Acetic Acid → 6-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

HRID 462769ノート

反応式

HRID 462769 の反応式
[Si]([O:8][CH:9]([CH:29]1[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]1)/[CH:10]=[CH:11]/[CH:12]1[CH2:19][CH2:18][CH:17]2[CH:13]1[CH2:14]/[C:15](=[CH:21]\[CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])/[C:16]2=[O:20])(C(C)(C)C)(C)C.O.C(O)(=O)C.O1CCCC1>[Cl-].[Na+]>[CH:29]1([CH:9]([OH:8])/[CH:10]=[CH:11]/[CH:12]2[CH2:19][CH2:18][CH:17]3[CH:13]2[CH2:14]/[C:15](=[CH:21]\[CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])/[C:16]3=[O:20])[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]1

参加物

6

反応物 4

HCID 176Acetic AcidHCID 962WaterHCID 8028TetrahydrofuranHCID 203972036-[(E)-3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octane-2-one

生成物 1

HCID 203972086-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one収率 138.1%

試薬・触媒・溶媒 1

HCID 5234Sodium Chloride溶媒

実験手順

6-[(E)-3-tert-Butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octane-2-one (12 mg), prepared as described in Reference Example 15 and in the form of (±)-6β-[(E)-3β-tert-butyldimethylsilyloxy-3-cyclohexylprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl(5E,13E)-(9S,15S)-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-15-cyclohexyl-16,17,18,19,20-pentanorprosta-5,13-dienoate, and a solution of water, glacial acetic acid and tetrahydrofuran (0.5 ml; 35:65:10 by volume) were stirred together at 40° C. for 4 hours. After cooling, the mixture was diluted with saturated aqueous sodium chloride solution and extracted with diethyl ether. The ethereal extracts were washed with aqueous sodium bicarbonate solution (1M) and then with saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulphate. Concentration under reduced pressure gave 6-[(E)-3-cyclohexyl-3-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (12.7 mg), in the form of (35)-6β-[(E)-3-cyclohexyl-3β-hydroxyprop-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl(5E,13E)-(9S,15S)-6a-oxo-6,9-methano-15-cyclohexyl-15-hydroxy-16,17,18,19,20-pentanorprosta-5,13-dienoate.

後処理

  1. temperatureAfter cooling
  2. extractionextracted with diethyl ether
  3. washThe ethereal extracts were washed with aqueous sodium bicarbonate solution (1M)
  4. dry with materialwith saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulphate
  5. concentrationConcentration under reduced pressure

出典と根拠

ORDレコード
ord-b8398b7d30ce48ff990df89272f4ee35
出典データセット
uspto-grants-1985_05
特許番号
US04517202

反応ノート

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