Sodium Carbonate → 5-Bromo-2-ethylaniline

HRID 1191552Notes

Reaction equation

HRID 1191552 reaction equation
[CH2:1]([C:3]1[CH:8]=[CH:7][C:6]([Br:9])=[CH:5][C:4]=1[N+:10]([O-])=O)[CH3:2].O.O.[Sn](Cl)Cl.C(=O)([O-])[O-].[Na+].[Na+]>C(O)C.C(OCC)(=O)C>[Br:9][C:6]1[CH:7]=[CH:8][C:3]([CH2:1][CH3:2])=[C:4]([CH:5]=1)[NH2:10]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 61436Stannous chloride dihydrateHCID 75669964-Bromo-1-ethyl-2-nitrobenzene

Product 1

HCID 233467565-Bromo-2-ethylanilineYield 17.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 2-ethyl-5-bromo nitrobenzene (9.71 g, 230 mmol) in ethanol (125 ml) is added tin(II) chloride dihydrate (35.72 g, 225.71 mmol), followed by heating at 70° C. for 2 hours. After cooling to room temperature the solution is poured into crushed ice (1 litre) then diluted with ethyl acetate (200 ml). Solid sodium carbonate is cautiously added until pH 7 is achieved, at which stage the viscous mixture is filtered through diatomaceous earth (further washing with ethyl acetate/aqueous sodium carbonate) and the phases separated. After additional extraction of the aqueous phase, all organic phases are combined, dried over anhydrous magnesium sulfate then concentrated in vacuo. The crude oil is purified by flash column chromatography on silica gel (hexane/ethyl acetate 8:2 ratio) to afford 5-bromo-2-ethylaniline (7.89 g) as a brown oil.

Workup

  1. temperatureAfter cooling to room temperature the solution
  2. additionis poured
  3. filtrationis filtered through diatomaceous earth (
  4. washfurther washing with ethyl acetate/aqueous sodium carbonate) and the phases
  5. customseparated
  6. extractionAfter additional extraction of the aqueous phase
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationthen concentrated in vacuo
  9. customThe crude oil is purified by flash column chromatography on silica gel (hexane/ethyl acetate 8:2 ratio)

Sources & evidence

ORD record
ord-89e44700349f42d3ba346aace7617f47
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

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