Hydrochloric Acid → 4-Methyl-6-phenylpyridazin-3(2H)-one

HRID 1479214노트

반응식

HRID 1479214 반응식
[CH3:1][CH:2]1[CH2:7][C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[N:5][NH:4][C:3]1=[O:14].Cl.[OH-].[Na+]>C(#N)C.[Cu].[Cu]Cl>[CH3:1][C:2]1[C:3](=[O:14])[NH:4][N:5]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:7]=1

참가 물질

7

반응물 3

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 139013904-Methyl-6-phenyl-4,5-dihydropyridazin-3(2H)-one

생성물 1

HCID 833194-Methyl-6-phenylpyridazin-3(2H)-one수율 93.8%

시약·촉매·용매 3

HCID 23978Copper촉매HCID 62652Cuprous chloride촉매HCID 6342Acetonitrile용매

실험 절차

(Csende, F et al. Synthesis, 1995, 1240-1242) 7.0 g (35 mmol) of 13 was dissolved in 30 ml of acetonitrile in a 250 ml single-necked round bottom flask. 11.3 g (84 mmol, 2.4 equiv) of anhydrous copper (H) chloride Was added to the solution and the reaction mixture was heated to reflux for 2 hours. To control the HCl gas that formed during the course of the reaction, a NaOH solution was used to absorb the HCl that escapes from dry tube. The reaction mixture was cooled to ambient temperature, and placed into an ice-water bath. 150 mL of ice-water was added to quench the reaction. The mixture was stirred vigorously for 10 minutes to give a gray precipitate and blue liquid containing copper (I) chloride. The precipitate was then collected by filtration (pH of the filtrate is 0-1) and washed first with 1N HCl (100 mL), then with Milli-Q water (5×100 mL). To remove remaining copper by-products, the filter cake was stirred in 1N HCl (150 mL) for 0.5 h and then filtered. The filter cake was washed with water until the filtrate is at pH 7 (approximately 7 washes). The solid was dried over a medium flit sintered glass funnel in vacuo to give 14 as a light gray powder in 93.8% yield, 1H NMR (DMSO-d6): δ 7.95 (s, 1H), 7.85 (d, J=7.5 Hz; 2H), 7.47 (m, 2H), 7.43 (m, 1H), 2.13 (s, 3H). HPLC (tr/purity): 21.48 min, >97%; ESI m/z (MeOH) 187.36 (MH+).

후처리

  1. temperaturethe reaction mixture was heated
  2. temperatureto reflux for 2 hours
  3. customformed during the course of the reaction
  4. customto absorb the HCl that escapes
  5. customfrom dry tube
  6. customplaced into an ice-water bath
  7. addition150 mL of ice-water was added
  8. customto quench
  9. customthe reaction
  10. customto give a gray precipitate and blue liquid
  11. filtrationThe precipitate was then collected by filtration (pH of the filtrate
  12. washwashed first with 1N HCl (100 mL)
  13. customTo remove
  14. stirringthe filter cake was stirred in 1N HCl (150 mL) for 0.5 h
  15. filtrationfiltered
  16. washThe filter cake was washed with water until the filtrate
  17. customThe solid was dried over a medium flit sintered glass funnel in vacuo

출처 및 근거

ORD 기록
ord-308720f5065c44d3b5d948bc0470052a
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09408845B2

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