Acetic Anhydride → HCID 86703444, compound

HRID 245597Notes

Reaction equation

HRID 245597 reaction equation
[Si:1]([O:8][C@H:9]1[C@H:22](/[CH:23]=[CH:24]/[C@@H:25]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[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].[C:39](OC(=O)C)(=[O:41])[CH3:40]>C1(C)C=CC=CC=1.CN(C1C=CN=CC=1)C.C(=O)(O)[O-].[Na+]>[C:39]([O:21][C:18]1[CH:17]=[CH:16][CH:15]=[C:14]2[C:19]=1[CH2:20][C@H:11]1[CH2:10][C@@H:9]([O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[C@H:22](/[CH:23]=[CH:24]/[C@@H:25]([O:31][Si:32]([C:35]([CH3:37])([CH3:36])[CH3:38])([CH3:34])[CH3:33])[CH2:26][CH2:27][CH2:28][CH2:29][CH3:30])[C@H:12]1[CH2:13]2)(=[O:41])[CH3:40]

Participants

6

Reactant 2

HCID 7918Acetic AnhydrideHCID 86677387HCID 86677387, compound

Product 1

HCID 86703444HCID 86703444, compoundYield 84.1%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1140TolueneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

(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 toluene (5 ml) was treated with acetic anhydride (0.1 ml, 1.07 mmol) and DMAP (1.1 mg, 0.09 mmol) at room temperature for 30 minutes. The reaction was diluted with saturated sodium bicarbonate aqueous (10 ml) and extracted with ethyl acetate (10 ml). The reaction mixture was phase separated and the aqueous layer was extracted 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. 0.45 g (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-yl acetate was obtained. The product was then dissolved in tetrahydrofuran (0.9 ml), and treated with acetic acid (2.7 ml) and distilled water (0.9 ml) overnight at room temperature. The reaction was then diluted with saturated sodium bicarbonate aqueous (12 ml) and extracted with ethyl acetate (15 ml). The reaction mixture was phase separated and the aqueous layer was extracted 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. The titled compound was obtained in a crystalline form. Melting range was 54˜65° C. Yield: 65%.

Workup

  1. extractionextracted with ethyl acetate (10 ml)
  2. customseparated
  3. extractionthe aqueous layer was extracted with ethyl acetate
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationThe solid was filtered off
  6. customThe solvent was evaporated off under vacuum
  7. customThe crude product was purified by chromatography on silica gel using
  8. additiona mixture of hexane and ethyl acetate as a gradient eluent

Sources & evidence

ORD record
ord-57d5be37235448198c12ccdc41fc011e
Source dataset
uspto-grants-2014_02
Patent number
US08658837B2

Reaction notes

Loading…