Triethylamine → HCID 68468881、化合物

HRID 218069ノート

反応式

HRID 218069 の反応式
[O:1]=[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.N1CCCC1.C(N(CC)CC)C.Br[CH2:28][CH:29]([CH2:34]Br)[C:30]([O:32][CH3:33])=[O:31]>C1C=CC=CC=1.O>[C:11]([O:10][C:8]([N:5]1[CH2:4][CH:3]2[C:2](=[O:1])[CH:7]([CH2:28][CH:29]([C:30]([O:32][CH3:33])=[O:31])[CH2:34]2)[CH2:6]1)=[O:9])([CH3:14])([CH3:13])[CH3:12]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 31268PyrrolidineHCID 140895Methyl 3-bromo-2-(bromomethyl)propanoateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

生成物 1

HCID 68468881HCID 68468881、化合物収率 69.8%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 962Water溶媒

実験手順

To a solution of tert-butyl 4-oxopiperidine-1-carboxylate (15.2 g, 76.3 mmol) in benzene (200 mL) was added pyrrolidine (13.9 g, 195 mmol). The resulting solution was refluxed with a Dean-Stark trap for 16 h. After removing the solvent by rotary evaporation, the residue was dried on high vacuum and re-dissolved in anhydrous acetonitrile (200 mL). This solution was combined with triethylamine (17.3 g, 170 mmol) and maintained at reflux as methyl 3-bromo-2-(bromomethyl)propanoate (20 g, 77 mmol) was added drop-wise. The reaction was further refluxed for 4 h, cooled to ambient temperature, diluted with water (200 mL) and stirred at ambient temperature for 16 h. The volatile solvents were removed by rotary evaporation, and the residue was partitioned between chloroform and water (200 mL each). The aqueous layer was extracted with chloroform (2×100 mL). The combined organic extracts were dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The residue was purified by flash chromatography, using an ethyl acetate in hexane gradient, to give 15.8 g (69.8% yield) of methyl 3-(tert-butoxycarbonyl)-9-oxo-3-azabicyclo[3.3.1]nonane-7-carboxylate, as a colorless syrup (1H NMR (CDCl3): δ 4.43-4.2 (m, 2H), 3.7 (s, 3H), 3.12-3.0 (m, 2H), 2.55-2.43 (m, 2H), 2.41-2.35 (m, 4H), 1.52 (s, 9H); LC-MS (MH+): 298).

後処理

  1. temperatureThe resulting solution was refluxed with a Dean-Stark trap for 16 h
  2. customAfter removing the solvent
  3. customby rotary evaporation
  4. customthe residue was dried on high vacuum
  5. dissolutionre-dissolved in anhydrous acetonitrile (200 mL)
  6. temperaturemaintained
  7. additionwas added drop-wise
  8. temperatureThe reaction was further refluxed for 4 h
  9. customThe volatile solvents were removed by rotary evaporation
  10. customthe residue was partitioned between chloroform and water (200 mL each)
  11. extractionThe aqueous layer was extracted with chloroform (2×100 mL)
  12. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  13. concentrationconcentrated by rotary evaporation
  14. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-51854ed72a4c43588e46a327db0dddc1
出典データセット
uspto-grants-2012_06
特許番号
US08198296B2

反応ノート

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