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

HRID 1945536

반응식

HRID 1945536 반응식
[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]

참가 물질

7

반응물 4

HCID 1049PyridineHCID 8028Tetrahydrofuran2회HCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 69515632,2-Diethylpropanedioate

생성물 1

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

시약·촉매·용매 2

HCID 24193Titanium Tetrachloride촉매HCID 5943Carbon Tetrachloride용매

실험 절차

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, 4 H); 3.55-3.44 (m, 4 H); 2.65 (m, 4 H); 1.49 (s, 9 H) and 1.32-1.26 (m, 6 H).

후처리

  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

출처 및 근거

ORD 기록
ord-9f7fc99e3ec54273a7c741d68772394a
출처 데이터셋
uspto-grants-2013_03
특허 번호
US08394796B2

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