:17]([CH:18]=[CH:19][C:20]#[N:21])=[CH:16][CH:15]=1.[H-].[Na+].C(O)(=O)C>C(O)C>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([CH:18]([P:8]([CH:4]([O:5][CH2:6][CH3:7])[O:3][CH2:1][CH3:2])(=[O:12])[O:9][CH2:10][CH3:11])[CH2:19][C:20]#[N:21])=[CH:22][CH:23]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 24758Sodium hydrideHCID 342433-(4-Chlorophenyl)prop-2-enenitrileHCID 85631043Ethyl(diethoxymethyl)phophonite

Product 1

HCID 14362807Ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A solution of 25.8 g of ethyl (diethoxymethyl)phosphonite and 18.0 g of 4-chlorocinnamonitrile in 100 ml of ethanol is added to a stirred mixture of 1.2 g of sodium hydride (50% dispersion in oil) in 30 ml of ethanol at 0° C. under an atmosphere of nitrogen. The reaction mixture is allowed to warm to room temperature and stirred for 4 hours. 1 ml of glacial acetic acid is added and the mixture is concentrated under reduced pressure. The resulting crude product is dissolved in 50 ml of ethyl acetate, washed twice with 25 ml of water and the organic extract is dried over magnesium sulphate, and then concentrated under reduced pressure. The crude product is distilled under reduced pressure to give ethyl 1-(4-chlorophenyl)-2-cyanoethyl(diethoxymethyl)phosphinate, b.p. 180°-200° C./0.02 mbar, 31P=+37.9 and +37.8 ppm (CDCl3).

Workup

  1. concentrationthe mixture is concentrated under reduced pressure
  2. dissolutionThe resulting crude product is dissolved in 50 ml of ethyl acetate
  3. washwashed twice with 25 ml of water
  4. extractionthe organic extract
  5. dry with materialis dried over magnesium sulphate
  6. concentrationconcentrated under reduced pressure
  7. distillationThe crude product is distilled under reduced pressure

Sources & evidence

ORD record
ord-2de2c6fe6c0c4dcb801df761e28c7b2f
Source dataset
uspto-grants-1990_03
Patent number
US04908465

Reaction notes

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