反应 #2286343

反应方程式

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

收率 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

收率 58.0%

溶剂

water

water

water

hydrochloric acid

water

反应条件

后处理

1. 1
   洗涤rinse (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
   其他The solids were removed by filtration
5. 5
   过滤through filter paper
6. 6
   洗涤were rinsed with water
7. 7
   温度cooled to 0° C
8. 8
   workup.ADDITIONUpon mixing
9. 9
   其他orange-red solids immediately formed
10. 10
    workup.STIRRINGThis mixture was stirred at 0° C. for 1 h
11. 11
    过滤At this time, the solids were collected by filtration
12. 12
    过滤through filter paper
13. 13
    洗涤The solids were washed with water
14. 14
    其他air-dried under house vacuum for 2 h
15. 15
    其他dried under vacuum

实验过程

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

来源