Stannous chloride dihydrate → 3-Amino-5-bromobenzonitrile

HRID 2070936Notes

Reaction equation

HRID 2070936 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([N+:10]([O-])=O)[CH:9]=1)[C:5]#[N:6].O.O.Cl[Sn]Cl>CCO.C1COCC1>[NH2:10][C:8]1[CH:7]=[C:4]([CH:3]=[C:2]([Br:1])[CH:9]=1)[C:5]#[N:6]

Participants

5

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 51524253-Bromo-5-nitrobenzonitrile

Product 1

HCID 534069613-Amino-5-bromobenzonitrileYield 61.8%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirring solution of 1.8 g of 3-bromo-5-nitrobenzonitrile in 8 mL of EtOH and 8 mL of THF was added 8.8 g (38.6 mmol) of SnCl2.2H2O in several portions. The mixture was allowed to stir at r.t. for 10.5 h and then concentrated. A solution of 2N NaOH (60 mL) was added and stirring continued for 2 h. EtOAc was added, and the layers were separated. The organic layer was washed with H2O and brine. The aqueous layer was reextracted with EtOAc and washed with brine. The combined extracts were dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (35% EtOAc/hexanes) provided 965 mg of 3-amino-5-bromobenzonitrile.

Workup

  1. concentrationconcentrated
  2. additionA solution of 2N NaOH (60 mL) was added
  3. stirringstirring
  4. waitcontinued for 2 h
  5. additionEtOAc was added
  6. customthe layers were separated
  7. washThe organic layer was washed with H2O and brine
  8. washwashed with brine
  9. dry with materialThe combined extracts were dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customPurification by flash silica gel chromatography (35% EtOAc/hexanes)

Sources & evidence

ORD record
ord-f4c91ecd7cc0438da14a105d26448c32
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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