Acetic Acid → 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

HRID 462776Notes

Reaction equation

HRID 462776 reaction equation
[CH3:1][O:2][C:3]([CH2:5][CH2:6][CH2:7]/[CH:8]=[C:9]1/[C:10](=[O:17])[CH:11]2[CH:15]([CH2:16]/1)[CH2:14][CH2:13][CH2:12]2)=[O:4].[OH2:18].[C:19]([OH:22])(=O)[CH3:20].O1[CH2:27][CH2:26][CH2:25][CH2:24]1>[Cl-].[Na+]>[OH:18][CH:6]([CH2:7][O:22][C:19]1[CH:20]=[CH:24][CH:25]=[CH:26][CH:27]=1)/[CH:5]=[CH:3]/[CH:14]1[CH2:13][CH2:12][CH:11]2[CH:15]1[CH2:16]/[C:9](=[CH:8]\[CH2:7][CH2:6][CH2:5][C:3]([O:2][CH3:1])=[O:4])/[C:10]2=[O:17]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 8028TetrahydrofuranHCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Product 1

HCID 203971966-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Reagents, catalysts & solvents 1

HCID 5234Sodium ChlorideSolvent

Procedure

6-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl)]-3-[(E)-4-methoxycarbonylbutylidene]-bicyclo[3,3,0]octan-2-one (21 mg), prepared as described in Reference Example 48 and in the form of (±)-6β-[(E)-3β-tert-butyldimethylsilyloxy-4-phenoxybut-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-tert-butyldimethylsilyloxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate, and a solution of water, glacial acetic acid and tetrahydrofuran (0.86 ml; 7:13:2 by volume) were stirred together at 40° C. for 4 hours. After cooling, the mixture was diluted with saturated aqueous sodium chloride solution and extracted with diethyl ether. The ethereal extract was washed with aqueous sodium bicarbonate solution (1M) and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue was subjected to medium pressure chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (1:1 v/v), to give 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (15.9 mg), in the form of (±)-6β-[(E)-3β-hydroxy-4-phenoxybut-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-hydroxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate [NMR (in deuterochloroform): multiplets at 6.6-7.2, 6.3-6.6, 5.3-5.6, 4.3-4.5, 3.7-3.9, 1.3-2.8 p.p.m., singlet at 3.6 p.p.m⟧

Workup

  1. temperatureAfter cooling
  2. extractionextracted with diethyl ether
  3. extractionThe ethereal extract
  4. washwas washed with aqueous sodium bicarbonate solution (1M)
  5. dry with materialwith saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  6. concentrationconcentrated under reduced pressure
  7. washeluting with a mixture of ethyl acetate and hexane (1:1 v/v)

Sources & evidence

ORD record
ord-54e9ea6ef5ca4031b06709683a37628e
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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