Reaktion #63693

Reaktionsgleichung

2,4-dichlorophenylhydrazine hydrochloride

pyruvic acid

thionyl chloride

Urethane

hydrochloric acid

→

2-(2,4-dichlorophenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione

Ausbeute 36.8%

Lösungsmittel

water

ethanol

water

toluene

ethanol

sodium hydroxide

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONUpon complete addition
2. 2
   Sonstigea precipitate formed
3. 3
   Filtrationwas collected by filtration
4. 4
   Sonstigedried under reduced pressure at ambient temperature
5. 5
   workup.ADDITIONwas added
6. 6
   Temperaturheated
7. 7
   Temperaturat reflux for 0.5 hour
8. 8
   workup.DISTILLATIONDistillation of the solvent under reduced pressure
9. 9
   workup.WAITleft a solid residue, which
10. 10
    workup.DISSOLUTIONwas dissolved in 100 mL of toluene
11. 11
    Temperaturat reflux
12. 12
    SonstigeThe solvent was removed from the mixture by distillation under reduced pressure
13. 13
    Sonstigeto leave a residue
14. 14
    Wascheneluting with ethyl acetate:heptane (1:1)
15. 15
    Sonstigethe solvent removed by evaporation
16. 16
    Sonstigeto leave a gummy residue
17. 17
    SonstigeA solid formed which
18. 18
    Filtrationwas collected by filtration
19. 19
    Sonstigedried under reduced pressure
20. 20
    SonstigeRecrystallization from tetrahydrofuran

Vorschrift

To a stirred solution of 4.32 g (0.020 mole) of 2,4-dichlorophenylhydrazine hydrochloride in 100 mL of water and 50 mL of ethanol was added dropwise 2.14 g (0.024 mole) of pyruvic acid in 50 mL of water. Upon complete addition, a precipitate formed and was collected by filtration and dried under reduced pressure at ambient temperature. The solid hydrazone product was dissolved in 100 mL of toluene to which 4.8 g (0.041 mole) of thionyl chloride was added. The resultant mixture was stirred and heated at reflux for 0.5 hour. Distillation of the solvent under reduced pressure left a solid residue, which was dissolved in 100 mL of toluene. Urethane (2.2 g, 0.024 mole) was added, and the resultant solution heated at reflux with stirring for two hours. The solvent was removed from the mixture by distillation under reduced pressure to leave a residue. This residue was subjected to column chromatography on silica gel, eluting with ethyl acetate:heptane (1:1). Appropriate fractions were combined, and the solvent removed by evaporation to leave a gummy residue. The residue was dissolved in 75 mL of ethanol and 75 mL of 1N sodium hydroxide. The resultant solution was heated to 60° C., then poured into a mixture of 3N hydrochloric acid and ice. A solid formed which was collected by filtration and dried under reduced pressure. Recrystallization from tetrahydrofuran:heptane provided 2.0 g of 2-(2,4-dichlorophenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione (mp 197° C. dec), Compound 4 in the tables.

Quelle