3-Chloro-2-methylaniline → 4-Bromo-3-chloro-2-methylaniline

HRID 1057128Notes

Reaction equation

HRID 1057128 reaction equation
[Cl:1][C:2]1[C:3]([CH3:9])=[C:4]([CH:6]=[CH:7][CH:8]=1)[NH2:5].C1C(=O)N([Br:17])C(=O)C1.[O-]S([O-])(=S)=O.[Na+].[Na+]>CC#N>[Br:17][C:8]1[CH:7]=[CH:6][C:4]([NH2:5])=[C:3]([CH3:9])[C:2]=1[Cl:1]

Participants

5

Reactant 3

HCID 68943-Chloro-2-methylanilineHCID 24477Sodium ThiosulfateHCID 67184N-bromobutanimide

Product 1

HCID 71719114-Bromo-3-chloro-2-methylanilineYield 64.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 3-chloro-2-methylaniline (30 g, 0.212 mol) in CH3CN (300 mL) was added NBS (45.2 g, 0.254 mol) in portions at 10° C. The resulting mixture was stirred at room temperature for 30 minutes. Upon completion, saturated Na2S2O3 (500 mL) was added slowly into the reaction mixture at 10° C. The organic layer was separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The residue was washed with petroleum ether to afford the title compound (30 g), which was used in the next step without further purification. 1H NMR (300 MHz, CDCl3): δ 7.24 (d, 1H), 6.48 (d, 1H), 3.70 (br, 2H), 2.28 (s, 3H).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer was extracted with EtOAc
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated in vacuo
  5. washThe residue was washed with petroleum ether

Sources & evidence

ORD record
ord-b274900a050d4a579c41311d3a392116
Source dataset
uspto-grants-2016_07
Patent number
US09399646B2

Reaction notes

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