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

HRID 1813901노트

반응식

HRID 1813901 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

반응 조건

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 mol) 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 67.39-7.31, 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-ac4544eaa4b6400e9b07205adfffec85
출처 데이터셋
uspto-grants-2005_04
특허 번호
US06875762B2

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