Hydrochloric Acid → Dimethyl 4-fluoro-2-nitrophenylmalonate

HRID 2109012Notes

Reaction equation

HRID 2109012 reaction equation
CC(C)([O-])C.[K+].[C:7]([O:14][CH3:15])(=[O:13])[CH2:8][C:9]([O:11][CH3:12])=[O:10].F[C:17]1[CH:22]=[CH:21][C:20]([F:23])=[CH:19][C:18]=1[N+:24]([O-:26])=[O:25].Cl>CN1CCCC1=O>[F:23][C:20]1[CH:21]=[CH:22][C:17]([CH:8]([C:7]([O:14][CH3:15])=[O:13])[C:9]([O:11][CH3:12])=[O:10])=[C:18]([N+:24]([O-:26])=[O:25])[CH:19]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 677672,5-DifluoronitrobenzeneHCID 23665647Potassium tert-butoxide

Product 1

HCID 9838325Dimethyl 4-fluoro-2-nitrophenylmalonate

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

185 g of potassium-tert-butoxide are added to a solution of 188 ml of dimethyl malonate in 970 ml of N-methylpyrrolidone, while cooling with ice, and the mixture is stirred for 2 hours. 150 ml of 2,5-difluoronitrobenzene are added dropwise to the resulting suspension over a period of 30 minutes and then stirred for 6 hours at 85° C. The mixture is poured onto 4 litres of ice water and 250 ml of concentrated hydrochloric acid and extracted with 2 litres of ethyl acetate. The organic phase is dried with sodium sulphate and evaporated down. The oily residue is stirred twice with water and then taken up in 600 ml ethyl acetate. The solution is dried with sodium sulphate and evaporated to dryness. The crystallised crude product is recrystallised from 600 ml ethyl acetate/hexane=2:8 and dried.

Workup

  1. temperaturewhile cooling with ice
  2. stirringstirred for 6 hours at 85° C
  3. extractionextracted with 2 litres of ethyl acetate
  4. dry with materialThe organic phase is dried with sodium sulphate
  5. customevaporated down
  6. stirringThe oily residue is stirred twice with water
  7. dry with materialThe solution is dried with sodium sulphate
  8. customevaporated to dryness
  9. customThe crystallised crude product
  10. customis recrystallised from 600 ml ethyl acetate/hexane=2:8
  11. customdried

Sources & evidence

ORD record
ord-3c5d3711526c4024bf8e47c5279253d4
Source dataset
uspto-grants-2009_04
Patent number
US07514468B2

Reaction notes

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