Hydrochloric Acid → HCID 10038811, compound

HRID 1392250Notes

Reaction equation

HRID 1392250 reaction equation
C(=O)([O-])[O-].[K+].[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]=[C:21]([F:23])[CH:20]=[CH:19][C:18]=1[N+:24]([O-:26])=[O:25].Cl>O.C(OCC)(=O)C.CN(C)C=O>[F:23][C:21]1[CH:20]=[CH:19][C:18]([N+:24]([O-:26])=[O:25])=[C:17]([CH:8]([C:7]([O:14][CH3:15])=[O:13])[C:9]([O:11][CH3:12])=[O:10])[CH:22]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 11430Potassium CarbonateHCID 679672,4-Difluoronitrobenzene

Product 1

HCID 10038811HCID 10038811, compoundYield 74.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

In a flask made of glass equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel and having an inner volume of 200 ml were charged 6.51 g (47.2 mmol) of potassium carbonate, 20 ml of N,N-dimethylformamide, 6.24 g (46.7 mmol) of dimethyl malonate with a purity of 99% and 5.00 g (30.8 mmol) of 2,4-difluoronitrobenzene with a purity of 98% under argon atmosphere, and under stirring, the mixture was reacted at room temperature for one hour and further by raising to 70° C. for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, 100 ml of ethyl acetate was added to the mixture, and 10.5 ml (62.8 mmol) of 6 mol/l hydrochloric acid was gradually added dropwise to the mixture while stirring. Then, after adding 50 ml of water to the reaction mixture, the organic layer was separated, and washed successively with 20 ml of water and 20 ml of a saturated saline solution in this order, and dried over anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography (filler:Daisogel 1002W, eluent:hexane:ethyl acetate=9:1 (volume ratio)) to obtain 6.22 g (isolation yield: 73%) of dimethyl 2-(5-fluoro-2-nitrophenyl)malonate as white crystals with a purity of 98% (areal percentage by high performance liquid chromatography).

Workup

  1. customIn a flask made of glass
  2. customequipped with a stirrer
  3. customthe mixture was reacted at room temperature for one hour
  4. customAfter completion of the reaction
  5. temperaturethe mixture was cooled to room temperature
  6. additionwas gradually added dropwise to the mixture
  7. stirringwhile stirring
  8. customthe organic layer was separated
  9. washwashed successively with 20 ml of water and 20 ml of a saturated saline solution in this order
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationAfter filtration
  12. concentrationthe filtrate was concentrated under reduced pressure
  13. concentrationthe resulting concentrate
  14. customwas purified by silica gel column chromatography (filler:Daisogel 1002W, eluent:hexane:ethyl acetate=9:1 (volume ratio))

Sources & evidence

ORD record
ord-c8766d570d3f4002957cb93edef242b8
Source dataset
uspto-grants-2008_03
Patent number
US07342040B2

Reaction notes

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