Sulfuric Acid → Crotophorbolone

HRID 2410650

反応式

HRID 2410650 の反応式
[CH3:1][C@H:2]1[C@:10]2([OH:24])[C@H:11]3[C@:16]([OH:22])([CH2:17][C:18]([CH2:20][OH:21])=[CH:19][C@H:9]2[C@@H:5]2[C:6]([CH3:8])([CH3:7])[C@:4]2([OH:25])[C@@H:3]1O)[C:14](=[O:15])[C:13]([CH3:23])=[CH:12]3.S(=O)(=O)(O)O>>[CH3:1][C@H:2]1[C@:10]2([OH:24])[CH:11]3[C@:16]([OH:22])([CH2:17][C:18]([CH2:20][OH:21])=[CH:19][C@H:9]2[C@H:5]([C:6]([CH3:8])=[CH2:7])[C:4](=[O:25])[CH2:3]1)[C:14](=[O:15])[C:13]([CH3:23])=[CH:12]3

参加物

3

反応物 2

HCID 1118Sulfuric AcidHCID 442070Phorbol

生成物 1

HCID 102259583Crotophorbolone収率 39.2%

反応条件

温度
90 °C

実験手順

To a 50 mL round-bottom flask containing a stirbar and phorbol (1.76 g, 4.82 mmol, 1.0 eq) at ambient temperature (23° C.) was added sulfuric acid (0.01 M aqueous H2SO4 solution: 16 mL, 0.3 M with respect to phorbol). The flask was equipped with a reflux condenser, the system flushed with a stream of dry nitrogen, and the cloudy, slightly yellow mixture heated to 90° C. After 1 h, the reaction vessel was cooled to room temperature (23° C.), the aqueous solution extracted with EtOAc, and the organic phase washed with brine. The organic phase was dried over Na2SO4, filtered, concentrated under reduced pressure, and purified by flash chromatography on a 4.5×18 cm silica gel column eluting with a solvent gradient from 75% to 90% EtOAc/petrol ether followed by elution with 100% EtOAc. The eluant was collected in 75 mL portions, and the crotophorbolone containing fractions were combined and concentrated to give crotophorbolone (654 mg).

後処理

  1. customThe flask was equipped with a reflux condenser
  2. customthe system flushed with a stream of dry nitrogen
  3. temperaturethe reaction vessel was cooled to room temperature (23° C.)
  4. extractionthe aqueous solution extracted with EtOAc
  5. washthe organic phase washed with brine
  6. dry with materialThe organic phase was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. custompurified by flash chromatography on a 4.5×18 cm silica gel column
  10. washeluting with a solvent gradient from 75% to 90% EtOAc/petrol ether
  11. washfollowed by elution with 100% EtOAc
  12. customThe eluant was collected in 75 mL portions
  13. concentrationconcentrated

出典と根拠

ORDレコード
ord-e9888d26bdbe4aa0a53ebf628679228a
出典データセット
uspto-grants-2014_08
特許番号
US08816122B2

関連ノート

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