六水硝酸铽 → 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine

HRID 57092

反应方程式

HRID 57092 反应方程式
[Cl:1][C:2]1[CH:6]=[CH:5][N:4]([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)[N:3]=1.S(=O)(=O)(O)O.[N+:18]([O-])([OH:20])=[O:19].S(=O)(=O)(O)O.[N+]([O-])(O)=O.[OH-].[Na+]>O>[Cl:1][C:2]1[C:6]([N+:18]([O-:20])=[O:19])=[CH:5][N:4]([C:7]2[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=2)[N:3]=1

参与物

7

反应物 5

HCID 944六水硝酸铽HCID 1118四氧化硫2 次HCID 14798二甲基对苯二胺二盐酸HCID 674995403-(3-chloro-1H-pyrazol-1-yl)pyridineHCID 71777668硝化酸混合物

产物 1

HCID 675001483-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine

试剂、催化剂与溶剂 1

HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂

反应条件

温度
5 °C

实验过程

To a 100 mL round bottom flask was charged 3-(3-chloro-1H-pyrazol-1-yl)pyridine (2.0 g, 11 mmol) and concentrated sulfuric acid (4 mL). This suspension was cooled to ˜5° C. and 2:1 (v/v) concentrated nitric acid/sulfuric acid (3 mL, prepared by adding the concentrated sulfuric acid to a stirring and cooling solution of the nitric acid) was added dropwise at a rate such that the internal temperature was maintained <15° C. The reaction was allowed to warm to 20° C. and stirred for 18 hours. A sample of the reaction mixture was carefully diluted into water, basified with 50% sodium hydroxide (NaOH) and extracted with ethyl acetate. Analysis of the organic layer indicated that the reaction was complete. The reaction mixture was carefully added to ice cold water (100 mL) at <20° C. and basified with 50% sodium hydroxide at <20° C. The resulting light yellow suspension was stirred for 2 hours and filtered. The filter cake was rinsed with water (3×20 mL) and dried to afford an off-white solid (2.5 g, quantitative): mp 141-143° C.; 1H NMR (400 MHz, DMSO-d6) δ 9.86 (s, 1H), 9.23-9.06 (m, 1H), 8.75-8.60 (m, 1H), 8.33 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.64 (ddd, J=8.5, 4.7, 0.7 Hz, 1H); 13C NMR (101 MHz, DMSO-d6) δ 149.49, 140.75, 136.02, 134.43, 132.14, 131.76, 127.22, 124.31; EIMS m/z 224 ([M]+).

后处理

  1. additionwas added dropwise at a rate such that the internal temperature
  2. temperaturewas maintained <15° C
  3. temperatureto warm to 20° C.
  4. extractionextracted with ethyl acetate
  5. additionThe reaction mixture was carefully added to ice cold water (100 mL) at <20° C. and basified with 50% sodium hydroxide at <20° C
  6. stirringThe resulting light yellow suspension was stirred for 2 hours
  7. filtrationfiltered
  8. washThe filter cake was rinsed with water (3×20 mL)
  9. customdried
  10. customto afford an off-white solid (2.5 g, quantitative)

来源与证据

ORD记录
ord-fa9aa42b2639486b80cb3ef2c3a79e0b
来源数据集
uspto-grants-2016_09
专利号
US09434712B2

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