Dimethylformamide → (2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-dimethylaminocarbonylmethyl-4-acetylthiopyrrolidine

HRID 1088258Notes

Reaction equation

HRID 1088258 reaction equation
[N+:1]([C:4]1[CH:26]=[CH:25][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:17][C:18](=[O:20])[CH3:19])[CH2:14][C@H:13]2[CH2:21][C:22](O)=[O:23])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.[CH3:33][N:34](C)[CH:35]=O>C(Cl)Cl>[N+:1]([C:4]1[CH:26]=[CH:25][C:7]([CH2:8][O:9][C:10]([N:12]2[CH2:16][C@@H:15]([S:17][C:18](=[O:20])[CH3:19])[CH2:14][C@H:13]2[CH2:21][C:22]([N:34]([CH3:35])[CH3:33])=[O:23])=[O:11])=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 14830201(2R,4S)-1-(p-Nitrobenzyloxycarbonyl)-2-carboxymethyl-4-acetylthiopyrrolidine

Product 1

HCID 14830203(2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-dimethylaminocarbonylmethyl-4-acetylthiopyrrolidine

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(2R,4S)-1-(p-Nitrobenzyloxycarbonyl)-2-carboxymethyl-4-acetylthiopyrrolidine (125 mg) was dissolved in 1 ml of dry methylene chloride, and 0.1 ml of oxalyl chloride and a catalytic amount of dimethylformamide were added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was distilled to remove the solvent, and dry benzene was added to the residue, followed by distillation of benzene. After two times repetition of the above procedure, the resulting residue was dissolved in 2 ml of dry methylene chloride. The resultant mixture was added to a solution of 45 mg of dimethylamine in 1.5 ml of dry methylene chloride and 0.2 ml of dry tetrahydrofuran under nitrogen stream at 0° C., followed by stirring at the same temperature for 30 minutes. The reaction mixture was diluted with methylene chloride, washed successively with water, dilute hydrochloric acid, water, a saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulfate and distilled to remove the solvent. The residue was purified by silica gel thin layer chromatography to obtain (2R,4S)-1-(p-nitrobenzyloxycarbonyl)-2-dimethylaminocarbonylmethyl-4-acetylthiopyrrolidine.

Workup

  1. distillationThe reaction mixture was distilled
  2. customto remove the solvent, and dry benzene
  3. additionwas added to the residue
  4. distillationfollowed by distillation of benzene
  5. dissolutionAfter two times repetition of the above procedure, the resulting residue was dissolved in 2 ml of dry methylene chloride
  6. additionThe resultant mixture was added to a solution of 45 mg of dimethylamine in 1.5 ml of dry methylene chloride and 0.2 ml of dry tetrahydrofuran under nitrogen stream at 0° C.
  7. stirringby stirring at the same temperature for 30 minutes
  8. additionThe reaction mixture was diluted with methylene chloride
  9. washwashed successively with water, dilute hydrochloric acid, water
  10. dry with materiala saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulfate
  11. distillationdistilled
  12. customto remove the solvent
  13. customThe residue was purified by silica gel thin layer chromatography

Sources & evidence

ORD record
ord-94f1d598822d4fe193f34ed6ed52b39c
Source dataset
uspto-grants-1990_10
Patent number
US04962103

Reaction notes

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