Diethyl Ether → 3-Fluoro-p-anisaldehyde

HRID 1107927Notes

Reaction equation

HRID 1107927 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9].C[CH2:11][O:12]CC>C(Cl)Cl.[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:11]=[O:12]

Participants

5

Reactant 2

HCID 3283Diethyl EtherHCID 675762-Fluoroanisole

Product 1

HCID 676963-Fluoro-p-anisaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
15 °C

Procedure

A solution of o-fluoroanisole, 101 g (0.80 mol) in 500 ml dry methylene chloride is added dropwise over 30 minutes to a solution of titanium tetrachloride, 182 g (0.96 mol, 1.2 equiv.) and a,(x-dichloromethylmethyl ether, 110 g (0.96 mol) 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) is added, and the mixture stirred under nitrogen until solution occurs. The organic layer is extracted with water (3×), with sodium bicarbonate solution (3×) and is dried (MgSO4). The solvent is evaporated at 30° C. to give an oily crude product, which is distilled in vacuo 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 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×), with sodium bicarbonate solution (3×)
  5. dry with materialis dried (MgSO4)
  6. customThe solvent is evaporated at 30° C.
  7. customto give an oily crude product, which
  8. distillationis distilled in vacuo through a jacketed Vigreux column

Sources & evidence

ORD record
ord-e3517507c33c4ece92157656bbad2cf1
Source dataset
uspto-grants-2000_05
Patent number
US06063818

Reaction notes

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