Hydrochloric Acid → Diethyl 2,4,6-trichlorophenylmalonate

HRID 1066035Notes

Reaction equation

HRID 1066035 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].[Cl:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[C:17]([Cl:22])[C:16]=1Br.Cl>[Cu]Br.O1CCOCC1>[Cl:14][C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[C:17]([Cl:22])[C:16]=1[CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 1405262-Bromo-1,3,5-trichlorobenzene

Product 1

HCID 15869799Diethyl 2,4,6-trichlorophenylmalonateYield 63.6%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
55 °C

Procedure

Diethyl malonate (6.21 mol) is added to a mixture of sodium hydride (5.13 mol) and 1,4-dioxane (1400 ml) at 55 to 60° C. within 3 hours. The mixture is stirred for 10 minutes at 55° C. and copper(I) bromide (0.5 mol) is added. A mixture of 2,4,6-trichlorobromobenzene (2.50 mol) and 1,4-dioxane (600 ml) is added. The reaction mixture is heated at 100° C. for 14 hours and cooled to 15° C. Hydrochloric acid (12N, 350 ml) is added slowly at 15 to 20° C. The organic phase is separated off and the aqueous phase is extracted with ethyl acetate (250 ml) and toluene (200 ml). The combined organic phases are concentrated in vacuo. The residue is filtered over silica gel, washed with petroleum ether/ethyl acetate (15:1) and the solvent is distilled off. The residue is distilled in vacuo to yield 540 g of the product as a white solid, 144-150° C. at 0.4 mbar.

Workup

  1. additionis added
  2. temperatureThe reaction mixture is heated at 100° C. for 14 hours
  3. temperaturecooled to 15° C
  4. customThe organic phase is separated off
  5. extractionthe aqueous phase is extracted with ethyl acetate (250 ml) and toluene (200 ml)
  6. concentrationThe combined organic phases are concentrated in vacuo
  7. filtrationThe residue is filtered over silica gel
  8. washwashed with petroleum ether/ethyl acetate (15:1)
  9. distillationthe solvent is distilled off
  10. distillationThe residue is distilled in vacuo

Sources & evidence

ORD record
ord-59e762f7e8574e8187149284f4d6be33
Source dataset
uspto-grants-2001_06
Patent number
US06242451B1

Reaction notes

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