Stannous Chloride → 5-Bromo-2-cyclopropylaniline

HRID 40475Notes

Reaction equation

HRID 40475 reaction equation
[Sn](Cl)Cl.[Br:4][C:5]1[CH:6]=[CH:7][C:8]([CH:14]2[CH2:16][CH2:15]2)=[C:9]([N+:11]([O-])=O)[CH:10]=1>C(O)C.O>[Br:4][C:5]1[CH:6]=[CH:7][C:8]([CH:14]2[CH2:16][CH2:15]2)=[C:9]([CH:10]=1)[NH2:11]

Participants

5

Reactant 2

HCID 24479Stannous Chloride2×HCID 6713434-Bromo-1-cyclopropyl-2-nitrobenzene

Product 1

HCID 47122485-Bromo-2-cyclopropylaniline

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Tin(II)chloride (16.0 g, 0.10 mol) is added in one portion to a solution of crude 5-bromo-2-cyclopropylnitrobenzene (8.68 g) in ethanol (190 ml) and water (1.9 ml). The reaction mixture is stirred at room temperature overnight, followed by addition of further tin(II)chloride (28 g, 0.175 mol) and additional stirring overnight. After concentration in vacuo ice is added, and the solution is basified with 2M aqueous sodium hydroxide. After extraction with ethyl acetate (×2) the organic phase is washed again with 2M aqueous sodium hydroxide, then also distilled water and brine. After drying over magnesium sulfate the solution is concentrated in vacuo to give a brown oil which is purified by flash column chromatography on silica gel (9:1 isohexane/ethyl acetate eluant) to afford 5-bromo-2-cyclopropylaniline as a brown oil.

Workup

  1. stirringadditional stirring overnight
  2. concentrationAfter concentration in vacuo ice
  3. additionis added
  4. extractionAfter extraction with ethyl acetate (×2) the organic phase
  5. washis washed again with 2M aqueous sodium hydroxide
  6. dry with materialAfter drying over magnesium sulfate the solution
  7. concentrationis concentrated in vacuo
  8. customto give a brown oil which
  9. customis purified by flash column chromatography on silica gel (9:1 isohexane/ethyl acetate eluant)

Sources & evidence

ORD record
ord-a9f631c5e7aa400ea193390caf8a7d24
Source dataset
uspto-grants-2013_09
Patent number
US08530388B2

Reaction notes

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