반응 #792174

ord-6e206051077f4a788d0f3e7729061cd6

반응 방정식

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
수율 15.7%
CCOC(=O)c1cc(=O)[nH]n1-c1ncccc1Cl
Ethyl 1-(3-chloro-2-pyridinyl)-2,3-dihydro-3-oxo-1H-pyrazole-5-carboxylate
수율 15.7%

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타The reaction mixture thinned to form a pale green, nearly clear solution
  2. 2
    기타to form a pale yellow suspension
  3. 3
    온도the reaction mixture was heated
  4. 4
    온도at gentle reflux for 3.5 hours
  5. 5
    온도After cooling
  6. 6
    기타a precipitate of white solid was removed by filtration
  7. 7
    workup.ADDITIONThe filtrate was diluted with water (400 mL)
  8. 8
    추출extracted three times with ethyl ether (700 mL total)
  9. 9
    기타precipitation of an off-white solid (3.75 g), which
  10. 10
    여과was collected by filtration
  11. 11
    농축The ether mother liquor was further concentrated

실험 절차

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.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US09173400B2uspto-grants-2015_11