Acetic Acid → 4-Methylene-3-oxabicyclo[3.2.1]octan-2-one

HRID 1072769Notes

Reaction equation

HRID 1072769 reaction equation
[CH2:1]=[C:2]1[CH:7]2[CH2:8][CH:4]([CH2:5][CH2:6]2)[C:3]1=[O:9].O.O.O.C([O-])(=[O:15])C.[Na+].C(=O)=O.CC(C)=O.C(OO)(=O)C.C(O)(=O)C.S([O-])([O-])=O.[Na+].[Na+]>ClCCl.O>[CH2:1]=[C:2]1[CH:7]2[CH2:8][CH:4]([CH2:5][CH2:6]2)[C:3](=[O:9])[O:15]1

Participants

9

Reactant 6

HCID 176Acetic AcidHCID 6585Peracetic AcidHCID 24437Sodium SulfiteHCID 968753-Methylidenebicyclo[2.2.1]heptan-2-oneHCID 18522661Acetone cardiceHCID 23665404Sodium Acetate Trihydrate

Product 1

HCID 129939774-Methylene-3-oxabicyclo[3.2.1]octan-2-oneYield 247%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

98.7 g (0.81 mol) of 3-methylenebicyclo[2.2.1]heptan-2-one and 32.9 g (0.24 mol) of sodium acetate trihydrate in 400 ml of dichloromethane are used as the initial charge in a reaction vessel. While controlling the temperature (CO2/acetone bath), 230 g of 32% peracetic acid in acetic acid (0.97 mol) are then added dropwise in the course of 2.5 hours, at a temperature of from −8° C. to −10° C. with stirring. The reaction mixture is subsequently stirred at a temperature of −8° C. for a further hour. 200 g of ice are then added, followed by 20 g (0.16 mol) of sodium sulfite in 100 ml of water. The organic phase is separated off and washed with water, dried over magnesium sulfate and concentrated to yield, in the form of a liquid residue, 81.9 g of 4-methylene-3-oxabicyclo[3.2.1]octan-2-one with a 93% content and a yield of 68.2%.

Workup

  1. additioninitial charge in a reaction vessel
  2. additionare then added dropwise in the course of 2.5 hours, at a temperature of from −8° C. to −10° C.
  3. stirringThe reaction mixture is subsequently stirred at a temperature of −8° C. for a further hour
  4. customThe organic phase is separated off
  5. washwashed with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-8989ec513b304636ba1904d3a6242de9
Source dataset
uspto-grants-2005_06
Patent number
US06911547B1

Reaction notes

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