Dichloromethane → 1,3-Benzodioxole-4-carboxaldehyde

HRID 260157Notes

Reaction equation

HRID 260157 reaction equation
[OH:1][C:2]1[C:9]([OH:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[C:11](=O)([O-])[O-].[K+].[K+].C(Cl)Cl>[Cu]=O.CN(C)C=O>[CH2:11]1[O:10][C:9]2[C:2](=[C:3]([CH:6]=[CH:7][CH:8]=2)[CH:4]=[O:5])[O:1]1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 905792,3-Dihydroxybenzaldehyde

Product 1

HCID 822641,3-Benzodioxole-4-carboxaldehydeYield 80%

Reagents, catalysts & solvents 2

HCID 14829Copper oxideCatalystHCID 6228DimethylformamideSolvent

Procedure

138.0 g (1.0 mol) of 2,3-dihydroxybenzaldehyde, 415.0 g (3.0 mol) of potassium carbonate, 4.7 g of copper oxide, 255.0 g (3.0 mol) of methylene chloride and 1500 ml of distilled dimethylformamide are boiled for 7 hours, while stirring intensively. The reaction mixture is evaporated to dryness-in vacuo and, after addition of 1000 ml of ice-water to the residue, the mixture is extracted four times by shaking with 300 ml of methyl tert-butyl ether each time. The combined ether extracts are washed with 5% strength sodium hydroxide solution and water and dried over sodium sulphate. The methyl tert-butyl ether is then stripped off (and can be reused) and the residue is distilled in vacuo at 92°-93° C./1 mbar. 120 g (80% of theory) of 2,3-methylenedioxybenzaldehyde having a melting point of 32°-33° C. are obtained.

Workup

  1. customThe reaction mixture is evaporated to dryness-in vacuo
  2. additionafter addition of 1000 ml of ice-water to the residue
  3. extractionthe mixture is extracted four times
  4. stirringby shaking with 300 ml of methyl tert-butyl ether each time
  5. washThe combined ether extracts are washed with 5% strength sodium hydroxide solution and water
  6. dry with materialdried over sodium sulphate
  7. distillationthe residue is distilled in vacuo at 92°-93° C./1 mbar

Sources & evidence

ORD record
ord-f561deed3bad45f0b72e6e69ef478593
Source dataset
uspto-grants-1996_06
Patent number
US05525739

Reaction notes

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