Methyl iodide → 2-Bromo-4-chloroanisole

HRID 1361515Notes

Reaction equation

HRID 1361515 reaction equation
[C:1]([O-:4])([O-])=O.[K+].[K+].[Br:7][C:8]1[CH:13]=[C:12]([Cl:14])[CH:11]=[CH:10][C:9]=1O.CI>CC(C)=O>[Br:7][C:8]1[CH:13]=[C:12]([Cl:14])[CH:11]=[CH:10][C:9]=1[O:4][CH3:1]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 696702-Bromo-4-chlorophenol

Product 1

HCID 5219352-Bromo-4-chloroanisole

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A mixture of K2CO3 (68 g, 0.5 mol), 2-bromo-4-chorophenol (50 g, 0.24 mol) and MeI (42.6 g, 0.3 mol) in acetone (1000 mL) was heated to reflux for 5 h and then cooled to room temperature. The solid was filtered off and washed with dichloromethane (100 mL×3). The combined filtrate was concentrated to dryness. The residue was diluted with diethyl ether (500 mL) and washed HCl (1 M, 100 mL×2), H2O (100 mL×2) and brine (200 mL). The separated organic layer was dried over Na2SO4 and concentrated to give 2-bromo-4-chloroanisole 5a as light yellow liquid. 1H NMR (CDCl3): δ 7.52 (d, J=2.8 Hz, 1H), 7.24 (q, J1=8.8 Hz, J2=2.8 Hz, 1H), 6.81 (d, J=8.8 Hz, 1H), 3.86 (s, 3H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 5 h
  3. filtrationThe solid was filtered off
  4. washwashed with dichloromethane (100 mL×3)
  5. concentrationThe combined filtrate was concentrated to dryness
  6. additionThe residue was diluted with diethyl ether (500 mL)
  7. washwashed HCl (1 M, 100 mL×2), H2O (100 mL×2) and brine (200 mL)
  8. dry with materialThe separated organic layer was dried over Na2SO4
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-7bb55a3208584323b36c07017728c14b
Source dataset
uspto-grants-2011_02
Patent number
US07880007B2

Reaction notes

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