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

HRID 459723

반응식

HRID 459723 반응식
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]

참가 물질

6

반응물 3

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

생성물 1

HCID 219309943-(Di-tert-butoxycarbonylamino)-1-methylpiperidine수율 54.2%

시약·촉매·용매 2

HCID 66321Lithium iodide촉매HCID 6342Acetonitrile용매

반응 조건

온도
70 °C

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-8ba102ce69bc4771939241965a0d0990
출처 데이터셋
uspto-grants-2007_03
특허 번호
US07196078B2

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