Dabco → Ethyl 1-oxa-2-azaspiro[4.5]dec-2-ene-3-carboxylate

HRID 1518109노트

반응식

HRID 1518109 반응식
[CH2:1]=[C:2]1[CH2:7][CH2:6][CH2:5][CH2:4][CH2:3]1.[CH2:8]([O:10][C:11](=[O:16])[CH2:12][N+:13]([O-])=[O:14])[CH3:9].C1N2CCN(CC2)C1>CCO>[O:14]1[C:2]2([CH2:7][CH2:6][CH2:5][CH2:4][CH2:3]2)[CH2:1][C:12]([C:11]([O:10][CH2:8][CH3:9])=[O:16])=[N:13]1

참가 물질

5

반응물 3

HCID 9237DabcoHCID 14502MethylenecyclohexaneHCID 69379Ethyl nitroacetate

생성물 1

HCID 59280111Ethyl 1-oxa-2-azaspiro[4.5]dec-2-ene-3-carboxylate수율 64%

시약·촉매·용매 1

HCID 702Ethanol용매2회

반응 조건

온도
80 °C

실험 절차

To a 300 mL pressure vessel equipped with a magnetic stir bar was added methylenecyclohexane (5.83 g, 60.6 mmol) and EtOH (150 mL). Nitro-acetic acid ethyl ester (16.8 mL, 152 mmol) and DABCO (680 mg, 6.06 mmol) were then added. Additional EtOH (30 mL) was added to rinse the sides of the vessel, which was tightly capped. The mixture was heated to 80° C. for 42 h and then cooled to RT. The solvent was removed under reduced pressure, and the residue was divided into three equal portions. Each portion was purified by column chromatography using an 80-g SiO2 pre-packed column eluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min, yielding 8.12 g (64%) of the desired ester. 1H-NMR (400 MHz, CDCl3) δ: 4.34 (q, J=7.2 Hz, 2H), 2.91 (s, 2H), 1.71-1.88 (m, 4H), 1.60-1.71 (m, 2H), 1.39-1.53 (m, 4H), 1.37 (t, J=7.1 Hz, 3H).

후처리

  1. customTo a 300 mL pressure vessel equipped with a magnetic stir bar
  2. washto rinse the sides of the vessel, which
  3. customwas tightly capped
  4. temperaturecooled to RT
  5. customThe solvent was removed under reduced pressure
  6. customEach portion was purified by column chromatography
  7. washeluting with EtOAc/hexanes, 0:1 to 1:4, v/v over 30 min

출처 및 근거

ORD 기록
ord-a7575c5bb32f418985e1521db5215578
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08232409B2

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