Ammonia → 2-Amino-3-methylbenzonitrile

HRID 44351Notes

Reaction equation

HRID 44351 reaction equation
Br[C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([CH3:9])[C:3]=1[NH2:4].[C:10]([Cu])#[N:11].N>CN1C(=O)CCC1>[NH2:4][C:3]1[C:5]([CH3:9])=[CH:6][CH:7]=[CH:8][C:2]=1[C:10]#[N:11]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 27562502-Bromo-6-methylanilineHCID 178418546HCID 178418546, compound

Product 1

HCID 108554942-Amino-3-methylbenzonitrile

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To a solution of 2-bromo-6-methylaniline (126 μL, 1 mmol) in dry NMP (3 mL) was added CuCN (197 mg, 2.2 mmol). The mixture was irradiated in a microwave at 220° C. for 40 minutes, cooled to room temperature and poured into a mixture of ammonia (50% w/v, 10 mL) and ice. The mixture was stirred for 30 min and the product was extracted with dichloromethane (3×20 mL). The organic layers were combined, washed with water and brine, dried over MgSO4 and concentrated. The crude material was purified on silica gel (50% EtOAc/hexanes) to yield a brown oil that crystallized on standing (128 mg, 96%). 1H NMR (400 MHz, DMSO-d6) δ2.08 (s, 3H), 5.68 (bs, 2H), 6.51-6.55 (t, 1H), 7.17-7.19 (d, 1H), 7.22-7.24 (dd, 1H). MS 133 (MH+).

Workup

  1. customThe mixture was irradiated in a microwave at 220° C. for 40 minutes
  2. extractionthe product was extracted with dichloromethane (3×20 mL)
  3. washwashed with water and brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customThe crude material was purified on silica gel (50% EtOAc/hexanes)
  7. customto yield a brown oil that
  8. customcrystallized

Sources & evidence

ORD record
ord-3251c8f4428449ff9aed65e0d8c97f0e
Source dataset
uspto-grants-2013_09
Patent number
US08541421B2

Reaction notes

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