Hydrochloric Acid → Benzyl 2-cyano-2-(2-nitro-4-methylphenyl)ethanoate

HRID 1798021Notes

Reaction equation

HRID 1798021 reaction equation
[C:1]([CH2:3][C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5])#[N:2].C(=O)([O-])[O-].[K+].[K+].[N+:20]([C:23]1[CH:24]=[C:25]([CH3:30])[CH:26]=[CH:27][C:28]=1Cl)([O-:22])=[O:21].Cl>CN(C=O)C.O.CCOCC>[C:1]([CH:3]([C:28]1[CH:27]=[CH:26][C:25]([CH3:30])=[CH:24][C:23]=1[N+:20]([O-:22])=[O:21])[C:4]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:5])#[N:2]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 69764-Chloro-3-nitrotolueneHCID 11430Potassium CarbonateHCID 560818Benzyl 2-cyanoacetate

Product 1

HCID 10935797Benzyl 2-cyano-2-(2-nitro-4-methylphenyl)ethanoateYield 75%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
70 °C

Procedure

benzyl cyanoacetate (3.50 g; 20 mmol) is added to a suspension of potassium carbonate (6.08 g; 44 mmol) in 5 mL of DMF. The carbonate is washed with 2 mL of DMF. A solution of 3-nitro-4-chlorotoluene (3.41 g, 20 mmol) in 5 mL of DMF is added and the resulting reaction mixture is stirred at 70° C. for 24 hours. After cooling down to ambient temperature, it is treated with a 5N aqueous solution of HCl (12.5 mL). The mixture is divided between ether (100 mL) and water (50 mL) then the organic phase is re-extracted with ether. The ethereal phases are washed with water, dried over anhydrous MgSO4, filtered under vacuum and evaporated. The residue is purified by chromatography on silica gel (eluent: CH2Cl2/pentane, 1/1) in order to produce benzyl 2-cyano-2-(2-nitro-4-methylphenyl)ethanoate with a yield of 75%.

Workup

  1. washThe carbonate is washed with 2 mL of DMF
  2. customthe resulting reaction mixture
  3. temperatureAfter cooling down to ambient temperature
  4. extractionthe organic phase is re-extracted with ether
  5. washThe ethereal phases are washed with water
  6. dry with materialdried over anhydrous MgSO4
  7. filtrationfiltered under vacuum
  8. customevaporated
  9. customThe residue is purified by chromatography on silica gel (eluent: CH2Cl2/pentane, 1/1) in order

Sources & evidence

ORD record
ord-ee76062ee6064e0abc2bcf803b446e58
Source dataset
uspto-grants-2013_01
Patent number
US08343964B2

Reaction notes

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