Tin dichloride dihydrate → 3-Bromo-N2-phenylbenzene-1,2-diamine

HRID 243148Notes

Reaction equation

HRID 243148 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-])=O)[C:3]=1[NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.Cl[Sn]Cl.O>CCOC(C)=O.C([O-])(O)=O.[Na+]>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([NH2:8])[C:3]=1[NH:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

5

Reactant 2

HCID 43835034Tin dichloride dihydrateHCID 68157569(2-Bromo-6-nitrophenyl)phenylamine

Product 1

HCID 681577803-Bromo-N2-phenylbenzene-1,2-diamineYield 77%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 516892Sodium BicarbonateSolvent2×

Procedure

(2-Bromo-6-nitrophenyl)phenylamine (6.5 g, 22.7 mmol) was dissolved in EtOAc (100 mL) and SnCl2.H2O (25 g) added under a nitrogen atmosphere. The resulting mixture was heated at reflux for 5 h. The cooled reaction mixture was diluted with NaHCO3 (aq. satd. solution, 100 mL) and additional NaHCO3 added until all effervescence had ceased. The mixture was filtered through Celite® to remove insoluble inorganic material. The EtOAc layer was separated, washed with brine, dried (Na2SO4) and concentrated in vacuo. The residue was purified by chromatography (Si—PCC, 0-50% EtOAc in cyclohexane) to give the product as a yellow crystalline solid (4.41 g, 77%). 1H NMR (300 MHz, CDCl3): δ 7.24-7.17 (2H, m), 7.01 (1H, dd, J=8.0, 1.5 Hz), 6.94 (1H, d, J=7.9 Hz), 6.85 (1H, dt, J=7.4, 1.0 Hz), 6.72 (1H, dd, J=7.9, 1.5 Hz), 6.67-6.61 (2H, m), 5.36 (1H, br s), 3.97 (2H, br s)

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 5 h
  3. customThe cooled reaction mixture
  4. additionadded until all effervescence
  5. filtrationThe mixture was filtered through Celite®
  6. customto remove insoluble inorganic material
  7. customThe EtOAc layer was separated
  8. washwashed with brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by chromatography (Si—PCC, 0-50% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-11ec8fdf5c4746b6996ac5f52e7519a8
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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