Sodium hydride → 1-t-Butyloxycarbonyl-4-[(3-phenyl-2-propynyloxy)ethyl]piperidine

HRID 1655966

反応式

HRID 1655966 の反応式
[H-].[Na+].[C:3]([O:7][C:8]([N:10]1[CH2:15][CH2:14][CH:13]([CH2:16][CH2:17][OH:18])[CH2:12][CH2:11]1)=[O:9])([CH3:6])([CH3:5])[CH3:4].[CH:19]1[CH:24]=[CH:23][C:22]([C:25]#[C:26][CH2:27]Cl)=[CH:21][CH:20]=1>CN(C)C=O>[C:3]([O:7][C:8]([N:10]1[CH2:15][CH2:14][CH:13]([CH2:16][CH2:17][O:18][CH2:27][C:26]#[C:25][C:22]2[CH:23]=[CH:24][CH:19]=[CH:20][CH:21]=2)[CH2:12][CH2:11]1)=[O:9])([CH3:6])([CH3:5])[CH3:4]

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 287343(3-Chloroprop-1-yn-1-yl)benzeneHCID 8541401-(tert-Butoxycarbonyl)-4-(2-hydroxyethyl)piperidine

生成物 1

HCID 538709501-t-Butyloxycarbonyl-4-[(3-phenyl-2-propynyloxy)ethyl]piperidine収率 16%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒2 回

反応条件

温度
0 °C

実験手順

Sodium hydride (0.912 g, 23 mmol, 60% oil disp.) which had been rinsed with hexanes (3×10 mL), and dry N,N-dimethylformamide (50 mL) were cooled to 0° C. with stirring under a nitrogen atmosphere. A solution of 1-t-butyloxycarbonyl-4-hydroxyethylpiperidine (4.3 g, 19 mmol) in dry DMF (15 mL) was added, and the mixture stirred for 1 hour. 3-Phenylpropargyl chloride (2.8 g, 19 mmol) was added, and the mixture was heated to reflux for 24 hours. After cooling, the solvent was removed by distillation under reduced pressure. The residue was dissolved in ethyl acetate and extracted with water (3×100 mL), brine (100 mL), dried (MgSO4), filtered, and concentrated under reduced pressure. The crude product was purified by chromatography on silica gel, eluting with 5% ethyl acetate in hexanes, and concentrated under reduced pressure to yield 1-t-butyloxycarbonyl-4-[(3-phenyl-2-propynyloxy)ethyl]piperidine (1.02 g, 16%) as a dark oil. 1H NMR (300 MHz, CDCl3 /TMS, δ): 7.5(m,2H), 7.3(m,3H), 4.4(s,2H), 4.1(m,2H), 3.6(t,2H), 2.7(br t,2H), 1.8-1.1(m,16H). MSCI: 344 (MH+, base).

後処理

  1. stirringthe mixture stirred for 1 hour
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 24 hours
  4. temperatureAfter cooling
  5. customthe solvent was removed by distillation under reduced pressure
  6. dissolutionThe residue was dissolved in ethyl acetate
  7. extractionextracted with water (3×100 mL), brine (100 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe crude product was purified by chromatography on silica gel
  12. washeluting with 5% ethyl acetate in hexanes
  13. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-450e5204bc9f4f7187bea0a53bbe1c6d
出典データセット
uspto-grants-1993_10
特許番号
US05252586

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