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

HRID 462778ノート

反応式

HRID 462778 の反応式
[Si]([O:8][CH:9]([CH2:29][O:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=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.COC(CCC/C=C1/C(=O)C2C(C/1)CCC2)=O.O.C(O)(=O)C>[Cl-].[Na+].O1CCCC1>[OH:8][CH:9]([CH2:29][O:30][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=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]

参加物

7

反応物 4

HCID 176Acetic AcidHCID 962WaterHCID 203971906-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-oneHCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

生成物 1

HCID 203971966-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one収率 28.2%

試薬・触媒・溶媒 2

HCID 5234Sodium Chloride溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

6-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (4.1 mg), prepared as described in Reference Example 54, and in the form of (±)-6β-[(E)-(mixture of 3α and 3β)-tert-butyldimethylsilyloxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl (5E,13E)-(9S), [mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-tert-butyldimethylsilyloxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate, and a solution of water, glacial acetic acid and tetrahydrofuran (1.0 ml; 7:13:2 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 extract was washed with aqueous sodium bicarbonate solution (1M) and then with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue (3.0 mg) was subjected to preparative thin layer chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (3:2 v/v), to give 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl] -3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (0.9 mg), in the form of (±)-6β-[(E)-(mixture of 3α and 3β)-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one, otherwise known as (±)-methyl (5E,13E)-(9S), [mixture of (15R) and (15S)]-6a-oxo-6,9-methano-15-hydroxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate.

後処理

  1. temperatureAfter cooling
  2. extractionextracted with diethyl ether
  3. washThe extract was washed with aqueous sodium bicarbonate solution (1M)
  4. dry with materialwith saturated aqueous sodium chloride solution, dried over anhydrous sodium sulphate
  5. concentrationconcentrated under reduced pressure
  6. washeluting with a mixture of ethyl acetate and hexane (3:2 v/v)

出典と根拠

ORDレコード
ord-a9b6913a7d294618a054b26effe7121b
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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