Sodium borohydride → 9-Keto-15-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester

HRID 27287Notes

Reaction equation

HRID 27287 reaction equation
C1CO[CH:17]2[CH:3]([C@@H:4]([C@@H:15]([CH2:20][CH2:21][C:22](=[O:31])[C:23]([CH3:30])([CH3:29])[CH2:24][CH:25]=[C:26]([CH3:28])[CH3:27])[CH2:16]2)[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12])[O:2]1.[BH4-].[Na+]>CO.O>[O:2]=[C:3]1[CH2:17][CH2:16][C@H:15]([CH2:20][CH2:21][CH:22]([OH:31])[C:23]([CH3:30])([CH3:29])[CH2:24][CH:25]=[C:26]([CH3:27])[CH3:28])[C@H:4]1[CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([O:13][CH3:14])=[O:12]

Participants

5

Reactant 2

HCID 4311764Sodium borohydrideHCID 867371919-Ethylenedioxy-15-keto-16,16,19-trimethyl-prost-18-enoic acid, methyl ester

Product 1

HCID 867371909-Keto-15-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To the solution of 2.4 g of 9-ethylenedioxy-15-keto-16,16,19-trimethyl-prost-18-enoic acid, methyl ester in methanol (20 ml.) 0.4 g of sodium borohydride are gradually added while the temperature is kept under 35° C. The mixture is stirred for 30 minutes, then diluted with water (150 ml.) and extracted with ethyl acetate (3×70 ml.). The organic layer is washed with water to neutrality, dried over sodium sulphate and the solvent is removed in vacuo. The oily residue (2.2 g) is suspended in 65% acetic acid (30 ml.) and stirred at room temperature for 60 minutes. The obtained solution is diluted with water (100 ml.) and extracted with diethyl ether (3×70 ml). The organic layer is washed with aqueous saturated NaHCO3 solution to neutrality, dried over sodium sulphate and the solvent is evaporated. From the oily residue (1.8 g), by chromatography on silica (200 g) and elution with benzene/ethyl acetate (4:1), 0.48 g of 9 -keto-15β-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester, 0.40 g of 9-keto-15α-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester and 0.48 g of a mixture of 15α and 15β are obtained.

Workup

  1. customis kept under 35° C
  2. extractionextracted with ethyl acetate (3×70 ml.)
  3. washThe organic layer is washed with water to neutrality
  4. dry with materialdried over sodium sulphate
  5. customthe solvent is removed in vacuo
  6. stirringstirred at room temperature for 60 minutes
  7. additionThe obtained solution is diluted with water (100 ml.)
  8. extractionextracted with diethyl ether (3×70 ml)
  9. washThe organic layer is washed with aqueous saturated NaHCO3 solution to neutrality
  10. dry with materialdried over sodium sulphate
  11. customthe solvent is evaporated
  12. washFrom the oily residue (1.8 g), by chromatography on silica (200 g) and elution with benzene/ethyl acetate (4:1), 0.48 g of 9 -keto-15β-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester, 0.40 g of 9-keto-15α-hydroxy-16,16,19-trimethyl-prost-18-enoic acid, methyl ester and 0.48 g of a mixture of 15α and 15β
  13. customare obtained

Sources & evidence

ORD record
ord-3d71d1176bbd4706aaaf87e3dd1f006a
Source dataset
uspto-grants-1980_09
Patent number
US04220798

Reaction notes

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