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

HRID 462776노트

반응식

HRID 462776 반응식
[CH3:1][O:2][C:3]([CH2:5][CH2:6][CH2:7]/[CH:8]=[C:9]1/[C:10](=[O:17])[CH:11]2[CH:15]([CH2:16]/1)[CH2:14][CH2:13][CH2:12]2)=[O:4].[OH2:18].[C:19]([OH:22])(=O)[CH3:20].O1[CH2:27][CH2:26][CH2:25][CH2:24]1>[Cl-].[Na+]>[OH:18][CH:6]([CH2:7][O:22][C:19]1[CH:20]=[CH:24][CH:25]=[CH:26][CH:27]=1)/[CH:5]=[CH:3]/[CH:14]1[CH2:13][CH2:12][CH:11]2[CH:15]1[CH2:16]/[C:9](=[CH:8]\[CH2:7][CH2:6][CH2:5][C:3]([O:2][CH3:1])=[O:4])/[C:10]2=[O:17]

참가 물질

6

반응물 4

HCID 176Acetic AcidHCID 962WaterHCID 8028TetrahydrofuranHCID 867400973-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one

생성물 1

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

시약·촉매·용매 1

HCID 5234Sodium Chloride용매

실험 절차

6-[(E)-3-tert-Butyldimethylsilyloxy-4-phenoxybut-1-enyl)]-3-[(E)-4-methoxycarbonylbutylidene]-bicyclo[3,3,0]octan-2-one (21 mg), prepared as described in Reference Example 48 and in the form of (±)-6β-[(E)-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,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 (0.86 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 ethereal 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 was subjected to medium pressure chromatography on silica gel, eluting with a mixture of ethyl acetate and hexane (1:1 v/v), to give 6-[(E)-3-hydroxy-4-phenoxybut-1-enyl]-3-[(E)-4-methoxycarbonylbutylidene]bicyclo[3,3,0]octan-2-one (15.9 mg), in the form of (±)-6β-[(E)-3β-hydroxy-4-phenoxybut-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-hydroxy-16-phenoxy-17,18,19,20-tetranorprosta-5,13-dienoate [NMR (in deuterochloroform): multiplets at 6.6-7.2, 6.3-6.6, 5.3-5.6, 4.3-4.5, 3.7-3.9, 1.3-2.8 p.p.m., singlet at 3.6 p.p.m⟧

후처리

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

출처 및 근거

ORD 기록
ord-54e9ea6ef5ca4031b06709683a37628e
출처 데이터셋
uspto-grants-1985_05
특허 번호
US04517202

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