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

HRID 2060024Notes

Reaction equation

HRID 2060024 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 (D90, 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 (D91, 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-85f513a2a2264bd99a6e16b6ff05e75f
Source dataset
uspto-grants-2012_10
Patent number
US08278328B2

Reaction notes

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