Acetic Acid → (+/-)-(5Z)-7-{(1R,2R,3R,5R)-5-chloro-2-[(E)-4,4-dimethyl-3-oxo-1-octenyl]-3-(tetrahydropyran-2-yloxy)-cyclopentyl}-5-heptenic acid methyl ester

HRID 1382531

反応式

HRID 1382531 の反応式
[H-].[Na+].COP([CH2:9][C:10](=[O:18])[C:11]([CH3:17])([CH3:16])[CH2:12][CH2:13][CH2:14][CH3:15])(=O)OC.[CH3:19][O:20][C:21](=[O:43])[CH2:22][CH2:23][CH2:24]/[CH:25]=[CH:26]\[CH2:27][C@H:28]1[C@H:32]([Cl:33])[CH2:31][C@@H:30]([O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[C@@H:29]1[CH:41]=O.C(O)(=O)C>C(COC)OC.O1CCCC1.C(OCC)C.O>[CH3:19][O:20][C:21](=[O:43])[CH2:22][CH2:23][CH2:24]/[CH:25]=[CH:26]\[CH2:27][C@H:28]1[C@H:32]([Cl:33])[CH2:31][C@@H:30]([O:34][CH:35]2[CH2:40][CH2:39][CH2:38][CH2:37][O:36]2)[C@@H:29]1/[CH:41]=[CH:9]/[C:10](=[O:18])[C:11]([CH3:16])([CH3:17])[CH2:12][CH2:13][CH2:14][CH3:15]

参加物

9

反応物 4

HCID 176Acetic AcidHCID 24758Sodium hydrideHCID 11234130methyl (5Z)-7-[(1R,2R,3R,5R)-5-chloro-2-formyl-3-(tetrahydro-2H-pyran-2-yloxy)cyclopentyl]-5-heptenoateHCID 13018035Dimethyl (3,3-dimethyl-2-oxoheptyl)phosphonate

生成物 1

HCID 13853246(+/-)-(5Z)-7-{(1R,2R,3R,5R)-5-chloro-2-[(E)-4,4-dimethyl-3-oxo-1-octenyl]-3-(tetrahydropyran-2-yloxy)-cyclopentyl}-5-heptenic acid methyl ester収率 61.4%

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒HCID 80711,2-Dimethoxyethane溶媒2 回

反応条件

温度
-20 °C

実験手順

294 mg of 55% sodium hydride is suspended in 25 ml of dimethoxyethane, and 1.53 g of 3,3-dimethyl-2-oxoheptanephosphonic acid dimethyl ester is instilled. It is stirred for another 30 minutes, cooled to -20° C., and a solution of 1.98 g of VII in instilled in 10 ml of dimethoxyethane and 10 ml of tetrahydrofuran. After 1 hour it is allowed to warm to room temperature, mixed with 0.5 ml of glacial acetic acid, diluted with 200 ml of diethyl ether, shaken three times with 20 ml of salt water each, dried over magnesium sulfate and evaporated in a vacuum to dryness. The residue is chromatographed on silica gel with hexane/5-25% diethyl ether. 1.62 g of VIII is obtained as colorless oil. IR: 2998, 2955, 2863, 1730, 1684, 1621, 1437, 1060, 978/cm.

後処理

  1. waitAfter 1 hour it is allowed
  2. temperatureto warm to room temperature
  3. dry with materialdried over magnesium sulfate
  4. customevaporated in a vacuum to dryness
  5. customThe residue is chromatographed on silica gel with hexane/5-25% diethyl ether

出典と根拠

ORDレコード
ord-48d6969b3e31458bb371923dbbf040b3
出典データセット
uspto-grants-1989_02
特許番号
US04806668

関連ノート

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