Ethyl Acrylate → (4R,9aR)-6-(2-Ethoxycarbonyl-vinyl)-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester

HRID 11919

反応式

HRID 11919 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15](Br)=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:23]([O:27][CH2:28][CH3:29])(=[O:26])[CH:24]=[CH2:25].C([O-])(=O)C.[Na+].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[C:1]([O:5][C:6]([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:25]=[CH:24][C:23]([O:27][CH2:28][CH3:29])=[O:26])=[CH:14][CH:13]=3)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 5

HCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 86590113(4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester2 回

生成物 1

HCID 69557653(4R,9aR)-6-(2-Ethoxycarbonyl-vinyl)-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester収率 91.2%

試薬・触媒・溶媒 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-触媒HCID 1140Toluene溶媒

実験手順

To a solution of 1.0 g (2.71 mmol) (4R,9aR)-6-bromo-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester (Example 5, intermediate b) and 0.36 ml (3.25 mmol) ethyl acrylate in 30 ml toluene were added 0.67 g (8.15 mmol) sodium acetate, 82.6 mg (0.27 mmol) tri(o-tolyl)phosphine and 0.04 mg (0.1 mmol) allylpalladium chloride dimer. The reaction mixture was heated under reflux for 20 h, then poured into saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic phase was washed with 10% aqueous citric acid solution and brine, dried over magnesium sulfate, filtered and evaporated. The crude product was purified by column chromatography on silica gel (0.032–0.063 mm) with n-hexane:ethyl acetate (9:1) as eluant to afford the desired compound as a yellow solid (91.2%).

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 20 h
  3. extractionextracted with ethyl acetate
  4. washThe organic phase was washed with 10% aqueous citric acid solution and brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe crude product was purified by column chromatography on silica gel (0.032–0.063 mm) with n-hexane:ethyl acetate (9:1) as eluant

出典と根拠

ORDレコード
ord-c7a4f3c997774bd4bc1869e396fb93b7
出典データセット
uspto-grants-2006_08
特許番号
US07098337B2

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