Hydrochloric Acid → Methyl 2-(5-chloro-2-nitrophenyl)-2-cyanoacetate

HRID 2184295Notes

Reaction equation

HRID 2184295 reaction equation
C(=O)([O-])[O-].[K+].[K+].[C:7]([CH2:9][C:10]([O:12][CH3:13])=[O:11])#[N:8].Cl[C:15]1[CH:20]=[C:19]([Cl:21])[CH:18]=[CH:17][C:16]=1[N+:22]([O-:24])=[O:23].Cl>O.C(OCC)(=O)C.CN(C)C=O>[Cl:21][C:19]1[CH:18]=[CH:17][C:16]([N+:22]([O-:24])=[O:23])=[C:15]([CH:9]([C:7]#[N:8])[C:10]([O:12][CH3:13])=[O:11])[CH:20]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7747Methyl cyanoacetateHCID 11430Potassium CarbonateHCID 118992,4-Dichloronitrobenzene

Product 1

HCID 22476318Methyl 2-(5-chloro-2-nitrophenyl)-2-cyanoacetateYield 87.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

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 7.13 g (51.6 mmol) of potassium carbonate, 20 ml of N,N-dimethylformamide, 5.06 g (50.6 mmol) of methyl cyanoacetate with a purity of 99% and 5.00 g (25.8 mmol) of 2,4-dichloronitrobenzene with a purity of 99% under argon atmosphere, and under stirring, the mixture was reacted at 45° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, 100 ml of ethyl acetate was added to the mixture, and 12.9 ml (77.4 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 mixture, the organic layer was separated, and washed with 50 ml of a saturated saline solution, 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=20:1 (volume ratio)) to obtain 5.76 g (isolation yield: 83%) of methyl 2-(5-chloro-2-nitrophenyl)-2-cyanoacetate as white crystals with a purity of 95% (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 45° C. for 4 hours
  4. customAfter completion of the reaction
  5. additionwas gradually added dropwise to the mixture
  6. stirringwhile stirring
  7. customthe organic layer was separated
  8. washwashed with 50 ml of a saturated saline solution
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationAfter filtration
  11. concentrationthe filtrate was concentrated under reduced pressure
  12. concentrationthe resulting concentrate
  13. customwas purified by silica gel column chromatography (filler: Daisogel 1002W, eluent: hexane:ethyl acetate=20:1 (volume ratio))

Sources & evidence

ORD record
ord-7a469547703741a9a7792b2a580ffab5
Source dataset
uspto-grants-2005_05
Patent number
US06900335B2

Reaction notes

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