Hydrochloric Acid → 2-Amino-6-nitrobenzonitrile

HRID 471600Notes

Reaction equation

HRID 471600 reaction equation
Cl.[N+:2]([C:5]1[CH:12]=[CH:11][CH:10]=[C:9]([N+:13]([O-])=O)[C:6]=1[C:7]#[N:8])([O-:4])=[O:3].CCOC(C)=O.O>CO.O1CCOCC1.[Fe]>[NH2:13][C:9]1[CH:10]=[CH:11][CH:12]=[C:5]([N+:2]([O-:4])=[O:3])[C:6]=1[C:7]#[N:8]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 8857Ethyl AcetateHCID 520718Dinitrobenzonitrile

Product 1

HCID 127157292-Amino-6-nitrobenzonitrileYield 68.1%

Reagents, catalysts & solvents 3

HCID 23925IronCatalyst2×HCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

Concentrated HCl (39 mL) was added to a solution of 2,6-dinitrobenzonitrile (11.3 g, 58.5 mmol) in MeOH (235 mL) and 1,4-dioxane (145 mL) at 70° C. External heating was removed, and iron powder (11.44 g, 205 mmol) was added slowly in portions at a rate which maintained a temperature of 70° C. After the addition of iron was complete, the reaction was heated at reflux for a further 30 min, then cooled to room temperature and poured into EtOAc (400 mL) and water (400 mL). The solids were filtered out and extracted twice with boiling EtOAc (300 mL). The combined organic extract was dried with MgSO4, filtered and evaporated to give 2-amino-6-nitrobenzonitrile (6.5 g, 68%) as a red solid, which was used without further purification. 1H-NMR (400 MHz, DMSO-d6) δ 7.48-7.54 (m, 1H), 7.41-7.45 (m, 1H), 7.18-7.22 (m, 1H), 6.74 (broad s, 2H).

Workup

  1. temperatureExternal heating
  2. customwas removed
  3. temperaturethe reaction was heated
  4. temperatureat reflux for a further 30 min
  5. temperaturecooled to room temperature
  6. filtrationThe solids were filtered out
  7. extractionextracted twice with boiling EtOAc (300 mL)
  8. extractionThe combined organic extract
  9. dry with materialwas dried with MgSO4
  10. filtrationfiltered
  11. customevaporated

Sources & evidence

ORD record
ord-0609f4aa410144d587d59fd804bdcd6a
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Reaction notes

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