반응 #2286343

반응 방정식

sodium nitrite

6-(4-amino-2,6-dichloro-phenylsulfanyl)-4-isopropyl-2H-pyridazin-3-one

6-(4-Amino-2,6-dichloro-phenylsulfanyl)-4-isopropyl-2H-pyridazin-3-one

cyanoacetylurethane

pyridine

→

(2-cyano-2-{[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]hydrazono}-acetyl)-carbamic acid ethyl ester

수율 58.0%

(2-Cyano-2-{[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]-hydrazono}-acetyl)-carbamic acid ethyl ester

수율 58.0%

용매

water

water

water

hydrochloric acid

water

반응 조건

후처리

1. 1
   세척rinse (1.0 mL) of the Pasteur pipette
2. 2
   workup.ADDITIONMore concentrated hydrochloric acid (7.0 mL) was added
3. 3
   workup.STIRRINGThe reaction was stirred at 0° C. for an additional 1.3 h
4. 4
   기타The solids were removed by filtration
5. 5
   여과through filter paper
6. 6
   세척were rinsed with water
7. 7
   온도cooled to 0° C
8. 8
   workup.ADDITIONUpon mixing
9. 9
   기타orange-red solids immediately formed
10. 10
    workup.STIRRINGThis mixture was stirred at 0° C. for 1 h
11. 11
    여과At this time, the solids were collected by filtration
12. 12
    여과through filter paper
13. 13
    세척The solids were washed with water
14. 14
    기타air-dried under house vacuum for 2 h
15. 15
    기타dried under vacuum

실험 절차

A mixture of 6-(4-amino-2,6-dichloro-phenylsulfanyl)-4-isopropyl-2H-pyridazin-3-one (85) (3.40 g, 10.4 mmol) in water (135 mL) and concentrated hydrochloric acid (68 mL) cooled to 0° C. was treated with a solution of sodium nitrite (853 mg, 12.36 mmol) in water (7.0 mL) via Pasteur pipette under the surface of the reaction mixture. This was followed by a water rinse (1.0 mL) of the Pasteur pipette. The resulting yellow mixture was stirred at 0° C. for 30 min. More concentrated hydrochloric acid (7.0 mL) was added. The reaction was stirred at 0° C. for an additional 1.3 h. The solids were removed by filtration through filter paper and were rinsed with water. The clear, yellow diazonium salt solution of the filtrate was quickly poured into a solution of cyanoacetylurethane (1.77 g, 11.33 mmol), pyridine (75 mL) and water (204 mL) cooled to 0° C. Upon mixing, orange-red solids immediately formed. This mixture was stirred at 0° C. for 1 h. At this time, the solids were collected by filtration through filter paper. The solids were washed with water, air-dried under house vacuum for 2 h, and then dried under vacuum to afford (2-cyano-2-{[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]hydrazono}-acetyl)-carbamic acid ethyl ester (86) (2.98 g, 58%) as an orange solid; ES(+)-HRMS m/e calcd for C19H18Cl2N6O4S (M+H)+ 497.0560, found 497.0559. Exact Mass=496.0487; Molecular weight=497.36

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