Acetic Acid → TERT-BUTYL 4-(1-CYANO-2-ETHOXY-2-OXOETHYLIDENE)PIPERIDINE-1-CARBOXYLATE

HRID 1992057노트

반응식

HRID 1992057 반응식
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.[C:15]([CH2:17][C:18]([O:20][CH2:21][CH3:22])=[O:19])#[N:16].C([O-])(=O)C.[NH4+].C(O)(=O)C>C1C=CC=CC=1>[C:15]([C:17](=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1)[C:18]([O:20][CH2:21][CH3:22])=[O:19])#[N:16]

참가 물질

6

반응물 4

HCID 176Acetic AcidHCID 7764Ethyl cyanoacetateHCID 517165Ammonium AcetateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

생성물 1

HCID 11551073TERT-BUTYL 4-(1-CYANO-2-ETHOXY-2-OXOETHYLIDENE)PIPERIDINE-1-CARBOXYLATE

시약·촉매·용매 1

HCID 241Benzene용매

실험 절차

A mixture of tert-butyl 4-oxo-1-piperidinecarboxylate (25.25 g, 127 mmol), ethyl cyanoacetate (13.8 ml, 130 mmol), ammonium acetate (2.73 g, 35.4 mmol), glacial acetic acid (6.3 ml) and benzene (250 ml) was heated for 4 hours at reflux under Dean Stark conditions. The reaction mixture was cooled to room temperature and washed successively with water, sodium bicarbonate solution and brine. Drying, filtration and evaporation of the organic phase provided tert-butyl 4-(1-cyano-2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate as an oil that crystallized on standing (37 g, 99%). 1H NMR (400 MHz, CDCl3): δ 4.28 (q, 2H, J=7 Hz), 3.60 (br t, 2H, J=6 Hz), 3.54 (br t, 2H, J=6 Hz), 3.12 (t, 2H, J=6 Hz), 2.76 (t, 2H, J=6 Hz), 1.47 (s, 9H), and 1.35 (t, 3H, J=7 Hz). ES-LCMS m/z 293 (M−1).

후처리

  1. temperaturewas heated for 4 hours
  2. temperatureat reflux under Dean Stark conditions
  3. washwashed successively with water, sodium bicarbonate solution and brine
  4. customDrying
  5. filtrationfiltration and evaporation of the organic phase

출처 및 근거

ORD 기록
ord-2bcba03b9b5c4d91a83543a1f16dc8ba
출처 데이터셋
uspto-grants-2010_01
특허 번호
US07645771B2

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