反応 #2286300

ord-36cfd63f35184d3bb2ebbe46f72f409a

反応方程式

CC(=O)[O-].[Na+]
sodium acetate
CC(C)c1cc(Oc2c(Cl)cc(NC(=O)C(=O)O)cc2Cl)nnc1Cl
N-[3,5-dichloro-4-(6-chloro-5-isopropyl-pyridazin-3-yloxy)-phenyl]-oxalamic acid
CC(C)c1cc(Oc2c(Cl)cc(NC(=O)C(=O)O)cc2Cl)nnc1Cl
N-[3,5-Dichloro-4-(6-chloro-5-isopropyl-pyridazin-3-yloxy)-phenyl]-oxalamic acid
CC(C)c1cc(Oc2c(Cl)cc(NC(=O)C(=O)O)cc2Cl)n[nH]c1=O
N-[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-yloxy)-phenyl]-oxalamic acid
収率 56.1%
CC(C)c1cc(Oc2c(Cl)cc(NC(=O)C(=O)O)cc2Cl)n[nH]c1=O
N-[3,5-Dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-yloxy)-phenyl]-oxalamic acid
収率 56.1%

反応条件

温度
100°CELSIUS
詳細条件
See reaction.notes.procedure_details.

後処理

  1. 1
    温度The reaction mixture was cooled to room temperature
  2. 2
    濃縮was concentrated under vacuum
  3. 3
    workup.ADDITIONThe resulting solid was diluted with water (50 mL)
  4. 4
    workup.ADDITIONThe mixture was made acidic to pH=3 by the addition of glacial acetic acid
  5. 5
    ろ過The solids were filtered
  6. 6
    洗浄rinsed well with water
  7. 7
    その他dried on the funnel
  8. 8
    温度methyl tert-butyl ether: hexanes (3 mL) and then was heated to reflux
  9. 9
    温度The mixture was cooled
  10. 10
    ろ過filtered
  11. 11
    ろ過filtered
  12. 12
    その他The resulting pure solid was dried under high vacuum for 24 h
  13. 13
    その他dried in a vacuum oven at 80° C. for 24 h

実験手順

A mixture of glacial acetic acid (55 mL), sodium acetate (1.2 g, 14.7 mmol) and N-[3,5-dichloro-4-(6-chloro-5-isopropyl-pyridazin-3-yloxy)-phenyl]-oxalamic acid (28) (1.7 g, 4.2 mmol) was heated to 100° C. for 24 h. The reaction mixture was cooled to room temperature and was concentrated under vacuum. The resulting solid was diluted with water (50 mL). The mixture was made acidic to pH=3 by the addition of glacial acetic acid. The solids were filtered and rinsed well with water and dried on the funnel. The solid was slurried in 1:1:2 isopropyl acetate: methyl tert-butyl ether: hexanes (3 mL) and then was heated to reflux. The mixture was cooled and filtered. A slight amount of impurity was detected by TLC. The solid was slurried in isopropyl acetate (10 mL) and filtered. The resulting pure solid was dried under high vacuum for 24 h and then dried in a vacuum oven at 80° C. for 24 h to afford N-[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-yloxy)-phenyl]-oxalamic acid (29) (0.91 g, 56%) as a white solid; EI(+)-HRMS m/z calcd for C15H13Cl2N3O5 (M+H) 386.0305, found 386.0308. Molecular Weight=386.1940; Exact Mass=385.0232

出典

DOI: 10.6084/m9.figshare.5104873.v1特許: USRE046024E1uspto-grants-2016_06