Sodium Hydroxide → (2S,4R)-4-methanesulfonyloxy-2-(4-methylthiosemicarbazidocarbonyl)-1-(4-nitrobenzyloxycarbonyl)pyrrolidine

HRID 846931Notes

Reaction equation

HRID 846931 reaction equation
P(Cl)(Cl)(Cl)=O.[C:6]([C@@H:9]1[CH2:13][C@@H:12]([O:14][S:15]([CH3:18])(=[O:17])=[O:16])[CH2:11][N:10]1[C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1)=[O:20])(O)=[O:7].[CH3:32][NH:33][C:34](=[S:37])[NH:35][NH2:36].[OH-].[Na+]>O1CCCC1.O.CN(C)C=O>[CH3:18][S:15]([O:14][C@H:12]1[CH2:11][N:10]([C:19]([O:21][CH2:22][C:23]2[CH:24]=[CH:25][C:26]([N+:29]([O-:31])=[O:30])=[CH:27][CH:28]=2)=[O:20])[C@H:9]([C:6]([NH:36][NH:35][C:34]([NH:33][CH3:32])=[S:37])=[O:7])[CH2:13]1)(=[O:17])=[O:16]

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 2723853N-MethylhydrazinecarbothioamideHCID 13502650trans-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)-L-proline

Product 1

HCID 14305077(2S,4R)-4-methanesulfonyloxy-2-(4-methylthiosemicarbazidocarbonyl)-1-(4-nitrobenzyloxycarbonyl)pyrrolidineYield 81.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To a mixture of dimethylformamide (2.9 ml) and tetrahydrofuran (6 ml) was dropwise added phosphorus oxychloride (2.8 ml) at -5~5° C. and the mixture was stirred at the same temperature for 30 minutes. To the mixture was added a solution of (2S,4R)-2-carboxy-4-methanesulfonyloxy-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (9.65 g) in tetrahydrofuran (20 ml) at -5~5° C., followed by stirring at the same temperature for 30 minutes. The mixture was dropwise added to a solution of 4-methylthiosemicarbazide (25 g) in a mixture of water (200 ml) and tetrahydrofuran (200 ml) at 0°-10° C. with sitrring, keeping the pH between 8-9 with 1N aqueous sodium hydroxide. The mixture was stirred at the same condition for 2 hours. Tetrahydrofuran was evaporated under reduced pressure to give precipitates. The precipitates were collected by filtration, washed with water and diisopropyl ether successively, and dried over phosphorus pentoxide to give (2S,4R)-4-methanesulfonyloxy-2-(4-methylthiosemicarbazidocarbonyl)-1-(4-nitrobenzyloxycarbonyl)pyrrolidine (9.61 g).

Workup

  1. customat -5~5° C.
  2. stirringby stirring at the same temperature for 30 minutes
  3. stirringThe mixture was stirred at the same condition for 2 hours
  4. customTetrahydrofuran was evaporated under reduced pressure
  5. customto give
  6. customprecipitates
  7. filtrationThe precipitates were collected by filtration
  8. washwashed with water and diisopropyl ether successively
  9. dry with materialdried over phosphorus pentoxide

Sources & evidence

ORD record
ord-952301b10f9244708cb6a16a7cdbddb7
Source dataset
uspto-grants-1992_08
Patent number
US05138064

Reaction notes

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