Diethyl Ether → 3-Fluoro-p-anisaldehyde

HRID 377750Notes

Reaction equation

HRID 377750 reaction equation
Cl[CH:2]([O:4]C)Cl.[F:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[O:13][CH3:14].CCOCC>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[F:6][C:7]1[CH:12]=[C:11]([CH:10]=[CH:9][C:8]=1[O:13][CH3:14])[CH:2]=[O:4]

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 21004Methane, dichloromethoxy-HCID 675762-Fluoroanisole

Product 1

HCID 676963-Fluoro-p-anisaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of titanium tetrachloride (182 g, 0.96 mol, 1.2 equiv.) and α,α, -dichloromethylmethyl ether (110 g, 0.96 mol) in an equal volume of methylene chloride is slowly added (30 minutes) to a solution of o-fluoroanisole (101 g, 0.80 mol) in dry methylene chloride (50 ml) at 10-20° C. The mixture is stirred at room temperature for one hour, is poured over crushed ice water and ether (1 l ) with stirring. This mixture is stirred under nitrogen until solution occurs. The organic layer is extracted with water, aqueous sodium bicarbonate, and is dried (MgSO4). The solvent is evaporated at 30° C. The residual oil is vacuum-distilled through a jacketed Vigreux column to give 3-fluoro-4-methoxybenzaldehyde, B.P. 120-121° C. (10 mm Hg) Rf 0.6 on a silica-gel G plate with methylene chloride.

Workup

  1. additionis poured
  2. stirringwith stirring
  3. stirringThis mixture is stirred under nitrogen until solution
  4. extractionThe organic layer is extracted with water, aqueous sodium bicarbonate
  5. dry with materialis dried (MgSO4)
  6. customThe solvent is evaporated at 30° C
  7. distillationThe residual oil is vacuum-distilled through a jacketed Vigreux column

Sources & evidence

ORD record
ord-d25e1f7545944dadba2540c5aceee07b
Source dataset
uspto-grants-2000_02
Patent number
US06028116

Reaction notes

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