Ammonium Chloride → (4R,6R)-6-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]-2-methoxycarbonyl-4-hydroxy-1-heptene

HRID 1603277

反応式

HRID 1603277 の反応式
[Br:1][CH:2]=[C:3]1[CH2:11][CH2:10][CH2:9][C@@:8]2([CH3:12])[CH:4]1[CH2:5][CH2:6][C@@H:7]2[C@H:13]([CH3:17])[CH2:14][CH2:15][OH:16].[CH3:18][O:19][C:20](=[O:25])[C:21]([CH2:23]Br)=[CH2:22].[Cl-].[NH4+]>[Zn].O1CCCC1>[Br:1][CH:2]=[C:3]1[CH2:11][CH2:10][CH2:9][C@@:8]2([CH3:12])[CH:4]1[CH2:5][CH2:6][C@@H:7]2[C@H:13]([CH3:17])[CH2:14][C@H:15]([OH:16])[CH2:23][C:21]([C:20]([O:19][CH3:18])=[O:25])=[CH2:22].[Br:1][CH:2]=[C:3]1[CH2:11][CH2:10][CH2:9][C@@:8]2([CH3:12])[CH:4]1[CH2:5][CH2:6][C@@H:7]2[C@H:13]([CH3:17])[CH2:14][C@@H:15]([OH:16])[CH2:23][C:21]([C:20]([O:19][CH3:18])=[O:25])=[CH2:22]

参加物

7

反応物 3

HCID 25517Ammonium ChlorideHCID 5210932-Propenoic acid, 2-(bromomethyl)-, methyl esterHCID 70187597(3R)-3-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]butanol

生成物 2

HCID 57100754(4R,6R)-6-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]-2-methoxycarbonyl-4-hydroxy-1-hepteneHCID 57127874(4S,6R)-6-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]-2-methoxycarbonyl-4-hydroxy-1-heptene

試薬・触媒・溶媒 2

HCID 23994Zinc触媒HCID 8028Tetrahydrofuran溶媒

実験手順

A 105 mg amount of (3R)-3-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]butanol was taken in a 50 ml eggplant-shaped flask, then 8 ml of dried tetrahydrofuran was then added to dissolve the same. The solution was cooled by an ice cooled bath, then 84 μl of methyl-2-bromomethylacrylate was added dropwise. Further, 35 mg of zinc powder and 10 ml of a saturated aqueous solution of ammonium chloride were added, then the solution was stirred at the same temperature for 1 hour. The reaction solution was extracted by ethyl acetate, the organic layer was washed with saturated saline, then was dried over anhydrous magnesium sulfate. The desiccant was filtered out, then the solvent was distilled off under reduced pressure to obtain a crude product in an amount of 166 mg. This was purified by a silica gel column (Merck gel, hexane/ethyl acetate=9/1) to obtain (4S,6R)-6-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]-2-methoxycarbonyl-4-hydroxy-1-heptene in an amount of 43 mg and (4R,6R)-6-[(1R,7aR)-octahydro-4-bromomethylene-7a-methyl-1H-inden-1-yl]-2-methoxycarbonyl-4-hydroxy-1-heptene in an amount of 55 mg.

後処理

  1. dissolutionto dissolve the same
  2. temperatureThe solution was cooled by an ice cooled bath
  3. extractionThe reaction solution was extracted by ethyl acetate
  4. washthe organic layer was washed with saturated saline
  5. dry with materialwas dried over anhydrous magnesium sulfate
  6. filtrationThe desiccant was filtered out
  7. distillationthe solvent was distilled off under reduced pressure
  8. customto obtain a crude product in an amount of 166 mg
  9. customThis was purified by a silica gel column (Merck gel, hexane/ethyl acetate=9/1)

出典と根拠

ORDレコード
ord-9f3487b410ea4677820f43b41d48ebf4
出典データセット
uspto-grants-1999_11
特許番号
US05986112

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