Reacción #82452

Ecuación de reacción

Vilsmeier reagent

Phosphorous oxychloride

Dimethylformamide

dimethyl [(1-methylpyrazol-4-yl)amino]butenedicarboxylate

→

product

Rendimiento 71.4%

Dimethyl 1-methylpyrazolo[4,3-b]pyridine-5,6-dicarboxylate

Rendimiento 71.4%

Disolventes

dichloroethane

dichloroethane

Condiciones de reacción

Tratamiento posterior

1. 1
   Temperaturato warm slowly to room temperature
2. 2
   Otrothe reaction temperature below 5° C
3. 3
   Temperaturato warm slowly to room temperature over four hours
4. 4
   Temperaturais heated
5. 5
   Temperaturato reflux for one hour
6. 6
   ConcentraciónThe mixture is concentrated to a solid which
7. 7
   Otrois chromatographed
8. 8
   workup.ADDITIONThe fractions containing the desired product
9. 9
   Concentraciónconcentrated

Procedimiento

Dimethylformamide (7.4 mL, 0.096 mol) is dissolved in 125 mL dichloroethane and the mixture cooled to -5° C. in an acetone/ice bath. Phosphorous oxychloride (8.9 mL, 0.095 mol) is added in one portion and the clear colorless solution is allowed to warm slowly to room temperature, gradually turning yellow. The unpurified dimethyl [(1-methylpyrazol-4-yl)amino]butenedicarboxylate is dissolved in 75 mL of dichloroethane and added to the chilled Vilsmeier reagent dropwise keeping the reaction temperature below 5° C. The mixture is allowed to warm slowly to room temperature over four hours, and then is heated to reflux for one hour. The mixture is concentrated to a solid which is chromatographed using 3:1 hexanes/ethyl acetate. The fractions containing the desired product are combined and concentrated to give the product as a white solid (16.93 g, 71.4%), melting point 148°-149° C.

Fuente