Citric Acid → HCID 68128026, compound

HRID 1076054Notes

Reaction equation

HRID 1076054 reaction equation
[C:1]([O:4][C@@H:5]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])/[CH:6]=[CH:7]/[C@@H:8]1[C@@H:12]([CH2:13]/[CH:14]=[CH:15]\[CH2:16][CH2:17][CH2:18][C:19]([OH:21])=[O:20])[C:11](=O)[CH:10]2[O:23][CH:9]12)(=[O:3])[CH3:2].O.NN.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CO.C(O)(=O)C>[C:1]([O:4][C@@H:5]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])/[CH:6]=[CH:7]/[C@@H:8]1[C@@H:12]([CH2:13]/[CH:14]=[CH:15]\[CH2:16][CH2:17][CH2:18][C:19]([OH:21])=[O:20])[CH:11]=[CH:10][CH:9]1[OH:23])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 311Citric AcidHCID 24654Hydrazine hydrate (1:1)HCID 86733392HCID 86733392, compound

Product 1

HCID 68128026HCID 68128026, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent3×

Procedure

to a solution of 30 parts of (5Z,13E,15S)-15-acetyloxy-10ξ,11ξ-epoxy-9-oxoprosta-5,13-dien-1-oic acid in 1200 parts of methanol at 5° is added a solution of 12 parts of 100% hydrazine hydrate in 96 parts of methanol followed by a solution of 1 part of acetic acid in 5 parts of methanol. The resultant mixture is stirred at 5° for 30 minutes, then acidified with aqueous 2% citric acid. The mixture thus obtained is extracted with dichloromethane. The extract is washed with water, dried over anhydrous sodium sulfate, and stripped of solvent by vacuum distillation. The residual red oil is taken up in benzene; and the benzene solution is chromatographed on silica gel, using benzene and mixtures thereof with increasing amounts of ethyl acetate as developing solvents. From an eluate comprising 20% ethyl acetate in benzene, on evaporation of solvent, (5Z,13E,15S)-15-acetyloxy-11ξ-hydroxyprosta-5,9,13-trien-1-oic acid is obtained as a colorless oil which gradually darkens upon standing.

Workup

  1. customThe mixture thus obtained
  2. extractionis extracted with dichloromethane
  3. washThe extract is washed with water
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationstripped of solvent by vacuum distillation
  6. customand the benzene solution is chromatographed on silica gel
  7. customFrom an eluate comprising 20% ethyl acetate in benzene, on evaporation of solvent

Sources & evidence

ORD record
ord-a87c4e49db5d4aaa800d9f95d9b8b00e
Source dataset
uspto-grants-1976_05
Patent number
US03954844

Reaction notes

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