Hydrochloric Acid → HCID 178459712, compound

HRID 1109808Notes

Reaction equation

HRID 1109808 reaction equation
[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10]([OH:12])[CH2:9][C@@H:8]1[C:13]([OH:15])=O)=[O:6])[CH:2]=[CH2:3].C(Cl)(=O)OC(C)C.[CH3:23][S:24](Cl)(=[O:26])=[O:25].[SH2:28].Cl.[OH-].[Na+]>C(Cl)Cl.C1(C)C=CC=CC=1.C(OCC)(=O)C.C(N(CC)CC)C>[CH2:1]([O:4][C:5]([N:7]1[CH2:11][C@H:10]([O:12][S:24]([CH3:23])(=[O:26])=[O:25])[CH2:9][C@H:8]1[C:13](=[S:28])[OH:15])=[O:6])[CH:2]=[CH2:3]

Participants

11

Reactant 6

HCID 313Hydrochloric AcidHCID 402Hydrogen SulfideHCID 7917Isopropyl chloroformateHCID 14798Sodium HydroxideHCID 31297Methanesulfonyl chlorideHCID 54470509HCID 54470509, compound

Product 1

HCID 178459712HCID 178459712, compound

Reagents, catalysts & solvents 4

HCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-10 °C

Procedure

To a solution of (2R,4R)-1-allyloxycarbonyl-4-hydroxy-2-pyrrolidinecarboxylic acid (559 mg) in methylene chloride (15ml), cooled to -10° C., were added triethylamine (329 mg) and isopropyl chlorocarbonate (366 mg). The mixture was stirred at -10° C. for 20 minutes. Triethylamine (329 mg) and methanesulfonyl chloride (342 mg) were added thereto, and the mixture was stirred at -10° C. for 20 minutes. After triethylamine (657 mg) was added, an excessive amount of hydrogen sulfide was passed through for 30 minutes. Concentrated hydrochloric acid (790 mg) and ethyl acetate (20 ml) were added thereto, and the mixture was dried above magnesium sulfate. After a substance left undissolved was separated by filtration, the solvent was removed by vacuum distillation, thereby to give oily crude (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy -2-pyrrolidinethiocarboxylic acid (800 mg). This compound was mixed with 1N-sodium hydroxide solution (4 ml) and toluene (4 ml). Liquid layers were separated and the aqueous layer was further washed with toluene (3 ml). Aqueous layer was acidified with 1N-hydrochloric acid (5 ml) and extracted with ethyl acetate (10 ml) and again with ethyl acetate (5 ml). Organic layers were combined and dried over magnesium sulfate. Distillation of the solvent gave (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy-2-pyrrolidinethiocarboxylic acid.

Workup

  1. stirringthe mixture was stirred at -10° C. for 20 minutes
  2. customwas passed through for 30 minutes
  3. dry with materialthe mixture was dried above magnesium sulfate
  4. waitAfter a substance left
  5. customundissolved was separated by filtration
  6. customthe solvent was removed by vacuum distillation
  7. customto give oily crude (2S,4R)-1-allyloxycarbonyl-4-methanesulfonyloxy -2-pyrrolidinethiocarboxylic acid (800 mg)
  8. customLiquid layers were separated
  9. washthe aqueous layer was further washed with toluene (3 ml)
  10. extractionextracted with ethyl acetate (10 ml) and again with ethyl acetate (5 ml)
  11. dry with materialdried over magnesium sulfate
  12. distillationDistillation of the solvent

Sources & evidence

ORD record
ord-32b547c94f9c4008bd1e27b97fbe9fa4
Source dataset
uspto-grants-1994_06
Patent number
US05322952

Reaction notes

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