Sodium hydride → 1-(Benzyloxycarbonyl)-4-(3-oxo-3-phenylprop-1-enyl)piperidine

HRID 1386766노트

반응식

HRID 1386766 반응식
[O:1]=[C:2]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:3]P(=O)(OCC)OCC.[H-].[Na+].[CH2:20]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33]([CH:36]=O)[CH2:32][CH2:31]1)=[O:29])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1COCC1>[CH2:20]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33]([CH:36]=[CH:3][C:2](=[O:1])[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH2:32][CH2:31]1)=[O:29])[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

참가 물질

5

반응물 3

HCID 24758Sodium hydrideHCID 372803Diethyl 2-oxo-2-phenylethylphosphonateHCID 2776272Benzyl 4-formylpiperidine-1-carboxylate

생성물 1

HCID 570744891-(Benzyloxycarbonyl)-4-(3-oxo-3-phenylprop-1-enyl)piperidine

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매3회

실험 절차

Diethyl (2-oxo-2-phenylethyl)phosphonate (0.96 mL,1.1 g, 4.4 mmol) was added in one portion to a stirred suspension of sodium hydride (60% oil dispersion, 158 mg, 3.95 mmol) in THF (20 mL). After 15 min. at RT, the clear solution was cooled in an ice bath and 1-(benzyloxycarbonyl)-4-piperidinecarboxaldehyde (840 mg, 3.40 mmol) was added in THF (1.0 mL) with additional THF (2×1.0 mL) for rinsing. Stirring was continued for a total of 2 h, with slow warming to RT. The mixure was then partitioned between ether (120 ml) and 2.5 N NaOH (60 mL). The organic layer was washed with saturated aq. NaCl (60 mL), dried (Na2SO4), decanted, and evaporated. The crude product was purified by flash column chromatography on silica gel eluting with 85:15 v/v to 80:20 v/v hexanes/EtOAc to give 0-95 g of the title compound as a colorless syrup: 1H NMR (400 MHz) δ 7.82 (d, J=8, 21), 7.57 (t, J=8, 1H), 7.48 (t, J=8, 2H), 7.39-7.29 (m, 51), 6.99 (dd, J=15, 6, 1H), 6.87 (dd, J=15, 1, 1H), 5.15 (s, 2H), 2.97-2.82 (m, 2H), 2.50-2.39 (m, 1H), 1.89-1.77 (m, 2H), 1.54-1.39 (m, 2H); ESI-MS 367 (M+NH3+H).

후처리

  1. temperaturethe clear solution was cooled in an ice bath
  2. washfor rinsing
  3. customwas continued for a total of 2 h
  4. customThe mixure was then partitioned between ether (120 ml) and 2.5 N NaOH (60 mL)
  5. washThe organic layer was washed with saturated aq. NaCl (60 mL)
  6. dry with materialdried (Na2SO4)
  7. customdecanted
  8. customevaporated
  9. customThe crude product was purified by flash column chromatography on silica gel eluting with 85:15 v/v to 80:20 v/v hexanes/EtOAc

출처 및 근거

ORD 기록
ord-ca371127a3f347b69c016190274631e8
출처 데이터셋
uspto-grants-2001_07
특허 번호
US06265434B1

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