4-Chloro-3,5-dinitrobenzonitrile → 3,5-Diamino-4-chlorobenzonitrile

HRID 921862Notes

Reaction equation

HRID 921862 reaction equation
[Cl:1][C:2]1[C:9]([N+:10]([O-])=O)=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:13]([O-:15])=[O:14]>[Fe].C(O)(=O)C>[NH2:10][C:9]1[CH:8]=[C:5]([CH:4]=[C:3]([N+:13]([O-:15])=[O:14])[C:2]=1[Cl:1])[C:6]#[N:7].[NH2:13][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([NH2:10])[C:2]=1[Cl:1])[C:6]#[N:7]

Participants

5

Reactant 1

HCID 160084-Chloro-3,5-dinitrobenzonitrile

Product 2

HCID 124029953,5-Diamino-4-chlorobenzonitrileHCID 717559993-Amino-4-chloro-5-nitrobenzonitrile

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
110 °C

Procedure

A 3-neck round bottom flask was equipped with a condenser. The flask was loaded with 4-chloro-3,5-dinitrobenzonitrile (4.5 g, 19.18 mmol) and acetic acid (60 mL). The solution was heated to 110° C. Iron (powder) (2.5 g, 44.8 mmol) was added slowly (in three portions), saw bubbling and also color changed to dark red. The mixture was stirred vigorously for 2 h at 110° C. LC-MS indicated desired monoamine and diamine. Then it was cooled to room temperature and diluted with DCM and saturated aqueous sodium bicarbonate solution was slowly added to neutralize. After separating the layers, the aqueous layer was further extracted with DCM. The combined organic extracts were washed with water, brine, dried over MgSO4, filtered and concentrated. Purification via flash chromatography (0-20% EtOAc in DCM, 120 g) gave 3-amino-4-chloro-5-nitrobenzonitrile (1.8 g) and 3,5-diamino-4-chlorobenzonitrile (1 g) as bright yellow solid and brown solid respectively.

Workup

  1. customA 3-neck round bottom flask was equipped with a condenser
  2. customsaw bubbling
  3. temperatureThen it was cooled to room temperature
  4. additiondiluted with DCM and saturated aqueous sodium bicarbonate solution
  5. additionwas slowly added
  6. customAfter separating the layers
  7. extractionthe aqueous layer was further extracted with DCM
  8. washThe combined organic extracts were washed with water, brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification via flash chromatography (0-20% EtOAc in DCM, 120 g)

Sources & evidence

ORD record
ord-4b4132db900b45ec935f5b07d43374ec
Source dataset
uspto-grants-2016_03
Patent number
US09273057B2

Reaction notes

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