Methylamine → 6-Chloro-2-(methylamino)-3-nitrobenzonitrile

HRID 1863892Notes

Reaction equation

HRID 1863892 reaction equation
Cl[C:2]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([Cl:13])[C:3]=1[C:4]#[N:5].[CH3:14][NH2:15]>C(OCC)(=O)C>[Cl:13][C:6]1[C:3]([C:4]#[N:5])=[C:2]([NH:15][CH3:14])[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=1

Participants

4

Reactant 2

HCID 6329Methylamine2×HCID 44619322,6-Dichloro-3-nitrobenzonitrile

Product 1

HCID 112180896-Chloro-2-(methylamino)-3-nitrobenzonitrileYield 96%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
5 °C

Procedure

To a 1 L two-neck round bottom flask was added 2,6-dichloro-3-nitrobenzonitrile (11.1 g, 51.1 mmol) followed by ethyl acetate (102 mL). The flask was equipped with an internal thermometer and magnetic stir bar and cooled to 5° C. by immersion into an ice bath. Methylamine was added dropwise to the cooled reaction mixture as a 40% aqueous solution (8.9 mL, 115 mmol) with vigorous stirring. The reaction mixture was stirred for an additional 3 hours with cooling, after which more methylamine (1.8 mL, 23 mmol) was added. The reaction vessel was removed from the ice bath and stirred for an additional 1.5 hours. To the reaction mixture was added water (30 mL) followed immediately by hexane (45 mL) and the resulting slurry was stirred for 15 minutes. The solid was recovered by filtration and washed with water followed by methanol to provide 6-chloro-2-methylamino-3-nitro-benzonitrile (10.49 g, 96%) as a bright yellow solid, which was used directly without further purification. 1H NMR (400 MHz, DMSO-d6) δ 8.55-8.53 (m, 1H), 8.28 (d, 1H, J=9.0 Hz), 6.95 (d, 1H), J=9.0 Hz), 3.30 (d, 1H, J=5.5 Hz).

Workup

  1. customThe flask was equipped with an internal thermometer and magnetic stir bar
  2. temperaturewith cooling
  3. customThe reaction vessel was removed from the ice bath
  4. stirringstirred for an additional 1.5 hours
  5. additionTo the reaction mixture was added water (30 mL)
  6. stirringthe resulting slurry was stirred for 15 minutes
  7. filtrationThe solid was recovered by filtration
  8. washwashed with water

Sources & evidence

ORD record
ord-2be861ab561d4c57a7e50da823d0794c
Source dataset
uspto-grants-2009_12
Patent number
US07625880B2

Reaction notes

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