甲酸 → 3-溴-5-(1-甲基-吡咯烷-2-基)-吡啶

HRID 1489410

反应方程式

HRID 1489410 反应方程式
[Br:1][C:2]1[CH:3]=[C:4]([CH:8]2[CH2:12][CH2:11][CH2:10][NH:9]2)[CH:5]=[N:6][CH:7]=1.[CH:13](O)=O>C=O>[Br:1][C:2]1[CH:3]=[C:4]([CH:8]2[CH2:12][CH2:11][CH2:10][N:9]2[CH3:13])[CH:5]=[N:6][CH:7]=1

参与物

4

反应物 2

HCID 284甲酸HCID 44038153-溴-5-(吡咯烷-2-基)吡啶

产物 1

HCID 110320273-溴-5-(1-甲基-吡咯烷-2-基)-吡啶

试剂、催化剂与溶剂 1

HCID 712多聚甲醛溶剂

反应条件

温度
80 °C

实验过程

Enantiomerically enriched 5-bromo-3-(2-pyrrolidinyl)pyridine (1.82 g, 8 mmol) was dissolved in a mixture of 98% formic acid (16 mL) and 37% aqueous formaldehyde (8 mL). The solution was heated with stirring for 3 h at 80° C. After cooling to 25° C. the mixture was concentrated in vacuo and water (30 mL) added. The mixture was basified with solid NaOH to pH 12 and extracted with methylene chloride (3×40 mL). The combined organic extracts were washed with brine (20 mL), dried (MgSO4) and concentrated in vacuo. The crude material was chromatographed on silica gel with ethyl acetate:hexane (1:3) as eluant to afford 5-bromo-3-(1-methyl-2-pyrrolidinyl)pyridine as an oil, 1.63 g,84%. LRMS (EI) m/e 242 (C10H13N281Br), 241 (C10 H13N279Br--+H), 240 (C10H13 N279Br), 239 (C10H13N279Br--+H); 1H NMR (DMSO-d6, 300 MHz) δ 8.55 (d, J=2.1 Hz, 1H), 8.44 (d, J=1.9 Hz, 1H), 7.88 (t, J=1.9 Hz, 1H), 3.24 (b-dt, J=8.1 Hz, 1H), 3.10 (t, J=8.0 Hz, 1H), 2.36 (m, 1H), 2.18 (s, 3H), 1.95 (m, 1H), 1.85 (m, 1H), 1.70 (m, 1H).

后处理

  1. temperatureThe solution was heated
  2. temperatureAfter cooling to 25° C. the mixture
  3. concentrationwas concentrated in vacuo and water (30 mL)
  4. additionadded
  5. extractionextracted with methylene chloride (3×40 mL)
  6. washThe combined organic extracts were washed with brine (20 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe crude material was chromatographed on silica gel with ethyl acetate:hexane (1:3) as eluant

来源与证据

ORD记录
ord-a2b26e29729f4281a22734f1fca92c45
来源数据集
uspto-grants-1997_10
专利号
US05677459

关联笔记

加载中…