Methane, dichloromethoxy- → 4-Chloro-5-ethyl-2-fluorobenzaldehyde

HRID 2105069Notes

Reaction equation

HRID 2105069 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[CH2:9][CH3:10].Cl[CH:12](Cl)[O:13]C>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[Cl:1][C:2]1[C:3]([CH2:9][CH3:10])=[CH:4][C:5]([CH:12]=[O:13])=[C:6]([F:8])[CH:7]=1

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 213412082-Chloro-1-ethyl-4-fluorobenzene

Product 1

HCID 578038014-Chloro-5-ethyl-2-fluorobenzaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

TiCl4 (0.90 mL) was added to 2-chloro-1-ethyl-4-fluorobenzene (645 mg, 4.1 mmol) at 0° C. and stirred to 10 min. Dichloro(methoxy)methane (0.725 mL) was added and the mixture was stirred overnight at ambient temperature. The mixture was diluted with CH2Cl2 (50 mL) and poured onto crushed ice (40 g). After stirring 30 min the layers were separated. The organic layer was washed with H2O (2×), brine (2×), dried (Na2SO4) and concentrated. Purification by flash chromatography (hexanes, EtOAc) yielded 440 mg of intermediate 390.2 as a light brown oil. 1H NMR (400 MHz, CDCl3) δ ppm 1.18 (t, J=7.58 Hz, 3H) 2.69 (q, J=7.58 Hz, 2H) 7.05-7.29 (m, 1H) 7.67 (m, 1H) 10.23 (s, 1H).

Workup

  1. stirringthe mixture was stirred overnight at ambient temperature
  2. additionpoured
  3. stirringAfter stirring 30 min the layers
  4. customwere separated
  5. washThe organic layer was washed with H2O (2×), brine (2×)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated
  8. customPurification by flash chromatography (hexanes, EtOAc)

Sources & evidence

ORD record
ord-01167c6df1c3458eb5b8d9ccfe6f9d00
Source dataset
uspto-grants-2009_08
Patent number
US07576098B2

Reaction notes

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