Benzenamine, 3-bromo-4-methyl- → 5-Bromo-2-iodo-4-methylaniline

HRID 523244

Reaction equation

HRID 523244 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[CH3:9])[NH2:5].[I:10]N1C(=O)CCC1=O.[B-](F)(F)(F)F.C1C=CN=CC=1.C1C=CN=CC=1.[IH2+]>C(Cl)Cl>[Br:1][C:2]1[C:8]([CH3:9])=[CH:7][C:6]([I:10])=[C:4]([CH:3]=1)[NH2:5]

Participants

5

Reactant 3

HCID 82187Benzenamine, 3-bromo-4-methyl-HCID 120273N-IodosuccinimideHCID 10883201Bis(pyridine)iodonium tetrafluoroborate

Product 1

HCID 1177764315-Bromo-2-iodo-4-methylanilineYield 83.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 3-bromo-4-methylaniline (5.00 g, 26.9 mmol), N-iodosuccinimide (4.53 g, 20.2 mmol) and bis(pyridine)iodonium tetrafluoroborate (2.70 g, 7.26 mmol) in DCM (100 mL) was stirred at room temperature overnight. The mixture was diluted with DCM, washed sequentially with saturated aqueous NaHSO3 and water, and dried and concentrated. The residue was purified by column chromatography on silica gel, eluting with EtOAc-hexanes (sequentially 1%, 2% and 3%), to provide 5-bromo-2-iodo-4-methylaniline as a yellow solid (5.27 g, 63% yield). Mass spectrum m/z 312, 314 (M+H)+. 1H NMR (500 MHz, CDCl3) δ 7.49 (d, J=0.6 Hz, 1H), 6.94 (s, 1H), 4.17-3.91 (br.s, 2H), and 2.25 (s, 3H).

Workup

  1. washwashed sequentially with saturated aqueous NaHSO3 and water
  2. customdried
  3. concentrationconcentrated
  4. customThe residue was purified by column chromatography on silica gel
  5. washeluting with EtOAc-hexanes (sequentially 1%, 2% and 3%),

Sources & evidence

ORD record
ord-6b1c575cf99143dd801aea8b8ea68062
Source dataset
uspto-grants-2016_05
Patent number
US09334290B2

Linked notes

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