Hydrochloric Acid → 5-Chloro-2-methyl-4-nitrobenzonitrile

HRID 1739834Notes

Reaction equation

HRID 1739834 reaction equation
[Cl:1][C:2]1[C:3]([N+:10]([O-:12])=[O:11])=[CH:4][C:5]([CH3:9])=[C:6]([CH:8]=1)N.Cl.N([O-])=O.[Na+].[C:18]([Cu])#[N:19].[C-]#N.[Na+]>CC(C)=O.O.CCOC(C)=O>[Cl:1][C:2]1[C:3]([N+:10]([O-:12])=[O:11])=[CH:4][C:5]([CH3:9])=[C:6]([CH:8]=1)[C:18]#[N:19]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8929Sodium CyanideHCID 837726-Chloro-4-nitro-o-toluidineHCID 23668193Sodium NitriteHCID 178418546HCID 178418546, compound

Product 1

HCID 102417995-Chloro-2-methyl-4-nitrobenzonitrileYield 77.5%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolvent4×HCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 5-chloro-4-nitro-2-methylaniline (40.0 g, 0.21 mol) in acetone (140 mL) and H2O (150 mL) at 0° C. was added concentrated aqueous HCl (45 mL). The mixture was well stirred and a solution of NaNO2 (18.0 g, 0.26 mol) in H2O (60 mL) was added dropwise over a period of 15 min. The mixture was further stirred for 20 min. and then added portionwise to a vigorously stirred mixture of CuCN (30.0 g, 0.34 mol) and NaCN (44.0 g, 0.90 mol) in H2O (200 mL):EtOAc (100 mL). After stirring at room temperature for 30 min., the mixture was diluted with H2O and extracted with EtOAc. The EtOAc extract was washed successively with 1N NaOH and brine, dried over anhydrous MgSO4 and concentrated. The residue was suspended in hexanes:Et2O (1:1), stirred for 15 min., and filtered to provide the title compound (32 g, 76%) as yellow solid.

Workup

  1. stirringThe mixture was further stirred for 20 min.
  2. stirringAfter stirring at room temperature for 30 min.
  3. extractionextracted with EtOAc
  4. extractionThe EtOAc extract
  5. washwas washed successively with 1N NaOH and brine
  6. dry with materialdried over anhydrous MgSO4
  7. concentrationconcentrated
  8. stirringstirred for 15 min.
  9. filtrationfiltered

Sources & evidence

ORD record
ord-edf593854bda4ae59ef7fe5da95e23a0
Source dataset
uspto-grants-1999_10
Patent number
US05968958

Reaction notes

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