Diiodomethane → 6-Bromo-2H-1,3-benzodioxole-4-carbaldehyde

HRID 1386039Notes

Reaction equation

HRID 1386039 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([OH:11])[C:5]([OH:10])=[C:6]([CH:9]=1)[CH:7]=[O:8].[C:12](=O)([O-])[O-].[K+].[K+].ICI>CN(C)C=O>[Br:1][C:2]1[CH:9]=[C:6]([CH:7]=[O:8])[C:5]2[O:10][CH2:12][O:11][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 6346DiiodomethaneHCID 11430Potassium CarbonateHCID 186155855-Bromo-2,3-dihydroxybenzaldehyde

Product 1

HCID 125140976-Bromo-2H-1,3-benzodioxole-4-carbaldehydeYield 79.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

Dimethylformamide, 750 mL, was purged with dry nitrogen gas and 5-bromo-2,3-dihydroxy-benzaldehyde (83 g, 382 mmol) was added. To the solution was added potassium carbonate (158 g, 1.14 mol) followed by diiodomethane (306 g, 1.14 mol). The mixture was warmed to 85° C. for 2.5 hours, and evaporated in vacuo to an oil. The mixture was partitioned between ethyl acetate and water and filtered through celite. The phases were separated, and the organic phase was washed with brine, dried over anhydrous magnesium sulfate, filtered, and evaporated to a small volume causing a solid to precipitate. The solid was filtered, washed with 50:50 hexane/ethyl acetate, and set aside. Three more crops of solid were subsequently isolated in this manner from the filtrate. The solids were combined and dried in vacuo giving a beige solid, 69.45 g, 79.4% yield. NMR spectra and elemental analysis were consistent with the structure.

Workup

  1. additionwas added
  2. customevaporated in vacuo to an oil
  3. customThe mixture was partitioned between ethyl acetate and water
  4. filtrationfiltered through celite
  5. customThe phases were separated
  6. washthe organic phase was washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customevaporated to a small volume
  10. customto precipitate
  11. filtrationThe solid was filtered
  12. washwashed with 50:50 hexane/ethyl acetate
  13. customThree more crops of solid were subsequently isolated in this manner from the filtrate
  14. customdried in vacuo
  15. customgiving a beige solid, 69.45 g, 79.4% yield

Sources & evidence

ORD record
ord-669cc1b6d5784c0ebcd5ad4f8ecbf142
Source dataset
uspto-grants-2001_07
Patent number
US06265399B1

Reaction notes

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