Formic Acid → 6-Hydroxyhexahydro-2H-3,5-methanocyclopenta[b]furan-2-one

HRID 651362Notes

Reaction equation

HRID 651362 reaction equation
[CH:1]12[CH2:7][CH:4]([CH:5]=[CH:6]1)[CH2:3][CH:2]2[C:8]([OH:10])=[O:9].C(O)=[O:12].OO.S([O-])([O-])=O.[Na+].[Na+]>O>[OH:12][CH:5]1[CH:6]2[CH:1]3[CH:2]([CH2:3][CH:4]1[CH2:7]3)[C:8](=[O:10])[O:9]2

Participants

6

Reactant 4

HCID 284Formic AcidHCID 784Hydrogen PeroxideHCID 24437Sodium SulfiteHCID 789495-Norbornene-2-carboxylic acid

Product 1

HCID 4326396-Hydroxyhexahydro-2H-3,5-methanocyclopenta[b]furan-2-oneYield 65.5%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

With 328.2 g of 5-norbornene-2-carboxylic acid was mixed 240.6 of formic acid. Below 50° C., 254.5 g of 35% aqueous hydrogen peroxide was added dropwise to the mixture over 6 hours. After the completion of addition, the reaction mixture was poured into a mixture of 1.5 liters of water and 0.8 kg of sodium sulfite. After three times of extraction with 1 liter of ethyl acetate, the organic phase was washed with water, dried, and concentrated in vacuum. The residue was dissolved in 1.2 liters of methanol, to which a catalytic amount of potassium carbonate was added. This was agitated for one hour at room temperature. The methanol was distilled off under vacuum, followed by conventional extraction and washing. There was obtained 247.6 g of 2-hydroxy-4-oxatricyclo[4.2.1.03,7]nonan-5-one. The yield was 65.5%.

Workup

  1. additionAfter the completion of addition
  2. extractionAfter three times of extraction with 1 liter of ethyl acetate
  3. washthe organic phase was washed with water
  4. customdried
  5. concentrationconcentrated in vacuum
  6. dissolutionThe residue was dissolved in 1.2 liters of methanol, to which a catalytic amount of potassium carbonate
  7. additionwas added
  8. distillationThe methanol was distilled off under vacuum
  9. extractionfollowed by conventional extraction
  10. washwashing

Sources & evidence

ORD record
ord-08c8783f048048fda1a806ff86e70d0a
Source dataset
uspto-grants-2001_08
Patent number
US06280898B1

Reaction notes

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