Carbamic acid, ethyl-, ethyl ester → 1-(4-Bromo-2-ethoxybenzyl)-piperidine

HRID 1505896ノート

反応式

HRID 1505896 の反応式
[H-].[Na+].[Br:3][C:4]1[CH:16]=[CH:15][C:7]([CH2:8][N:9]2[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]2)=[C:6](F)[CH:5]=1.C(NC([O:23][CH2:24][CH3:25])=O)C>O1CCOCC1.O>[Br:3][C:4]1[CH:16]=[CH:15][C:7]([CH2:8][N:9]2[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10]2)=[C:6]([O:23][CH2:24][CH3:25])[CH:5]=1

参加物

6

反応物 3

HCID 12195Carbamic acid, ethyl-, ethyl esterHCID 24758Sodium hydrideHCID 534861121-(4-Bromo-2-fluorobenzyl)piperidine

生成物 1

HCID 582664591-(4-Bromo-2-ethoxybenzyl)-piperidine収率 74%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
140 °C

実験手順

Sodium hydride (306 mg, 60%, 7.6 mmol) was added in portions to a solution of 1-(4-bromo-2-fluorobenzyl)-piperidine (520 mg, 1.9 mmol) and ethyl urethane (0.91 mL, 7.6 mmol) in dioxane (10 mL) under an atmosphere of nitrogen. The reaction mixture was then sonicated for 30 minutes until gas evolution ceased then heated at 140° C. overnight in a sealed tube. The reaction mixture was diluted with water and extracted with DCM (3×30 mL). The combined organic layer was dried over anhydrous sodium sulfate, filtered and evaporated in vacuo to afford a colourless oil that was then purified by flash chromatography (silica, 12 g column, ISCO, 0-10% methanol in DCM) to afford the title compound as a white solid (416 mg, 74%). 1H NMR (CDCl3, 400 MHz): 7.23 (d, J=8.1 Hz, 1H), 7.03 (dd, J=8.1, 1.9 Hz, 1H), 6.95 (d, J=1.9 Hz, 1H), 3.99 (q, J=7.0 Hz, 2H), 3.47 (s, 2H), 2.46-2.35 (m, 4H), 1.61-1.53 (m, 4H), 1.45-1.36 (m, 5H).

後処理

  1. customThe reaction mixture was then sonicated for 30 minutes until gas evolution
  2. extractionextracted with DCM (3×30 mL)
  3. dry with materialThe combined organic layer was dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. customevaporated in vacuo
  6. customto afford a colourless oil that
  7. customwas then purified by flash chromatography (silica, 12 g column, ISCO, 0-10% methanol in DCM)

出典と根拠

ORDレコード
ord-dd09fa19466249cbacb188286af2f7b4
出典データセット
uspto-grants-2015_12
特許番号
US09216980B2

反応ノート

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