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

HRID 1945536

Reaktionsgleichung

Reaktionsgleichung von HRID 1945536
[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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24193Titanium TetrachlorideKatalysatorHCID 5943Carbon TetrachlorideLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-9f7fc99e3ec54273a7c741d68772394a
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08394796B2

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