Sulfuric Acid → 7-(4-Hydroxycyclopent-2-en-1-on-2-yl)-5-heptynoic acid

HRID 1032505Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1032505
CO[C:3]1([CH2:10][CH2:11][C:12]#[C:13][CH2:14][CH2:15][CH2:16][C:17]([O:22]C)([O:20]C)OC)[CH:7]=[CH:6][CH:5]([O:8]C)O1.O.P([O-])(O)(O)=[O:26].[Na+].O1CCOCC1.S(=O)(=O)(O)O>P([O-])([O-])(O)=O.[Na+].[Na+].O>[OH:26][CH:7]1[CH2:6][C:5](=[O:8])[C:10]([CH2:11][C:12]#[C:13][CH2:14][CH2:15][CH2:16][C:17]([OH:20])=[O:22])=[CH:3]1

Komponenten

7

Edukt 4

HCID 1118Sulfuric AcidHCID 312751,4-DioxaneHCID 516949Sodium Phosphate, Monobasic, MonohydrateHCID 221661452,5-Dihydro-2,5-dimethoxy-2-(8,8,8-trimethoxy-3-octynyl)furan

Produkt 1

HCID 147744257-(4-Hydroxycyclopent-2-en-1-on-2-yl)-5-heptynoic acidAusbeute 112,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24203Sodium Phosphate, DibasicKatalysatorHCID 962WaterLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A stirred mixture of 7.1 g of 2,5-dihydro-2,5-di- methoxy-2-(8,8,8-trimethoxy-3-octynyl)furan, 2.76 g of sodium dihydrogen phosphate monohydrate, 140 mg of disodium hydrogen phosphate, 60 ml of dioxane and 40 ml of water was boiled under reflux for 19 hours, then cooled to 50° C. and treated dropwise with 4.1 ml of concentrated sulfuric acid. The resulting solution was boiled under reflux for 12 hours, cooled and partitioned with ether and brine. The ether layer was separated, washed with brine, dried and concentrated, giving 5.0 g of crude 7-(4-hydroxycyclopent-2-en-1-on-2-yl)-5-heptynoic acid. This crude product was dissolved in 40 ml of pyridine and the stirred solution treated at 0° to 10° C. with 10.5 ml of hexamethyldisilizane followed by 6.3 ml of chlorotrimethylsilane. The resulting mixture was stirred at 25° C. for 3 hours and then concentrated to dryness at 30° C. The residue was extracted with hexane, the extract filtered through diatomaceous earth and concentrated. The residue was distilled at 0.11 mm on a Kugelrohr at 155°-170° C., giving 1.66 g of the desired compound as an oil.

Aufarbeitung

  1. temperatureunder reflux for 19 hours
  2. temperatureunder reflux for 12 hours
  3. temperaturecooled
  4. custompartitioned with ether and brine
  5. customThe ether layer was separated
  6. washwashed with brine
  7. customdried
  8. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-ae5f0a12fbc64408afa0a03046e1bba2
Quelldatensatz
uspto-grants-1990_09
Patentnummer
US04958037

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