4-Chlorotoluene → 5-Chloro-2-methylbenzaldehyde

HRID 1700718Notes

Reaction equation

HRID 1700718 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.Cl[CH:10]([O:12][CH3:13])Cl>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[CH:10]=[O:12].[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:8])=[C:6]([CH:7]=1)[CH:13]=[O:12]

Participants

6

Reactant 2

HCID 78104-ChlorotolueneHCID 21004Methane, dichloromethoxy-

Product 2

HCID 123475655-Chloro-2-methylbenzaldehydeHCID 156472782-Chloro-5-methylbenzaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 4-chlorotoluene (25.0 g) and dichloromethylmethylether (45.4 g) in dichloromethane (160 ml) was added dropwise at room temperature a solution of titanium tetrachloride (74.9 g) in dichloromethane (40 ml), and the mixture was stirred at the same temperature for 15 hours. The reaction solution was poured into ice, and the organic layer was washed with water, sodium hydrogen carbonate solution, water and saturated brine, and dried with magnesium sulfate. Under reduced pressure, the solvent was evaporated, and the residue was subjected to silica gel column chromatography (ethyl acetate-hexane) to give oil of crude 2-chloro-5-methylbenzaldehyde (18.3 g) and 5-chloro-2-methylbenzaldehyde (4.1 g), respectively.

Workup

  1. additionThe reaction solution was poured into ice
  2. washthe organic layer was washed with water, sodium hydrogen carbonate solution, water and saturated brine
  3. dry with materialdried with magnesium sulfate
  4. customUnder reduced pressure, the solvent was evaporated

Sources & evidence

ORD record
ord-c13bf91271ea4887aa1f5b86547c8670
Source dataset
uspto-grants-2002_02
Patent number
US06350749B1

Reaction notes

Loading…