Acetic Acid → Ethyl 4-(dibenzylamino)-2-ethylcyclopentanecarboxylate

HRID 1854363ノート

反応式

HRID 1854363 の反応式
[CH2:1]([CH:3]1[CH2:7][C:6](=O)[CH2:5][CH:4]1[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH3:2].CC(O)=O.[CH2:18]([NH:25][CH2:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C([O-])(O)=O.[Na+]>ClCCCl>[CH2:26]([N:25]([CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH:6]1[CH2:5][CH:4]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:3]([CH2:1][CH3:2])[CH2:7]1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1

参加物

7

反応物 5

HCID 176Acetic AcidHCID 7656DibenzylamineHCID 516892Sodium Bicarbonate2 回HCID 5049666Sodium triacetoxyborohydrideHCID 58010012Cyclopentanecarboxylic acid, 2-ethyl-4-oxo-, ethyl ester

生成物 1

HCID 58009964Ethyl 4-(dibenzylamino)-2-ethylcyclopentanecarboxylate収率 72%

試薬・触媒・溶媒 1

HCID 111,2-Dichloroethane溶媒2 回

反応条件

温度
0 °C

実験手順

A round-bottom flask was charged with ethyl 2-ethyl-4-oxocyclopentanecarboxylate (95.9 g, 521 mmol, Preparation #DD.1) and DCE (1.8 L). The solution was cooled to about 0° C. and AcOH (45 mL, 780 mmol) and dibenzylamine (120 mL, 625 mmol) were added drop-wise, resulting in formation of a thick suspension. The reaction mixture was warmed to about 10° C. and additional DCE (500 mL) was added. Sodium triacetoxyborohydride (166 g, 781 mmol) was added portion-wise and the reaction mixture was stirred at room temperature for about 20 h. The reaction mixture was slowly poured into stirred saturated aqueous NaHCO3 (1.5 L), followed by the portion-wise addition of solid sodium bicarbonate (175 g,). The mixture was stirred for about 2 h and the organic layer was separated, dried over anhydrous Na2SO4, and concentrated to dryness under reduced pressure. The crude yellow oil was purified by silica gel chromatography using EtOAc/heptane as eluant (0-20% EtOAc in heptane). The solvent was removed under reduced pressure to yield ethyl 4-(dibenzylamino)-2-ethylcyclopentanecarboxylate (136.6 g, 72%) as a white solid: LC/MS (Table 2, Method a) Rt=3.26 min; MS m/z: 366 (M+H)+

後処理

  1. customresulting in formation of a thick suspension
  2. temperatureThe reaction mixture was warmed to about 10° C.
  3. additionThe reaction mixture was slowly poured
  4. stirringThe mixture was stirred for about 2 h
  5. customthe organic layer was separated
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated to dryness under reduced pressure
  8. customThe crude yellow oil was purified by silica gel chromatography
  9. customThe solvent was removed under reduced pressure

出典と根拠

ORDレコード
ord-1f2c5f1c63cd4afc9191211e28da295f
出典データセット
uspto-grants-2015_02
特許番号
US08962629B2

反応ノート

読み込み中…