Triethyl phosphonoacetate → Ethyl 4-amino-beta-(4-chlorophenyl)-3,5-dichloro-cinnamate

HRID 580602Notes

Reaction equation

HRID 580602 reaction equation
C(OP([CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])(OCC)=O)C.[H-].[Na+].[NH2:17][C:18]1[C:32]([Cl:33])=[CH:31][C:21]([C:22]([C:24]2[CH:29]=[CH:28][C:27]([Cl:30])=[CH:26][CH:25]=2)=O)=[CH:20][C:19]=1[Cl:34]>COCCOC>[NH2:17][C:18]1[C:19]([Cl:34])=[CH:20][C:21]([C:22]([C:24]2[CH:25]=[CH:26][C:27]([Cl:30])=[CH:28][CH:29]=2)=[CH:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:31][C:32]=1[Cl:33]

Participants

5

Reactant 3

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 133733144-Amino-3,4',5-trichlorobenzophenone

Product 1

HCID 54319747Ethyl 4-amino-beta-(4-chlorophenyl)-3,5-dichloro-cinnamate

Reagents, catalysts & solvents 1

HCID 80711,2-DimethoxyethaneSolvent3×

Procedure

A solution of 108 g (0.55 mol) of ethyl diethylphosphonoacetate in 150 ml of dry 1,2-dimethoxyethane was slowly added dropwise, while stirring and cooling with ice to a suspension of 13.2 g (0.55 mol) of sodium hydride (26.4 g of 50% oil suspension) in 50 ml of dry 1,2-dimethoxyethane, whereupon the mixture foamed vigorously. After all the solution had been added the mixture was stirred for another 30 minutes. It was then combined with a suspension of 150 g (0.5 mol) of 4-amino-3,4',5-trichloro-benzophenone in 800 ml of dry 1,2-dimethoxyethane and heated for one hour at reflux temperature, whereby a clear solution was formed. The solution was evaporated to dryness in vacuo, and the residue was distributed between chloroform and water. The organic phase was dried and evaporated to dryness in vacuo. After mixing with 150 ml of ethanol, crystallization set in. The crystals were suction-filtered off and washed with ethanol and petroleum ether.

Workup

  1. additionAfter all the solution had been added the mixture
  2. stirringwas stirred for another 30 minutes
  3. temperatureheated for one hour
  4. temperatureat reflux temperature, whereby a clear solution
  5. customwas formed
  6. customThe solution was evaporated to dryness in vacuo
  7. customThe organic phase was dried
  8. customevaporated to dryness in vacuo
  9. additionAfter mixing with 150 ml of ethanol, crystallization
  10. filtrationThe crystals were suction-filtered off
  11. washwashed with ethanol and petroleum ether

Sources & evidence

ORD record
ord-4d515572fbfd48bb9ccb740848061406
Source dataset
uspto-grants-1988_06
Patent number
US04753934

Reaction notes

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