Реакция #2286344

Уравнение реакции

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

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

sodium acetate

→

2-[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]-3,5-dioxo-2,3,4,5-tetrahydro-[1,2,4]triazine-6-carbonitrile

Выход 103.2%

2-[3,5-Dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]-3,5-dioxo-2,3,4,5-tetrahydro-[1,2,4]triazine-6-carbonitrile

Выход 103.2%

Растворители

methylene chloride

acetic acid

Условия реакции

Обработка

1. 1
   Другоеconsumption of the starting material and conversion to product
2. 2
   ТемператураThe reaction was cooled to 25° C.
3. 3
   workup.ADDITIONpoured onto water (200 mL)
4. 4
   Экстракцияwas extracted with ethyl acetate (2×150 mL)
5. 5
   ПромывкаThe organics were washed with a saturated aqueous sodium chloride solution (1×150 mL)
6. 6
   Сушкаdried with magnesium sulfate
7. 7
   Фильтрацияfiltered
8. 8
   Концентрированиеconcentrated under vacuum
9. 9
   Другоеto give an orange solid
10. 10
    Концентрированиеhexanes mixture and concentrated in vacuo three times
11. 11
    workup.DISSOLUTIONIt was then dissolved in a 1:1 methylene chloride
12. 12
    Концентрированиеmethanol mixture and concentrated under vacuum

Методика

A solution of (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, 5.99 mmol) in glacial acetic acid (60 mL) was treated with sodium acetate (2.46 g, 29.95 mmol). The resulting mixture was heated to 120° C. for 3 h. At this time, LCMS indicated complete consumption of the starting material and conversion to product. The reaction was cooled to 25° C., poured onto water (200 mL) and was extracted with ethyl acetate (2×150 mL). The organics were washed with a saturated aqueous sodium chloride solution (1×150 mL), dried with magnesium sulfate, filtered and concentrated under vacuum to give an orange solid. This solid was dissolved in a 1:1 methylene chloride:hexanes mixture and concentrated in vacuo three times. It was then dissolved in a 1:1 methylene chloride: methanol mixture and concentrated under vacuum to afford 2-[3,5-dichloro-4-(5-isopropyl-6-oxo-1,6-dihydro-pyridazin-3-ylsulfanyl)-phenyl]-3,5-dioxo-2,3,4,5-tetrahydro-[1,2,4]triazine-6-carbonitrile (87) (2.79 g) as an orange solid. The material was used without further purification; ES(+)-HRMS m/e calcd for C17H12Cl2N6O3S (M+H)+ 451.0142, found 451.0143. Exact Mass=450.0069; Molecular weight=451.29

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