Pyridine → Diethyl 2-(1-(tert-butoxycarbonyl)piperidin-4-ylidene)malonate

HRID 1922686

反応式

HRID 1922686 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([C:17](CC)([C:21]([O-:23])=[O:22])[C:18]([O-:20])=[O:19])C.N1C=CC=[CH:28][CH:27]=1.[CH2:32]1COC[CH2:33]1>C(Cl)(Cl)(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[CH2:27]([O:23][C:21](=[O:22])[C:17](=[C:11]1[CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]1)[C:18]([O:20][CH2:32][CH3:33])=[O:19])[CH3:28]

参加物

7

反応物 4

HCID 1049PyridineHCID 8028Tetrahydrofuran2 回HCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 69515632,2-Diethylpropanedioate

生成物 1

HCID 59605837Diethyl 2-(1-(tert-butoxycarbonyl)piperidin-4-ylidene)malonate収率 100%

試薬・触媒・溶媒 2

HCID 24193Titanium Tetrachloride触媒HCID 5943Carbon Tetrachloride溶媒

実験手順

To anhydrous THF (50 mL) at 0° C. a solution of TiCl4 (13.75 mL, 0.126 mol) in CCl4 (10 mL) was added dropwise. To the resulting yellow suspension were a solution of 4-oxopiperidine-1-carboxylic acid tert-butyl ester (10 g, 0.05 mol) and diethylmalonate (6.85 mL, 0.05 mol) in anhydrous THF (50 mL) added, followed by addition of pyridine (26 mL) The dark yellow suspension was allowed to warm to ambient temperature and stirred at ambient temperature for 17 h, then partitioned between EtOAc and citric acid (10%, aq.). The organic layer was separated and washed with water and brine, then dried (MgSO4) and concentrated in vacuo to afford 2-(1-(tert-Butoxycarbonyl)piperidin-4-ylidene)malonic acid diethyl ester as a brown oil (17 g, 100%). 1H NMR (CDCl3, 400 MHz) δ 4.27-4.18 (m, 4H); 3.55-3.44 (m, 4H); 2.65 (m, 4H); 1.49 (s, 9H) and 1.32-1.26 (m, 6H).

後処理

  1. additionadded
  2. custompartitioned between EtOAc and citric acid (10%, aq.)
  3. customThe organic layer was separated
  4. washwashed with water and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-3d33642c626c419db13c07e5ef3b1118
出典データセット
uspto-grants-2012_05
特許番号
US08173650B2

関連ノート

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