3-Amino-4-methylbenzonitrile → 3-Hydroxy-4-methylbenzonitrile

HRID 1584089Notes

Reaction equation

HRID 1584089 reaction equation
N([O-])=[O:2].[Na+].N[C:6]1[CH:7]=[C:8]([CH:11]=[CH:12][C:13]=1[CH3:14])[C:9]#[N:10]>O.Cl>[OH:2][C:6]1[CH:7]=[C:8]([CH:11]=[CH:12][C:13]=1[CH3:14])[C:9]#[N:10]

Participants

5

Reactant 2

HCID 70164283-Amino-4-methylbenzonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 177509203-Hydroxy-4-methylbenzonitrile

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Conditions

Temperature
2.5 °C

Procedure

A solution of 49.2 g (0.72 mol) of NaNO2 in 217 ml of water was added dropwise to 85 g (0.72 mol) of 3-amino-4-methylbenzonitrile in 1.8 l of 6N HCl at 0-5° C. over the course of 0.5 h. The mixture was then stirred at 0-5° C. for a further 30 min and subsequently at the boiling point for 1 h. After the solution had cooled, the product was extracted with ethyl acetate and, from this, in the form of the phenolate with ice-cooled 5 N NaOH. The aqueous phase was then acidified to pH 3 with 6N HCl, and the product was extracted with ethyl acetate. 41 g (43%) were obtained. 1H-NMR (DMSO-d6 ; δ in ppm): 10.3 (s, OH); 7.25 (dd, 1H); 7.15 (d, 1H); 7.1 (dd, 1H); 2.20 (s, 3H)

Workup

  1. temperatureAfter the solution had cooled
  2. extractionthe product was extracted with ethyl acetate
  3. temperaturefrom this, in the form of the phenolate with ice-cooled 5 N NaOH
  4. extractionthe product was extracted with ethyl acetate
  5. custom41 g (43%) were obtained

Sources & evidence

ORD record
ord-f4fb7954c1b541228c3e9b3578275026
Source dataset
uspto-grants-1999_08
Patent number
US05932567

Reaction notes

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