Sodium Hydroxide → HCID 54403008, compound

HRID 975685Notes

Reaction equation

HRID 975685 reaction equation
CC(C)([O-])C.[K+].[C:7]([OH:10])(=[S:9])[CH3:8].[CH2:11]([O:14][C:15]([N:17]1[CH2:21][C@H:20](OS(C)(=O)=O)[CH2:19][C@H:18]1[CH2:27][C:28]1[CH:29]=[N:30][CH:31]=[N:32][CH:33]=1)=[O:16])[CH:12]=[CH2:13].[OH-].[Na+]>CN(C)C=O.C1(C)C=CC=CC=1.C(OCC)(=O)C>[C:7]([S:9][C@@H:20]1[CH2:21][N:17]([C:15]([O:14][CH2:11][CH:12]=[CH2:13])=[O:16])[C@H:18]([CH2:27][C:28]2[CH:29]=[N:30][CH:31]=[N:32][CH:33]=2)[CH2:19]1)(=[O:10])[CH3:8]

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 23665647Potassium tert-butoxideHCID 54428075HCID 54428075, compoundHCID 178418634HCID 178418634, compound

Product 1

HCID 54403008HCID 54403008, compoundYield 72.9%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Under nitrogen atmosphere to a solution of potassium tert-butoxide (17.0 g) in N,N-dimethylformamide (77 ml) was slowly dropped thioacetic acid (12.1 g) at 0° to 10° C., and then the solution was stirred for 30 minutes at the same temperature. This solution was added to a solution of (2R,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy-2-(pyrimidin-5-ylmethyl) pyrrolidine (25.8 g) in N,N-dimethylformamide (154 ml) at 15° to 25° C. under nitrogen atmosphere, and the reaction mixture was stirred for 2 hours at 80° to 90° C. After the reaction mixture was cooled and poured into ice-water (500 ml) and ethyl acetate (300 ml), the aqueous layer was adjusted to pH 8.2 with 1N-sodium hydroxide. The organic layer was separated and washed with water containing 10% sodium chloride (300 ml). This fraction and the fraction reextracted from the aqueous layer were combined, dried over magnesium sulfate, and evaporated under reduced pressure to give an oil. The oil was dissolved in toluene (300 ml) and it was washed with water (150 ml), dried over magnesium sulfate and then evaporated. The residue was subjected to column chromatography on silica gel (250 g) (solvent; hexane:ethyl acetate=3:1 to 1:6) to give (2R,4S)-4-acetylthio-1-allyloxycarbonyl-2-(pyrimidin-5-ylmethyl) pyrrolidine (17.7 g) as an oil.

Workup

  1. customat 0° to 10° C.
  2. stirringthe reaction mixture was stirred for 2 hours at 80° to 90° C
  3. temperatureAfter the reaction mixture was cooled
  4. customThe organic layer was separated
  5. washwashed with water containing 10% sodium chloride (300 ml)
  6. dry with materialdried over magnesium sulfate
  7. customevaporated under reduced pressure
  8. customto give an oil
  9. washit was washed with water (150 ml)
  10. dry with materialdried over magnesium sulfate
  11. customevaporated

Sources & evidence

ORD record
ord-7d99303d99ef43679169fda4ebf1887f
Source dataset
uspto-grants-1997_03
Patent number
US05608056

Reaction notes

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