m-Chloroperbenzoic acid → tert-Butyl 7-Oxa-3-azabicyclo(4.1.0)heptane-3-carboxylate

HRID 276932Notes

Reaction equation

HRID 276932 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH:12]=[CH:11][CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[OH:15].[Na+].ClC1C=C(C=CC=1)C(OO)=O>ClCCl.CCCCCC>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][CH:11]2[O:15][CH:12]2[CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 13094787tert-Butyl 3,6-dihydropyridine-1(2H)-carboxylate

Product 1

HCID 21991116tert-Butyl 7-Oxa-3-azabicyclo(4.1.0)heptane-3-carboxylateYield 66.7%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8058HexaneSolvent

Procedure

To a solution of 1-tert-butoxycarbonyl-1,2,3,6-tetrahydropyridine (18.9 g) in dichloromethane (400 ml). was added in turn sodium hydrogen carbonate (11.3 g) and m-chloroperoxybenzoic acid (23.4 g) with care at 0° C., and which was stirred for 2 hours. Insoluble material was removed by filtration, mother liquor was washed saturated sodium chloride in water (100 ml) and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was dissolved in n-hexane (300 ml) and insoluble material was removed by filtration. Mother liquor was concentrated in vacuo, the remainings were dissolved in ethyl acetate (300 ml) and washed in turn with saturated sodium hydrogen carbonate in water (100 ml×5) and saturated sodium chloride in water (100 ml×2), which was dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (350 ml) eluting in turn with 10%, 20% and 30% ethyl acetate in n-hexane. Tractions, containing desired product, were collected and concentrated in vacuo to give 1-tert-butoxycarbonyl-3,4-epoxypiperidine (13.7 g).

Workup

  1. customInsoluble material was removed by filtration, mother liquor
  2. washwas washed saturated sodium chloride in water (100 ml)
  3. dry with materialdried over magnesium sulfate
  4. customEvaporation of the solvent
  5. customgave a residue, which
  6. custominsoluble material was removed by filtration
  7. concentrationMother liquor was concentrated in vacuo
  8. dissolutionthe remainings were dissolved in ethyl acetate (300 ml)
  9. washwashed in turn with saturated sodium hydrogen carbonate in water (100 ml×5) and saturated sodium chloride in water (100 ml×2)
  10. dry with materialwhich was dried over magnesium sulfate
  11. customEvaporation of the solvent
  12. customgave a residue, which
  13. customwas chromatographed on silica gel (350 ml)
  14. washeluting in turn with 10%, 20% and 30% ethyl acetate in n-hexane
  15. additionTractions, containing desired product
  16. customwere collected
  17. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-90a0bbd150364c378d936c1a7a0aabd1
Source dataset
uspto-grants-2002_03
Patent number
US06355640B1

Reaction notes

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