Acetic Acid → 3,3a,4,5,6,6a-hexahydro-2H-pentalen-1-one

HRID 462771Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 462771
COC(CCC/C=[C:9]1/[C:10](=[O:17])[CH:11]2[CH:15]([CH2:16]/1)[CH2:14][CH2:13][CH2:12]2)=O.[OH-].[Li+].C(O)(=O)C>CO>[CH:11]12[CH2:12][CH2:13][CH2:14][CH:15]1[CH2:16][CH2:9][C:10]2=[O:17]

Komponenten

5

Edukt 3

HCID 176Acetic AcidHCID 3939Lithium HydroxideHCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

Produkt 1

HCID 1406313,3a,4,5,6,6a-hexahydro-2H-pentalen-1-oneAusbeute 148 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
10 °C

Versuchsvorschrift

A stirred solution of 6-[(E)-(mixture of 3β and 3β)-hydroxyoct-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (90 mg), prepared as described in Example 4 and predominantly in the 6β-configuration, otherwise known as (±)-methyl(5E,13E)-(9S),[mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxyprosta-5,13-dienoate, in methanol (2 ml) at 5° C. was treated with aqueous lithium hydroxide solution (1.5 ml; 1.0N). The resulting solution was stirred for 3.3 hours at 10° C. and was then treated with glacial acetic acid (0.1 ml). The methanol was removed in vacuo and the residue was diluted with ethyl acetate (10 ml), washed with hydrochloric acid (2N), then with water, and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate and concentrated in vacuo, to give 3-[(E)-4-carboxybutylidene]-6-[(E)-(mixture of 3α and 3β)-hydroxyoct-1-enyl]bicyclo[3,3,0]octan-2-one (70.0 mg), thought to be in the 6β-configuration, otherwise known as (±)-(5E,13E)-(9S),[mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxyprosta-5,13-dienoic acid [NMR in deuterochloroform: multiplets at 6.6, 5.5, 4.8-3.7, 3.0-1.1, 1.1-0.7 p.p.m⟧

Aufarbeitung

  1. customThe methanol was removed in vacuo
  2. additionthe residue was diluted with ethyl acetate (10 ml)
  3. washwashed with hydrochloric acid (2N)
  4. dry with materialwith water, and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  5. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-8444afcb6dba4559979b26b713a2d9a1
Quelldatensatz
uspto-grants-1985_05
Patentnummer
US04517202

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