Hydrochloric Acid → Ethyl 3-(4-cyano-2-nitrophenyl)-2-oxopropanoate

HRID 1866232Notes

Reaction equation

HRID 1866232 reaction equation
[Na].C(O[C:5](=[O:11])[C:6]([O:8][CH2:9][CH3:10])=[O:7])C.[CH3:12][C:13]1[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][C:14]=1[N+:21]([O-:23])=[O:22].Cl>CCO>[CH2:9]([O:8][C:6](=[O:7])[C:5](=[O:11])[CH2:12][C:13]1[CH:20]=[CH:19][C:16]([C:17]#[N:18])=[CH:15][C:14]=1[N+:21]([O-:23])=[O:22])[CH3:10]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 5893334-Methyl-3-nitrobenzonitrileHCID 5360545Sodium

Product 1

HCID 10730167Ethyl 3-(4-cyano-2-nitrophenyl)-2-oxopropanoate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Dissolve sodium metal (0.345 g) in absolute EtOH (25 mL), add diethyloxalate (10 mL) and then add 4-methyl-3-nitrobenzonitrile (1b, m=0, 1.6 g, Aldrich) as an EtOH solution (25 mL). Stir the reaction mixture at rt for 16 hours, neutralize the reaction by addition of 5N HCl (3 mL) and remove the EtOH under reduced pressure. Partition the residue between CH2Cl2 (100 mL) and H2O (50 mL). Wash the organic layer successively with H2O (50 mL) and brine (50 mL), dry (MgSO4) and concentrate to give a crude oil. Purify the oil by chromatography on SiO2 eluting with cyclohexane-EtOAc, 70-30 v/v, to afford gave after drying (40° C., house vacuum), the title compound (1.5 g) as yellow crystals, mp 118° C.

Workup

  1. customthe reaction
  2. customremove the EtOH under reduced pressure
  3. customPartition the residue between CH2Cl2 (100 mL) and H2O (50 mL)
  4. washWash the organic layer successively with H2O (50 mL) and brine (50 mL)
  5. dry with materialdry (MgSO4)
  6. concentrationconcentrate
  7. customto give a crude oil
  8. customPurify the oil by chromatography on SiO2 eluting with cyclohexane-EtOAc, 70-30 v/v
  9. customto afford
  10. customgave
  11. customafter drying (40° C., house vacuum)

Sources & evidence

ORD record
ord-13b1971bfd8c4e2c8b62452dca5c01a4
Source dataset
uspto-grants-2009_12
Patent number
US07629376B2

Reaction notes

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