Methane, dichloromethoxy- → 2,3,4-Trimethoxy-6-methylbenzaldehyde

HRID 1835432Notes

Reaction equation

HRID 1835432 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH3:13])[CH:6]=[C:7]([O:11][CH3:12])[C:8]=1[O:9][CH3:10].[Cl-].[Al+3].[Cl-].[Cl-].[CH3:18][O:19]C(Cl)Cl>C(Cl)Cl>[CH3:12][O:11][C:7]1[C:8]([O:9][CH3:10])=[C:3]([O:2][CH3:1])[CH:4]=[C:5]([CH3:13])[C:6]=1[CH:18]=[O:19]

Participants

5

Reactant 3

HCID 21004Methane, dichloromethoxy-HCID 809223,4,5-TrimethoxytolueneHCID 6451240Aluminum(III) Chloride

Product 1

HCID 896832,3,4-Trimethoxy-6-methylbenzaldehydeYield 87%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

A dry methylene chloride (100 ml) solution of 128 g (0.7 mol) of 3,4,5-trimethoxytoluene was dropwise added to a dry methylene chloride 500 ml solution of 112 g (0.84 mol) of aluminum chloride gradually under cooling with ice. The mixture was stirred at the same temperature for 45 minutes, a dry methylene chloride solution of 88.5 g (0.77 mol) of dichloromethyl methyl ether was dropwise added thereto gradually over a period of 2 hours. Stirring was conducted at the same temperature for 2 hours, and the mixture was gradually recovered to room temperature, followed by stirring at room temperature for one night. The reaction mixture was poured into 1 l of ice water, the methylene chloride phase was separated, and the aqueous phase was extracted with 200 ml of methylene chloride twice. The extract and the methylene chloride phase were combined together, sequentially washed with 200 ml of water, 200 ml of a saturated aqueous sodium bicarbonate solution and 200 ml of a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. A seed for a crystal was inoculated into the residue, and the resulting crystal was collected by filtration, washed with hexane and air dried to obtain 128 g of 2,3,4-trimethoxy-6-methylbenzaldehyde (m.p. 55-57° C.).

Workup

  1. temperatureunder cooling with ice
  2. waitgradually over a period of 2 hours
  3. stirringStirring
  4. waitwas conducted at the same temperature for 2 hours
  5. customthe mixture was gradually recovered to room temperature
  6. stirringby stirring at room temperature for one night
  7. additionThe reaction mixture was poured into 1 l of ice water
  8. customthe methylene chloride phase was separated
  9. extractionthe aqueous phase was extracted with 200 ml of methylene chloride twice
  10. extractionThe extract
  11. washsequentially washed with 200 ml of water, 200 ml of a saturated aqueous sodium bicarbonate solution and 200 ml of a saturated aqueous sodium chloride solution
  12. dry with materialdried over anhydrous magnesium sulfate
  13. distillationthe solvent was distilled off under reduced pressure
  14. filtrationthe resulting crystal was collected by filtration
  15. washwashed with hexane and air
  16. customdried

Sources & evidence

ORD record
ord-7c9d9740f1ff41f5877806e8414be7b4
Source dataset
uspto-grants-2004_08
Patent number
US06770662B2

Reaction notes

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