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

HRID 622880Notes

Reaction equation

HRID 622880 reaction equation
[CH2:1]([O:3][P:4]([CH:6]([O:10][CH2:11][CH3:12])[O:7][CH2:8][CH3:9])[O-:5])[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:4]([CH:6]([O:10][CH2:11][CH3:12])[O:7][CH2:8][CH3:9])(=[O:5])[O:3][CH2:1][CH3:2])[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-171b3d1675df4d76876714b9a04b5216
Source dataset
uspto-grants-1988_09
Patent number
US04772738

Reaction notes

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