Acetic Acid → HCID 57296559, compound

HRID 1086799Notes

Reaction equation

HRID 1086799 reaction equation
[CH:1]12[CH2:7][CH:4]([CH:5]=[CH:6]1)[N:3]([C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:9])[O:2]2.C(O)(=O)C>N1C=CC=CC=1>[CH:1]12[CH2:7][CH:4]([CH2:5][CH2:6]1)[N:3]([C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:9])[O:2]2

Participants

4

Reactant 2

HCID 176Acetic Acid2×HCID 15817097Benzyl 2-oxa-3-azabicyclo[2.2.1]hept-5-ene-3-carboxylate

Product 1

HCID 57296559HCID 57296559, compoundYield 83.4%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

Azodicarbonamide (5.0 g) was stirred with a solution of potassium hydroxide (7.0 g) in water (12 ml) at 4°. After stirring in the ice bath for 1 h the mixture was diluted with ice/water (30 ml) and the solution was filtered. The filtrate was diluted with cool (2°) ethanol (100 ml) and the resultant solid was filtered off, washed with ethanol, methanol and ether to give potassium azodicarboxylate (6.9 g). This was then mixed with 3-aza-2-oxabicyclo[2.2.1]hept-5-ene-3-carboxylic acid, (phenylmethyl) ester (0.82 g) in dry pyridine (60 ml), and acetic acid (2.02 g) was added with stirring at room temperature. After one hour a further portion of glacial acetic acid (2.02 g) was added and the reaction mixture was stirred for 15.5 h. The mixture was evaporated to dryness under reduced pressure. Further acetic acid was then added to quench the remaining yellow colour of the diimide precursor. The residue was partitioned between 0.5M citric acid (75 ml) and ethyl acetate (75 ml) and the organic phase was separated, dried, and concentrated in vacuo. The residue was purified by FCC eluting with ethyl acetate:cyclohexane (1:2) to give the title compound (0.69 g) as an oil.

Workup

  1. additionwas added
  2. stirringthe reaction mixture was stirred for 15.5 h
  3. customThe mixture was evaporated to dryness under reduced pressure
  4. additionFurther acetic acid was then added
  5. customto quench the remaining yellow colour of the diimide precursor
  6. customThe residue was partitioned between 0.5M citric acid (75 ml) and ethyl acetate (75 ml)
  7. customthe organic phase was separated
  8. customdried
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by FCC
  11. washeluting with ethyl acetate:cyclohexane (1:2)

Sources & evidence

ORD record
ord-4c047233d4c94640b5d8d567cae3ffc3
Source dataset
uspto-grants-1991_07
Patent number
US05032583

Reaction notes

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