L-Hydroxyproline → trans-4-Hydroxy-1-(4-nitrobenzyloxycarbonyl)-L-proline

HRID 1088249Notes

Reaction equation

HRID 1088249 reaction equation
[OH:1][C@H:2]1[CH2:6][NH:5][C@H:4]([C:7]([OH:9])=[O:8])[CH2:3]1.C(N(CC)CC)C.[N+:17]([C:20]1[CH:38]=[CH:37][C:23]([CH2:24][O:25][C:26](SC2N=C(C)C=C(C)N=2)=[O:27])=[CH:22][CH:21]=1)([O-:19])=[O:18].[OH-].[Na+]>O.O1CCOCC1.C(OCC)C>[N+:17]([C:20]1[CH:21]=[CH:22][C:23]([CH2:24][O:25][C:26]([N:5]2[CH2:6][C@H:2]([OH:1])[CH2:3][C@H:4]2[C:7]([OH:9])=[O:8])=[O:27])=[CH:37][CH:38]=1)([O-:19])=[O:18]

Participants

8

Reactant 4

HCID 5810L-HydroxyprolineHCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 135043164,6-Dimethyl-2-(4-nitrobenzyloxycarbonylthio)pyrimidine

Product 1

HCID 10566895trans-4-Hydroxy-1-(4-nitrobenzyloxycarbonyl)-L-proline

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

Trans-4-Hydroxy-L-proline (6.55 g) and triethylamine (7.5 ml) were dissolved in 15 ml of water, and a solution of 15.95 g of S-p-nitrobenzyloxycarbonyl-4,6-dimethyl-2-mercaptopyrimidine in 35 ml of dioxane was dropwise added thereto. The resulting mixture was stirred at room temperature for 1.5 hours and allowed to stand overnight. To the reaction mixture was added 30 ml of 2N sodium hydroxide solution under ice-cooling, and the resultant mixture was shaken with diethyl ether. The aqueous layer was separated from the ethereal layer, the ethereal layer was washed with 20 ml of 1m hydroxide solution, and the washing was combined with the aqueous layer. The combined mixture was made acidic with 100 ml of 2N hydrochloric acid and extracted with ethyl acetate. The ethyl acetate extract was washed with 2N hydrochloric acid, dried over anhydrous sodium sulfate and distilled to remove the solvent. The resulting crude crystals were washed with ethyl acetate to obtain trans-1-(p-nitrobenzyloxycarbonyl)-4-hydroxy-L-proline. M.P., 134.3°-135.5° C.

Workup

  1. waitto stand overnight
  2. temperaturecooling
  3. customThe aqueous layer was separated from the ethereal layer
  4. washthe ethereal layer was washed with 20 ml of 1m hydroxide solution
  5. extractionextracted with ethyl acetate
  6. extractionThe ethyl acetate extract
  7. washwas washed with 2N hydrochloric acid
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationdistilled
  10. customto remove the solvent
  11. washThe resulting crude crystals were washed with ethyl acetate

Sources & evidence

ORD record
ord-b300bc7e0bee4db7a4acb7206a40679f
Source dataset
uspto-grants-1990_10
Patent number
US04962103

Reaction notes

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