Nitric Acid → 5-Hydroxy-2-methyl-4-nitrobenzonitrile

HRID 2070096Notes

Reaction equation

HRID 2070096 reaction equation
[OH:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7]#[N:8].[N+:11]([O-])([OH:13])=[O:12].O>C(Cl)Cl>[OH:1][C:2]1[C:3]([N+:11]([O-:13])=[O:12])=[CH:4][C:5]([CH3:10])=[C:6]([CH:9]=1)[C:7]#[N:8]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 594440865-Hydroxy-2-methylbenzonitrile

Product 1

HCID 594441745-Hydroxy-2-methyl-4-nitrobenzonitrileYield 29.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

5-Hydroxy-2-methylbenzonitrile (D36, 475 mg, 3.57 mmol) was dissolved in DCM (5 mL) and 70% nitric acid (1 mL, 22 mmol) was added dropwise to the reaction. The mixture was stirred for 45 min before the addition of H2O (15 mL). The two phases were separated and the aqueous phase was extracted with DCM (2×). The combined organics were dried (Na2SO4) and concentrated by rotary evaporation to give a yellow solid. The crude residues were purified by flash column chromatography (silica, 10% EtOAc/90% iso-hexane to 50% EtOAc/50% iso-hexane) to give 5-hydroxy-2-methyl-4-nitrobenzonitrile (D37, 186 mg, 26%) as a yellow solid.

Workup

  1. customThe two phases were separated
  2. extractionthe aqueous phase was extracted with DCM (2×)
  3. dry with materialThe combined organics were dried (Na2SO4)
  4. concentrationconcentrated by rotary evaporation
  5. customto give a yellow solid
  6. customThe crude residues were purified by flash column chromatography (silica, 10% EtOAc/90% iso-hexane to 50% EtOAc/50% iso-hexane)

Sources & evidence

ORD record
ord-c27e9a045cbf4e86af69632475e8fa7f
Source dataset
uspto-grants-2012_10
Patent number
US08299257B2

Reaction notes

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