Boron trifluoride etherate → 1-Benzyl 4-ethyl 5-oxoazepane-1,4-dicarboxylate

HRID 2186684노트

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HRID 2186684 반응식
[O:1]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH2:3]1.[CH2:18]([O:20][C:21](=[O:25])[CH:22]=[N+]=[N-])[CH3:19].B(F)(F)F.CCOCC>CCOCC>[O:1]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[O:9])[CH2:4][CH2:3][CH:22]1[C:21]([O:20][CH2:18][CH3:19])=[O:25]

참가 물질

5

반응물 3

HCID 8000Boron trifluoride etherateHCID 12192Ethyl diazoacetateHCID 643496Benzyl 4-oxopiperidine-1-carboxylate

생성물 1

HCID 146001211-Benzyl 4-ethyl 5-oxoazepane-1,4-dicarboxylate수율 88%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

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온도
-45 °C

실험 절차

A dry 500 ml 3-neck flask was charged with benzyl 4-oxo-1-piperidinecarboxylate (35.08 g, 150 mmol). It was dissolved in 130 ml Et2O and cooled to −45° C. Ethyldiazoacetate (20.5 ml, 195 mmol) and boron trifluoride ethyl ether (19.4 ml, 158 mmol) were added simultaneously by syringe pump over 45 minutes. The temperature was kept below −25° C. The reaction was stirred for 30 minutes longer, and then quenched with sat. NaHCO3. The ice bath was removed. The reaction was diluted with EtOAc (250 ml) and H2O (150 ml). The layers were separated, and the organic phase was dried over MgSO4. It was concentrated under reduced pressure to an orange oil. The product was purified by flash chromatography (silica gel, 40% EtOAc/hexane), yielding product as pale yellow oil (42.1 g, 88%). 1H NMR (CDCl3) δ 7.39-7.31, 5.15-5.12, 4.42-4.17, 3.96-3.83, 3.75-3.70, 3.65, 3.54-3.37, 2.08-2.03, 1.29-1.24; IR (liq.) 1743, 1702, 1476, 1455, 1443, 1425, 1371, 1318, 1295, 1238, 1213, 1178, 1098, 1068, 1028 cm−1.

후처리

  1. customwas kept below −25° C
  2. customquenched with sat. NaHCO3
  3. customThe ice bath was removed
  4. additionThe reaction was diluted with EtOAc (250 ml) and H2O (150 ml)
  5. customThe layers were separated
  6. dry with materialthe organic phase was dried over MgSO4
  7. concentrationIt was concentrated under reduced pressure to an orange oil
  8. customThe product was purified by flash chromatography (silica gel, 40% EtOAc/hexane)

출처 및 근거

ORD 기록
ord-1101a578e87c43a08f9f5c2c34b7b908
출처 데이터셋
uspto-grants-2002_06
특허 번호
US06407092B1

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