Methyl morpholine oxide → HCID 58913253, compound

HRID 1296822Notes

Reaction equation

HRID 1296822 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[S:10][CH:11]=[C:12]([CH:14]([CH2:20][CH:21]=C)[C:15]([O:17][CH2:18][CH3:19])=[O:16])[N:13]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[N+]1([O-])CC[O:27]CC1.CC(C)=O.O.S(=O)(=O)(O)[O-].[Na+]>C(OCC)(=O)C.[Os](=O)(=O)(=O)=O.CCCCCC>[C:1]([O:5][C:6]([NH:8][C:9]1[S:10][CH:11]=[C:12]([CH:14]([CH2:20][CH:21]=[O:27])[C:15]([O:17][CH2:18][CH3:19])=[O:16])[N:13]=1)=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

8

Reactant 4

HCID 82029Methyl morpholine oxideHCID 516919Sodium BisulfateHCID 18366337Propan-2-one--water (1/1)HCID 58913386HCID 58913386, compound2×

Product 1

HCID 58913253HCID 58913253, compoundYield 52.3%

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 150 g (460 mmol) of ethyl 2-(2-tert-butoxycarbonylaminothiazol-yl)-4-pentenoate (Intermediate 34), 57 g (470 mmol) of N-methyl morpholine oxide and 1.0 g of osmium tetroxide in 1250 mL of 4/1 v/v acetone/water was stirred at RT for 1.5 h. To the mixture was added 100 g of solid sodium bisulfate and continued to stir for 0.5 h. The solid was removed by filtration and washing with acetone. The filtrates were combined and evaporated. The residue was diluted with 1000 mL of water and 2000 mL of ethyl acetate. The organic phase was separated and washed with brine (3×1000 mL), dried over Na2SO4 and condensed in vacuo. The residue was redissolved in 1500 mL of methanol and 1000 mL of water. 148 g of sodium periodate was added. The mixture was stirred for one hour, The solid was discarded by filtration and washing with methanol. The filtrates were condensed in vacuo and the reside was dissolved in 1000 mL of ethyl acetate. The organic layer was washed with brine (2×1000 mL), dried over Na2SO4 and evaporated until the solid formed. 1000 mL of hexane was added and the flask was allowed to stand at RT to let crystallization proceed. The solid was collected by filtration and washing with hexane and drying in vacuo. 79 g of the title compound was obtained as white solid. The mother liquid was condensed and the residue was suspended in hexane. A second crop of solid (24 g) was obtained as a yellow solid. The mother liquid was condensed again to afford a brown solid (22 g) which contained impurity.

Workup

  1. stirringto stir for 0.5 h
  2. customThe solid was removed by filtration
  3. washwashing with acetone
  4. customevaporated
  5. additionThe residue was diluted with 1000 mL of water and 2000 mL of ethyl acetate
  6. customThe organic phase was separated
  7. washwashed with brine (3×1000 mL)
  8. dry with materialdried over Na2SO4 and condensed in vacuo
  9. dissolutionThe residue was redissolved in 1500 mL of methanol
  10. addition148 g of sodium periodate was added
  11. stirringThe mixture was stirred for one hour
  12. filtrationThe solid was discarded by filtration
  13. washwashing with methanol
  14. customcondensed in vacuo
  15. washThe organic layer was washed with brine (2×1000 mL)
  16. dry with materialdried over Na2SO4
  17. customevaporated until the solid
  18. customformed
  19. customto stand at RT
  20. customcrystallization
  21. filtrationThe solid was collected by filtration
  22. washwashing with hexane
  23. customdrying in vacuo

Sources & evidence

ORD record
ord-26a3edb9f3a344bdbcf4111d4bee2e75
Source dataset
uspto-grants-2007_07
Patent number
US07247725B2

Reaction notes

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