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

HRID 1392249Notes

Reaction equation

HRID 1392249 reaction equation
C[O-].[Na+].[C:4]([CH2:6][C:7]([O:9][CH3:10])=[O:8])#[N:5].Cl[C:12]1[CH:17]=[C:16]([Cl:18])[CH:15]=[CH:14][C:13]=1[N+:19]([O-:21])=[O:20].Cl>O.C(OC(=O)C)C.CS(C)=O>[Cl:18][C:16]1[CH:15]=[CH:14][C:13]([N+:19]([O-:21])=[O:20])=[C:12]([CH:6]([C:4]#[N:5])[C:7]([O:9][CH3:10])=[O:8])[CH:17]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7747Methyl cyanoacetateHCID 118992,4-DichloronitrobenzeneHCID 10942334Sodium Methoxide

Product 1

HCID 22476318Methyl 2-(5-chloro-2-nitrophenyl)-2-cyanoacetateYield 93%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 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 2.79 g (51.6 mmol) of sodium methoxide and 15 ml of dimethyl sulfoxide under argon atmosphere, and then, while stirring at room temperature, 5.16 g (51.6 mmol) of methyl cyanoacetate with a purity of 99% was gradually added dropwise over 5 minutes. Moreover, at room temperature, to the mixture was gradually added dropwise 5.00 g (25.8 mmol) of 2,4-dichloronitrobenzene with a purity of 98%, and the resulting mixture was reacted at 40 to 48° C. for 10 minutes and at 65° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 100 ml of ethylacetate was added to the mixture, and 4.30 ml (25.7 mmol) of 6 mol/l hydrochloric acid and 20 ml water were gradually added dropwise while stirring. Then, the organic layer was separated, 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=9:1 (volume ratio)) to obtain 6.11 g (isolation yield: 92%) of methyl 2-(5-chloro-2-nitrophenyl)-2-cyanoacetate as yellowish crystals with a purity of 99% (areal percentage by high performance liquid chromatography).

Workup

  1. customIn a flask made of glass
  2. customequipped with a stirrer
  3. customthe resulting mixture was reacted at 40 to 48° C. for 10 minutes and at 65° C. for 2 hours
  4. customAfter completion of the reaction
  5. temperaturethe mixture was cooled to room temperature
  6. additionwere gradually added dropwise
  7. stirringwhile stirring
  8. customThen, the organic layer was separated
  9. washwashed with 50 ml of a saturated saline solution
  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-bdd08a90772d41f58c1c369606c4034b
Source dataset
uspto-grants-2008_03
Patent number
US07342040B2

Reaction notes

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