Methanol → 3-[(E)-4-carboxybutylidene]-6-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]bicyclo[3,3,0]octan-2-one

HRID 462770Notes

Reaction equation

HRID 462770 reaction equation
[CH:1]1([CH:7]([OH:27])/[CH:8]=[CH:9]/[CH:10]2[CH2:17][CH2:16][CH:15]3[CH:11]2[CH2:12]/[C:13](=[CH:19]\[CH2:20][CH2:21][CH2:22][C:23]([O:25]C)=[O:24])/[C:14]3=[O:18])[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[OH-].[Li+].CO>O>[C:23]([CH2:22][CH2:21][CH2:20]/[CH:19]=[C:13]1/[C:14](=[O:18])[CH:15]2[CH:11]([CH2:12]/1)[CH:10](/[CH:9]=[CH:8]/[CH:7]([CH:1]1[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]1)[OH:27])[CH2:17][CH2:16]2)([OH:25])=[O:24]

Participants

5

Reactant 3

HCID 887MethanolHCID 3939Lithium HydroxideHCID 203972086-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Product 1

HCID 203972153-[(E)-4-carboxybutylidene]-6-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]bicyclo[3,3,0]octan-2-oneYield 54%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A mixture of 6-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (12.7 mg), prepared as described in Example 1 and in the form of (±)-6β-[(E)-3-cyclohexyl-3α-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)methyl(5E,13E)-(9S,15S)-6a-oxo-6,9-methano-15-cyclohexyl-15-hydroxy-16,17,18,19,20-pentanorprosta-5,13-dienoate, lithium hydroxide (21.5 mg), methanol (2 ml), and water (0.7 ml) was left to stand at the ambient temperature for 1 hour. The mixture was then diluted with water (5 ml) and washed with dichloromethane. The aqueous layer was separated and acidified to pH 3 by treatment with aqueous hydrochloric acid (2N). The acidic solution was extracted with dichloromethane, and this extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate, and concentrated under reduced pressure, to give 3-[(E)-4-carboxybutylidene]-6-[ (E)-3-cyclohexyl-3-hydroxyprop-1-enyl]bicyclo[3,3,0]octan-2-one (6.6 mg), in the form of (±)-3-[(E)-4-carboxybutylidene]-6β-[(E)-3-cyclohexyl-3α-hydroxyprop-1-enyl]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-(5E,13E)-(9S,15S)-6a-oxo-6,9-methano-15-cyclohexyl-15-hydroxy-16,17,18,19,20-pentanorprosta-5,13-dienoic acid.

Workup

  1. customprepared
  2. waitwas left
  3. washwashed with dichloromethane
  4. customThe aqueous layer was separated
  5. extractionThe acidic solution was extracted with dichloromethane
  6. washthis extract was washed with saturated aqueous sodium chloride solution
  7. dry with materialdried over anhydrous sodium sulphate
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-10325f45e1e042c3b031c09b4050c065
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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