Hydrochloric Acid → Diethyl (2,6-Dichloro-4-fluoro-phenyl)-malonate

HRID 1066034Notes

Reaction equation

HRID 1066034 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+].Br[C:15]1[C:20]([Cl:21])=[CH:19][C:18]([F:22])=[CH:17][C:16]=1[Cl:23].Cl>[Cu]Br.O1CCOCC1>[Cl:21][C:20]1[CH:19]=[C:18]([F:22])[CH:17]=[C:16]([Cl:23])[C:15]=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 211981432-Bromo-1,3-dichloro-5-fluorobenzene

Product 1

HCID 15510255Diethyl (2,6-Dichloro-4-fluoro-phenyl)-malonateYield 54.5%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
55 °C

Procedure

Diethyl malonate (0.49 mol) is added to a mixture of sodium hydride (0.51 mol) and 1,4-dioxane (140 ml) at 55 to 60° C. within 2 hours. The mixture is stirred for 10 minutes at 55° C. and copper(I) bromide (0.05 mol) is added. After 15 minutes a mixture of 1-bromo-2,6-dichloro-4-fluoro-benzene (0.25 mol) and 1,4-dioxane (10 ml) is added. The reaction mixture is heated at 100° C. for 15 hours and cooled to 15° C. Hydrochloric acid (12N, 35 ml) is added slowly at 15 to 20° C. The precipitate is filtered off. The filtrate is extracted with diethylether. The organic phase is separated, dried with anhydrous sodium sulphate and filtered. The filtrate is evaporated under reduced pressure to yield 44 g of the product as yellow crystals having a melting point of 170° C.

Workup

  1. additionis added
  2. temperatureThe reaction mixture is heated at 100° C. for 15 hours
  3. temperaturecooled to 15° C
  4. filtrationThe precipitate is filtered off
  5. extractionThe filtrate is extracted with diethylether
  6. customThe organic phase is separated
  7. dry with materialdried with anhydrous sodium sulphate
  8. filtrationfiltered
  9. customThe filtrate is evaporated under reduced pressure

Sources & evidence

ORD record
ord-293b5934e6b74932b22467f60352c185
Source dataset
uspto-grants-2001_06
Patent number
US06242451B1

Reaction notes

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