Methane, dichloromethoxy- → 2-Fluoro-4-hydroxy-5-methylbenzaldehyde

HRID 1693060Notes

Reaction equation

HRID 1693060 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:9])=[C:6]([OH:8])[CH:7]=1.Cl[CH:11]([O:13]C)Cl>ClCCl.[Cl-].[Ti+4].[Cl-].[Cl-].[Cl-]>[F:1][C:2]1[CH:7]=[C:6]([OH:8])[C:5]([CH3:9])=[CH:4][C:3]=1[CH:11]=[O:13]

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 27746165-Fluoro-2-methylphenol

Product 1

HCID 574581502-Fluoro-4-hydroxy-5-methylbenzaldehydeYield 71%

Reagents, catalysts & solvents 2

HCID 160960Diamminetetrachlorotitanate(IV)CatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 5-fluoro-2-methylphenol (630 mg, 5 mmol) in dichloromethane (5 ml) was added titanium chloride (1890 mg, 10 mmol) dropwise at 0° C. and then (dichloromethyl)-methyl ether (689 mg, 6 mmol) was added dropwise. The mixture was stirred at 0° C. for 1 hour, quenched with ice (50 g) and extracted with ethyl acetate. The organic layer was separated, dried over Na2SO4, concentrated and applied to a silica gel column, eluting with hexane/ethyl acetate (10:1), to furnish the title compound (545 mg, 71% yield) as a white solid. 1H NMR (270 MHz, CDCl3) δ 2.25 (3H, s), 6.04 (1H, brs), 6.60 (1H, d, J=11.2 Hz), 7.66 (1H, d, J=7.9 Hz), 10.18 (1H, s).

Workup

  1. customquenched with ice (50 g)
  2. extractionextracted with ethyl acetate
  3. customThe organic layer was separated
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated
  6. washeluting with hexane/ethyl acetate (10:1)

Sources & evidence

ORD record
ord-78ea0df6bceb4a97a7c842b77627f0c9
Source dataset
uspto-grants-2012_04
Patent number
US08158650B2

Reaction notes

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