Ethanol → 7-Methylcamptothecin

HRID 434804

反応式

HRID 434804 の反応式
[CH2:1](O)C.[CH3:4][CH2:5][C@@:6]1([OH:29])[C:11](=[O:12])[O:10][CH2:9][C:8]2[C:13]([N:15]3[C:27](=[CH:28][C:7]1=2)[C:26]1[N:25]=[C:24]2[C:19]([CH:20]=[CH:21][CH:22]=[CH:23]2)=[CH:18][C:17]=1[CH2:16]3)=[O:14].S(=O)(=O)(O)O.OO>O>[CH3:4][CH2:5][C@@:6]1([OH:29])[C:11](=[O:12])[O:10][CH2:9][C:8]2[C:13]([N:15]3[C:27](=[CH:28][C:7]1=2)[C:26]1[C:17](=[C:18]([CH3:1])[C:19]2[C:24]([N:25]=1)=[CH:23][CH:22]=[CH:21][CH:20]=2)[CH2:16]3)=[O:14]

参加物

6

反応物 4

HCID 702EthanolHCID 784Hydrogen Peroxide4 回HCID 1118Sulfuric AcidHCID 24360Camptothecin

生成物 1

HCID 97990667-Methylcamptothecin

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

Ferrous sulfate heptahydrate (4.17 g, 15 m-mol) and ethanol (3 ml, 60 m-mol) were dissolved in water (30 ml). Camptothecin (700 mg, 2 m-mol) was suspended in the solution and dissolved therein by adding concentrated sulfuric acid (15 ml) in small portions to the suspension. To the mixture was added dropwise under ice-cooling and agitation a 30% aqueous solution of hydrogen peroxide (1.63 ml, 16 m-mol). After addition of the hydrogen peroxide, the mixture was stirred for 6 hours at room temperature. To the reaction mixture was added ferrous sulfate heptahydrate (2.0 g, 7.2 m-mol) and then was added dropwise under ice-cooling and agitation a 30% aqueous solution of hydrogen peroxide (1 ml, 9.8 m-mol). The agitation was continued for 15 hours at room temperature. To complete the reaction, additional ferrous sulfate heptahydrate (4.2 g, 15 m-mol) and a 30% aqueous solution of hydrogen peroxide (1.5 ml, 14.7 m-mol) were added to the reaction mixture and the whole was stirred for 8 hours at room temperature. The reaction mixture was diluted with ice water (2.5 liters) and extracted with chloroform (3 liters). The chloroform layer was dried with anhydrous magnesium sulfate, filtered and evaporated until dryness under reduced pressure. The residue was purified by way of column chromatography (chloroform) through silica gel (10 g) followed by recrystallization from n-hexane-chloroform whereby 127 mg (17.5%) of the objective compound were obtained as yellow needle crystals. M.P. 280°-281° C.

後処理

  1. dissolutiondissolved
  2. additionTo the mixture was added dropwise under ice-
  3. temperaturecooling
  4. additionwas added dropwise under ice-
  5. temperaturecooling
  6. waitThe agitation was continued for 15 hours at room temperature
  7. stirringthe whole was stirred for 8 hours at room temperature
  8. extractionextracted with chloroform (3 liters)
  9. dry with materialThe chloroform layer was dried with anhydrous magnesium sulfate
  10. filtrationfiltered
  11. customevaporated until dryness under reduced pressure
  12. customThe residue was purified by way of column chromatography (chloroform) through silica gel (10 g)
  13. customfollowed by recrystallization from n-hexane-chloroform whereby 127 mg (17.5%) of the objective compound
  14. customwere obtained as yellow needle crystals

出典と根拠

ORDレコード
ord-87c61dbde0d841e89aff1195e245ef11
出典データセット
uspto-grants-1983_08
特許番号
US04399282

関連ノート

読み込み中…