Cesium carbonate → 3-(Di-tert-butoxycarbonylamino)-1-methylpiperidine

HRID 1157380Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1157380
BrC[CH:3]1[CH2:8][CH2:7][CH2:6][N:5]([CH3:9])[CH2:4]1.[CH3:10][C:11]([O:14][C:15]([NH:17][C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[O:16])([CH3:13])[CH3:12].C(=O)([O-])[O-].[Cs+].[Cs+]>C(#N)C.[I-].[Li+]>[C:21]([O:20][C:18]([N:17]([C:15]([O:14][C:11]([CH3:13])([CH3:12])[CH3:10])=[O:16])[CH:3]1[CH2:8][CH2:7][CH2:6][N:5]([CH3:9])[CH2:4]1)=[O:19])([CH3:24])([CH3:23])[CH3:22]

Komponenten

6

Edukt 3

HCID 10796Cesium carbonateHCID 279800Di-tert-butyl IminodicarboxylateHCID 219309923-(Bromomethyl)-1-methylpiperidine

Produkt 1

HCID 219309943-(Di-tert-butoxycarbonylamino)-1-methylpiperidineAusbeute 54,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 66321Lithium iodideKatalysatorHCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

3-(Bromomethyl)-1-methylpiperidine (1.5 g, 7.81 mmoles) (from Preparative Example 244, Step A above) and di-tert-butyliminodicarboxylate (1.697 g, 7.81 mmoles) were dissolved in anhydrous acetonitrile (25 mL). Cesium carbonate (5.1 g, 15.6 mmoles) and lithium iodide (52 mg, 0.391 mmoles) were added and the mixture was stirred at 70° C. for 20 h. The mixture was evaporated to dryness and the residue was partitioned between dichloromethane and saturated aqueous sodium bicarbonate. The organic layer was dried (MgSO4), filtered and evaporated to dryness. the residue was chromatographed on a silica gel column (30×5 cm) using 3% methanol in dichloromethane as the eluant to give 3-(di-tert-butoxycarbonylamino)-1-methylpiperidine (1.331 g, 52%): FABMS: m/z 329.2 (MH+); HRFABMS: m/z 329.2438 (MH+). Calcd. for C17H33N2O4: m/z 329.2440; δH (CDCl3) 1.10 (1H, m, CH2), 1.54 (18H, s, —COOC(CH3)3), 1.86 (2H, m, CH2), 2.01 (1H, m, CH2), 2.19 (1H m, CH), 2.34 (2H, bm, CH2), 2.59 (3H, —NCH3), 3.19 (2H, m, CH2) and 3.52/3.52 ppm (2H, —CH2N—); δC (CDCl3) CH3, 28.5, 28.5, 28.5, 28.5, 28.5, 28.5, 47.2; CH2, 25.4, 28.3, 50.4, 56.8, 60.8; CH, 37.2; C, 83.0, 83.0, 153.5, 153.5.

Aufarbeitung

  1. customThe mixture was evaporated to dryness
  2. customthe residue was partitioned between dichloromethane and saturated aqueous sodium bicarbonate
  3. dry with materialThe organic layer was dried (MgSO4)
  4. filtrationfiltered
  5. customevaporated to dryness
  6. customthe residue was chromatographed on a silica gel column (30×5 cm)

Quellen und Nachweise

ORD-Eintrag
ord-333d1cc38eea4715874b0360919b9887
Quelldatensatz
uspto-grants-2010_10
Patentnummer
US07807683B2

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