Hydrochloric Acid → 2,4,6,7-Tetramethyl-5-nitrodihydrobenzofuran-2-aldehyde

HRID 1987775Notes

Reaction equation

HRID 1987775 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C:13]1([CH3:28])[CH2:17][CH:16]2[CH:18]([CH3:27])[C:19]([N+:24]([O-:26])=[O:25])=[C:20]([CH3:23])[C:21]([CH3:22])=[C:15]2[O:14]1.Cl>C(Cl)Cl.C(N(CC)CC)C>[CH3:28][C:13]1([CH:12]=[O:11])[CH2:17][CH:16]2[CH:18]([CH3:27])[C:19]([N+:24]([O-:26])=[O:25])=[C:20]([CH3:23])[C:21]([CH3:22])=[C:15]2[O:14]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 688476092-Hydroxymethyl-2,4,6,7-tetramethyl-5-nitrodihydrobenzofuran

Product 1

HCID 866073542,4,6,7-Tetramethyl-5-nitrodihydrobenzofuran-2-aldehydeYield 64.7%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 8471TriethylamineSolvent

Conditions

Temperature
-78 °C

Procedure

Under an argon atmosphere, 0.57 ml of oxalic acid dichloride was dissolved in 12 ml of methylene chloride, followed by cooling to −78° C. To this solution, a solution prepared by dissolving 1.1 ml of DMSO in 2 ml of methylene chloride was added dropwise at −65 C or lower, followed by stirring for 10 minutes. Furthermore, a solution prepared by dissolving 1.34 g of 2-hydroxymethyl-2,4,6,7-tetramethyl-5-nitrodihydrobenzofuran in 4 ml of methylene chloride was added dropwise, followed by stirring at −78° C. for 3 hours. After the completion of the reaction, 4.2 ml of triethylamine was added dropwise and the reaction solution was heated to room temperature and then 1N-hydrochloric acid was added. The organic layer was extracted with chloroform, washed with saturated saline and dried over anhydrous magnesium sulfate, and then solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography (chloroform) to obtain 0.86 g of the objective product.

Workup

  1. customTo this solution, a solution prepared
  2. additionwas added dropwise at −65 C
  3. customFurthermore, a solution prepared
  4. additionwas added dropwise
  5. stirringby stirring at −78° C. for 3 hours
  6. additionwas added dropwise
  7. temperaturethe reaction solution was heated to room temperature
  8. extractionThe organic layer was extracted with chloroform
  9. washwashed with saturated saline
  10. dry with materialdried over anhydrous magnesium sulfate
  11. distillationsolvent was distilled off under reduced pressure
  12. customthe residue was purified by silica gel column chromatography (chloroform)

Sources & evidence

ORD record
ord-fcef1a27f88341499268bd2fd4b53c75
Source dataset
uspto-grants-2009_06
Patent number
US07553837B2

Reaction notes

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