Ethanol → Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate

HRID 1070366ノート

反応式

HRID 1070366 の反応式
[C:1]([NH:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2].[H-].[Na+].C(O)C.Br[CH2:22][C:23]1[C:36]2[C:37]3=[C:38]4[C:33](=[CH:34][CH:35]=2)[CH:32]=[CH:31][CH:30]=[C:29]4[CH:28]=[CH:27][C:26]3=[CH:25][CH:24]=1>C1COCC1>[CH2:9]([O:8][C:6](=[O:7])[C:5]([CH2:22][C:23]1[C:36]2[C:37]3=[C:38]4[C:33](=[CH:34][CH:35]=2)[CH:32]=[CH:31][CH:30]=[C:29]4[CH:28]=[CH:27][C:26]3=[CH:25][CH:24]=1)([NH:4][C:1](=[O:3])[CH3:2])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH3:10]

参加物

6

反応物 4

HCID 702EthanolHCID 14041Acetamidomalonic acid diethyl esterHCID 24758Sodium hydrideHCID 12740433-(Bromomethyl)pyrene

生成物 1

HCID 22395542Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate収率 83.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A 9.78 g (45.04 mmol) sample of diethyl acetamidomalonate, and 1.08 g sodium hydride (45.04 mmol) were suspended in 100 mL of anhydrous THF, under nitrogen, and at 0°C. After stirring for 5 min., 2.5 mL of anhydrous ethanol were added slowly, and the solution returned to room temperature. A solution of 1-(bromomethyl)pyrene (12.03 g, 40.9 mmol, dissolved in 100 mL dry THF) was slowly added to the reaction mixture, and the solution brought to reflux for 18 h. The bulk of the THF was removed under reduced pressure, and the remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2:H2O. The organic fraction was washed 3× with 100 mL H2O, and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to produce Diethyl-2-(1-pyrenylmethyl)-2-acetamidomalonate (14.70 g, 83.1%) as a light yellow powder. TLC (SiO2, 1:1 Hexane:EtOAc) Rƒ=0.57. Mp=135-140° C. 1H NMR (CDCl3), δ1.37 (t, 6H), 1.95 (s, 3H), 3.76 (s, 2H), 4.30 (q, 6H), 6.42 (s, NH), 8.00-825 (m, 9H from pyrene).

後処理

  1. customat 0°C
  2. customreturned to room temperature
  3. temperatureto reflux for 18 h
  4. customThe bulk of the THF was removed under reduced pressure
  5. dissolutionthe remaining yellow slurry was dissolved in 400 mL 1:1 CH2Cl2
  6. washThe organic fraction was washed 3× with 100 mL H2O
  7. dry with materialdried over anhydrous Na2SO4
  8. customSolvent was removed under reduced pressure

出典と根拠

ORDレコード
ord-473c372186044f259f42cd8a49ea3297
出典データセット
uspto-grants-2005_06
特許番号
US06902720B2

反応ノート

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