Methanol → 2-Hydroxy-6-nitrobenzonitrile

HRID 711721Notes

Reaction equation

HRID 711721 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[C:8]([N+]([O-])=O)[C:5]=1[C:6]#[N:7])([O-:3])=[O:2].Cl.N1C=CC=CC=1.C[OH:23]>>[OH:23][C:8]1[CH:9]=[CH:10][CH:11]=[C:4]([N+:1]([O-:3])=[O:2])[C:5]=1[C:6]#[N:7]

Participants

4

Reactant 3

HCID 887Methanol2×HCID 520718DinitrobenzonitrileHCID 10176127Pyridinium chloride

Product 1

HCID 125032052-Hydroxy-6-nitrobenzonitrileYield 87%

Procedure

To a solution of 2,6-dinitrobenzonitrile (10.0 g, 52.3 mmol) in MeOH (215 mL), was added a solution of Na (1.32 g, 57.5 mmol) in MeOH (23.3 mL). The reaction was refluxed under N2 for 2.5 hours, cooled to rt and the precipitate was collected by filtration. The resulting residue was combined with pyridine hydrochloride (15.1 g, 130 mmol), and the solids were melted at 200° C. for 18 hours. Upon completion, the reaction was cooled to rt, washed with brine (1×300 mL) and extracted with EtOAc (2×500 mL). The organic layers were combined, dried over MgSO4, filtered and concentrated to provide 2-hydroxy-6-nitrobenzonitrile (6.70 g, 87%). 1H NMR (400 MHz, MeOD) δ 7.35 (dd, J=8.3, 0.8 Hz, 1H), 7.67 (t, J=8.2 Hz, 1H), 7.77 (dd, J=8.2, 1.1 Hz, 1H).

Workup

  1. temperatureThe reaction was refluxed under N2 for 2.5 hours
  2. filtrationthe precipitate was collected by filtration
  3. customfor 18 hours
  4. temperatureUpon completion, the reaction was cooled to rt
  5. washwashed with brine (1×300 mL)
  6. extractionextracted with EtOAc (2×500 mL)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-7ca744a0b1ae4b33abb43d15f8d0c5ec
Source dataset
uspto-grants-2015_11
Patent number
US09181276B2

Reaction notes

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