10-Aminocamptothecin → Hydroxycamptothecin

HRID 463993

Reaktionsgleichung

Reaktionsgleichung von HRID 463993
[CH3:1][CH2:2][C@@:3]1([OH:27])[C:8](=[O:9])[O:7][CH2:6][C:5]2[C:10]([N:12]3[C:16](=[CH:17][C:4]1=2)[C:15]1[N:18]=[C:19]2[C:24](=[CH:25][C:14]=1[CH2:13]3)[CH:23]=[C:22](N)[CH:21]=[CH:20]2)=[O:11].N([O-])=[O:29].[Na+]>S(=O)(=O)(O)O.C(Cl)(Cl)Cl>[CH3:1][CH2:2][C@@:3]1([OH:27])[C:8](=[O:9])[O:7][CH2:6][C:5]2[C:10]([N:12]3[C:16](=[CH:17][C:4]1=2)[C:15]1[N:18]=[C:19]2[C:24]([CH:23]=[C:22]([OH:29])[CH:21]=[CH:20]2)=[CH:25][C:14]=1[CH2:13]3)=[O:11]

Komponenten

5

Edukt 2

HCID 10498610-AminocamptothecinHCID 23668193Sodium Nitrite2×

Produkt 1

HCID 97226HydroxycamptothecinAusbeute 66,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1118Sulfuric AcidLösungsmittel2×HCID 6212ChloroformLösungsmittel

Versuchsvorschrift

10-Aminocamptothecin (50 mg, 0.138 m-mol) is dissolved in a 10% aqueous solution of sulfuric acid (5 ml). To this solution in a salted ice bath is added dropwise slowly an aqueous solution of sodium nitrite (9.5 mg, 0.138 m-mol) with stirring. After the addition of sodium nitrite, the mixture is further stirred for 10 minutes in a salted ice bath. To the reaction mixture is added conc. sulfuric acid (1 ml), and the whole is boiled under reflux for 2 hours. The reaction mixture is diluted with ice water (200 ml) and chloroform (200 ml) is added. The mixture is shaken in a separating funnel and the resultant emulsion is filtered through celite. The chloroform phase containing camptothecin formed as by-product by side reactions is dried over magnesium sulfate, filtered and evaporated until dryness under reduced pressure whereby camptothecin (8 mg) is recovered. On the other hand, a solid on the celite, which is insoluble in chloroform-water, is taken up in 20% MeOH-CHCl3 (200 ml) and the solution is evaporated until dryness under reduced pressure whereby 28 mg (yield: 66.5% ) of the title compound is obtained as light yellow crystals. M.P. (with decomp.) 270°-272° C. (from pyridine-methanol)

Aufarbeitung

  1. stirringthe mixture is further stirred for 10 minutes in a salted ice bath
  2. temperatureunder reflux for 2 hours
  3. additionis added
  4. stirringThe mixture is shaken in a separating funnel
  5. filtrationthe resultant emulsion is filtered through celite
  6. additionThe chloroform phase containing camptothecin
  7. customformed as by-product by side reactions
  8. dry with materialis dried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated until dryness under reduced pressure whereby camptothecin (8 mg)
  11. customis recovered

Quellen und Nachweise

ORD-Eintrag
ord-25e678f0cb5a4839b4ecf8ff355f4148
Quelldatensatz
uspto-grants-1985_10
Patentnummer
US04545880

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