Sulfuric Acid → Diethyl (2,4-dichloro-5-fluoro-3-nitrobenzoyl)propanedioate

HRID 1723258Notes

Reaction equation

HRID 1723258 reaction equation
[Mg].[H][H].[C:4]([O:12][CH2:13][CH3:14])(=[O:11])[CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7].[Cl:15][C:16]1[C:24]([N+:25]([O-:27])=[O:26])=[C:23]([Cl:28])[C:22]([F:29])=[CH:21][C:17]=1[C:18](Cl)=[O:19].S(=O)(=O)(O)O>C(O)C.C1(C)C=CC=CC=1.ClC(Cl)(Cl)Cl.O>[Cl:15][C:16]1[C:24]([N+:25]([O-:27])=[O:26])=[C:23]([Cl:28])[C:22]([F:29])=[CH:21][C:17]=1[C:18]([CH:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])[C:4]([O:12][CH2:13][CH3:14])=[O:11])=[O:19]

Participants

10

Reactant 5

HCID 1118Sulfuric AcidHCID 7761Diethyl MalonateHCID 5462224MagnesiumHCID 11818130Benzoyl chloride, 2,4-dichloro-5-fluoro-3-nitro-HCID 178418361HCID 178418361, compound

Product 1

HCID 13733139Diethyl (2,4-dichloro-5-fluoro-3-nitrobenzoyl)propanedioateYield 91%

Reagents, catalysts & solvents 4

HCID 5943Carbon TetrachlorideCatalystHCID 702EthanolSolvent2×HCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
-7.5 °C

Procedure

2.1 g of tetrachloromethane are added to 10.1 g of magnesium turnings in 21 ml of ethanol and, after evolution of hydrogen has started, a mixture of 66.6 g of diethyl malonate, 40 ml of ethanol and 150 ml of toluene is added dropwise at 50°-60° C. The mixture is stirred at this temperature for 1 hour, then cooled to -5 to -10° C., and a solution of 109.2 g of 2,4-dichloro-5-fluoro-3-nitrobenzoyl chloride in 50 ml of toluene is slowly added dropwise. The mixture is then stirred at 0° C. for 1 hour, brought to room temperature overnight, and then heated at 40°-50° C. for 2 hours. The reaction mixture is cooled in ice, and a mixture of 160 ml of water and 10.4 ml of concentrated sulphuric acid is added, and the organic phase is separated off. The aqueous phase is extracted with toluene, and the combined organic extract is washed with saturated sodium chloride solution, dried with sodium sulphate, and the solvent is removed in vacuo. 144.5 g of diethyl (2,4-dichloro-5-fluoro-3-nitrobenzoyl)malonate are obtained as a crude product. 200 ml of water and 0.6 g of 4-toluenesulphonic acid are added to this, and the mixture is heated under reflux for 3 hours, extracted with methylene chloride, and the extract is dried with Sodium sulphate and the solvent is removed by distillation in vacuo. 118 g of substituted benzoyl acetic ester are obtained as a crude product. It is sufficiently pure for the subsequent reactions.

Workup

  1. additionis added dropwise at 50°-60° C
  2. stirringThe mixture is then stirred at 0° C. for 1 hour
  3. waitbrought to room temperature overnight
  4. temperatureheated at 40°-50° C. for 2 hours
  5. temperatureThe reaction mixture is cooled in ice
  6. additionis added
  7. customthe organic phase is separated off
  8. extractionThe aqueous phase is extracted with toluene
  9. extractionthe combined organic extract
  10. washis washed with saturated sodium chloride solution
  11. dry with materialdried with sodium sulphate
  12. customthe solvent is removed in vacuo

Sources & evidence

ORD record
ord-44efc8fdc378496dafb2986343c8e0e6
Source dataset
uspto-grants-1989_08
Patent number
US04859773

Reaction notes

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