Hydrochloric Acid → Methyl 2-((1R,2R,3aS,9aS)-2,3,3a,4,9,9a-hexahydro-2-(tert-butyldimethylsilyoxy)-1-((S,E)-3-hydroxyoct-1-enyl)-1H-cyclopenta[b]naphthalen-5-yloxy)acetate

HRID 245600ノート

反応式

HRID 245600 の反応式
[Si:1]([O:8][C@H:9]1[C@H:22](/[CH:23]=[CH:24]/[C@@H:25]([O:31][Si](C(C)(C)C)(C)C)[CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[C@H:12]2[CH2:13][C:14]3[CH:15]=[CH:16][CH:17]=[C:18]([OH:21])[C:19]=3[CH2:20][C@H:11]2[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[OH-].[Na+].Cl.[C:42]([O:45][CH2:46]C)(=[O:44])[CH3:43]>BrCC(OC)=O>[Si:1]([O:8][C@H:9]1[C@H:22](/[CH:23]=[CH:24]/[C@@H:25]([OH:31])[CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[C@H:12]2[CH2:13][C:14]3[C:19]([CH2:20][C@H:11]2[CH2:10]1)=[C:18]([O:21][CH2:43][C:42]([O:45][CH3:46])=[O:44])[CH:17]=[CH:16][CH:15]=3)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 14798Sodium HydroxideHCID 86677387HCID 86677387、化合物

生成物 1

HCID 86703445Methyl 2-((1R,2R,3aS,9aS)-2,3,3a,4,9,9a-hexahydro-2-(tert-butyldimethylsilyoxy)-1-((S,E)-3-hydroxyoct-1-enyl)-1H-cyclopenta[b]naphthalen-5-yloxy)acetate収率 58%

試薬・触媒・溶媒 1

HCID 60984Methyl bromoacetate溶媒

実験手順

(1R,2R,3aS,9aS)-2,3,3a,4,9,9a-hexahydro-2-(tert-butyldimethylsilyoxy)-1-((S,E)-3-(tert-butyldimethylsilyoxy)oct-1-enyl)-1H-cyclopenta[b]naphthalen-5-ol (0.5 g, 0.89 mmol) in methyl bromoacetate (3 ml) was treated with 50% NaOH (1 g). The mixture was stirred at room temperature for 60 min. The reaction mixture was cooled to 10° C. and 3N HCl was added slowly until pH=7, and then the reaction was exacted with ethyl acetate. The organic layers were combined and dried over anhydrous magnesium sulfate. The solid was filtered off. The solvent was evaporated off under vacuum. The crude product was purified by chromatography on silica gel using a mixture of hexane and ethyl acetate as a gradient eluent. 0.2 g of Methyl 2-((1R,2R,3aS,9aS)-2,3,3a,4,9,9a-hexahydro-2-(tert-butyldimethylsilyoxy)-1-((S,E)-3-hydroxyoct-1-enyl)-1H-cyclopenta[b]naphthalen-5-yloxy)acetate was obtained. The product was then dissolved in THF (1.3 ml), acetic acid (3.9 ml) and distilled water (1.3 ml) for overnight at room temperature. The reaction mixture was poured to saturated sodium bicarbonate aqueous (1.0 ml) and stirred for 30 minutes. The reaction mixture was phase separated and the aqueous layer was extracted with 20 ml ethyl acetate. The organic layers were combined and dried over anhydrous magnesium sulfate. The solid was filtered off. The solvent was evaporated off under vacuum. The crude product was purified by chromatography on silica gel using a mixture of hexane and ethyl acetate as a gradient eluent. The titled compound was obtained in a crystalline form. (Yield: 58%)

後処理

  1. temperatureThe reaction mixture was cooled to 10° C.
  2. dry with materialdried over anhydrous magnesium sulfate
  3. filtrationThe solid was filtered off
  4. customThe solvent was evaporated off under vacuum
  5. customThe crude product was purified by chromatography on silica gel using
  6. additiona mixture of hexane and ethyl acetate as a gradient eluent

出典と根拠

ORDレコード
ord-0c9e20cf26ca409c865d5db67fc0e97f
出典データセット
uspto-grants-2014_02
特許番号
US08658837B2

反応ノート

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