Acetic Acid → HCID 13241026, compound

HRID 462775Notes

Reaction equation

HRID 462775 reaction equation
[Si]([O:8][CH:9]([CH:32]1[CH2:37][CH2:36][CH2:35][CH2:34][CH2:33]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14][C:15](=[C:21]1[CH2:26][CH2:25][CH:24]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:23][CH2:22]1)[C:16]2=[O:20])(C(C)(C)C)(C)C.O.C(O)(=O)C.O1CCCC1>[Cl-].[Na+]>[CH:32]1([CH:9]([OH:8])/[CH:10]=[CH:11]/[CH:12]2[CH2:19][CH2:18][CH:17]3[CH:13]2[CH2:14][C:15](=[C:21]2[CH2:22][CH2:23][CH:24]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:25][CH2:26]2)[C:16]3=[O:20])[CH2:33][CH2:34][CH2:35][CH2:36][CH2:37]1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 8028TetrahydrofuranHCID 13241024HCID 13241024, compound

Product 1

HCID 13241026HCID 13241026, compoundYield 73.1%

Reagents, catalysts & solvents 1

HCID 5234Sodium ChlorideSolvent

Procedure

(E)-6-(3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)-3-(4-ethoxycarbonylcyclohexylidene)bicyclo[3,3,0]octan-2-one (15 mg), prepared as described in Reference Example 36 and in the form of (±)-(E)-6β-(3α-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl)-3-(4-ethoxycarbonylcyclohexylidene)bicyclo[3,3,0]-octan-2-one, otherwise known as (±)-ethyl(13E)-(9S,15S)-6a-oxo-2,5-ethano-6,9-methano-15-tert-butyldimethylsilyloxy-15-cyclohexyl-16,17,18,19,20-pentanorprosta-5,13-dienoate and a solution of water, glacial acetic acid and tetrahydrofuran (0.59 ml; 7:13:2 by volume) were stirred together at 45° C. for 5 hours. After cooling, the mixture was diluted with saturated aqueous sodium chloride solution and extracted with ethyl acetate. The extract was washed with aqueous sodium carbonate solution (2M) 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, short column chromatography on silica gel, using a mixture of ethyl acetate and hexane (2:1 v/v) as eluant, to give (E)-6-(3-cyclohexyl-3-hydroxyprop-1-enyl)-3-(4-ethoxycarbonylcyclohexylidene)bicyclo[3,3,0]octan-2-one (8.6 mg), in the form of (±)-(E)-6β-(3-cyclohexyl-3α-hydroxyprop-1-enyl)-3-(4-ethoxycarbonylcyclohexylidene)bicyclo[3,3,0]octan-2-one, otherwise known as (±)-ethyl(13E)-(9S,15S)-6a-oxo-2,5-ethano-6,9-methano-15-hydroxy-15-cyclohexyl-16,17,18,19,20-pentanorprosta-5,13-dienoate [NMR (in deuterochloroform): multiplets at 5.4-5.6, 3.6-4.3 and 0.8-3.0 p.p.m⟧

Workup

  1. temperatureAfter cooling
  2. extractionextracted with ethyl acetate
  3. washThe extract was washed with aqueous sodium carbonate solution (2M)
  4. dry with materialwith saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. additiona mixture of ethyl acetate and hexane (2:1 v/v) as eluant

Sources & evidence

ORD record
ord-1b4ac6c4cfd441308271ed461957cf17
Source dataset
uspto-grants-1985_05
Patent number
US04517202

Reaction notes

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