反応 #792174

ord-6e206051077f4a788d0f3e7729061cd6

反応方程式

O=S(=O)([O-])OOS(=O)(=O)[O-].[K+].[K+]
Potassium persulfate
CCOC(=O)C1CC(=O)NN1c1ncccc1Cl
ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate
O=S(=O)(O)O
sulfuric acid
CCOC(=O)c1cc(=O)[nH]n1-c1ncccc1Cl
precipitate
収率 15.7%
CCOC(=O)c1cc(=O)[nH]n1-c1ncccc1Cl
Ethyl 1-(3-chloro-2-pyridinyl)-2,3-dihydro-3-oxo-1H-pyrazole-5-carboxylate
収率 15.7%

反応条件

詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    その他The reaction mixture thinned to form a pale green, nearly clear solution
  2. 2
    その他to form a pale yellow suspension
  3. 3
    温度the reaction mixture was heated
  4. 4
    温度at gentle reflux for 3.5 hours
  5. 5
    温度After cooling
  6. 6
    その他a precipitate of white solid was removed by filtration
  7. 7
    workup.ADDITIONThe filtrate was diluted with water (400 mL)
  8. 8
    抽出extracted three times with ethyl ether (700 mL total)
  9. 9
    その他precipitation of an off-white solid (3.75 g), which
  10. 10
    ろ過was collected by filtration
  11. 11
    濃縮The ether mother liquor was further concentrated

実験手順

To a suspension of ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate (i.e. product of Example 12, Step A) (27 g, 100 mmol) stirred in dry acetonitrile (200 mL) was added sulfuric acid (20 g, 200 mmol) in one portion. The reaction mixture thinned to form a pale green, nearly clear solution before thickening again to form a pale yellow suspension. Potassium persulfate (33 g, 120 mmol) was added in one portion, and then the reaction mixture was heated at gentle reflux for 3.5 hours. After cooling using an ice bath, a precipitate of white solid was removed by filtration and discarded. The filtrate was diluted with water (400 mL) and then extracted three times with ethyl ether (700 mL total). Concentration of the combined ether extracts to a reduced volume (75 mL) caused precipitation of an off-white solid (3.75 g), which was collected by filtration. The ether mother liquor was further concentrated to yield a second crop of an off-white precipitate (4.2 g), which was also collected by filtration. An off-white solid also precipitated from the aqueous phase; this solid (4.5 g) was collected by filtration to provide a combined total of 12.45 g of the title compound.

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: US09173400B2uspto-grants-2015_11