Diethyl Ether → 3-Fluoro-p-anisaldehyde

HRID 1977185Notes

Reaction equation

HRID 1977185 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9].C(Cl)Cl.C[CH2:14][O:15]CC>[Ti](Cl)(Cl)(Cl)Cl>[F:1][C:2]1[CH:7]=[C:6]([CH:5]=[CH:4][C:3]=1[O:8][CH3:9])[CH:14]=[O:15]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 6344Dichloromethane2×HCID 675762-Fluoroanisole

Product 1

HCID 676963-Fluoro-p-anisaldehyde

Reagents, catalysts & solvents 1

HCID 24193Titanium TetrachlorideCatalyst

Conditions

Temperature
15 °C

Procedure

To a solution of o-fluoroanisole, 101 g. (0.80 mole) in 500 ml. dry methylene chloride is added dropwise over 30 minutes a solution of titanium tetrachloride, 182 g. (0.96 mole, 1.2 equiv.) and α,α-dichloromethylmethyl ether, 110 g. (0.96 mole) in an equal volume of methylene chloride. The temperature is maintained at 10-20° C. with an ice-bath. The mixture is stirred at room temperature for 1 hour longer and then poured over crushed ice-water with stirring. Ether (1 l.) is added, and the mixture stirred under nitrogen until solution occurs. The organic layer is extracted with water (3×), sodium bicarbonate solution (3×) and dried (MgSO4). The solvent is evaporated off at 30° to give crude product as an oil. The oil is vacuum distilled through a jacketed Vigreoux column when it gives 3-fluoro-4-methoxybenzaldehyde, B.P. 120-121° C., at 10 mm. Hg; Rf 0.6 on a silica-gel G plate with methylene chloride.

Workup

  1. additionpoured
  2. stirringwith stirring
  3. stirringthe mixture stirred under nitrogen until solution
  4. extractionThe organic layer is extracted with water (3×), sodium bicarbonate solution (3×)
  5. dry with materialdried (MgSO4)
  6. customThe solvent is evaporated off at 30°
  7. customto give crude product as an oil
  8. distillationdistilled through a jacketed Vigreoux column when it

Sources & evidence

ORD record
ord-e7f58a1d9a0b486d880e36c003286648
Source dataset
uspto-grants-2001_05
Patent number
US06232312B1

Reaction notes

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