Phosphoric Acid → Ethyl 3-chloro-1-methyl-1H-pyrazole-4-carboxylate

Temperature

0 °C

A solution of 41.4 g (267 mmol) of ethyl 3-amino-1-methylpyrazole-4-carboxylate in a mixture of 150 mL of concentrated hydrochloric acid, 50 mL of 85 percent phosphoric acid, and 100 mL of water was prepared and cooled to about 0° C. A solution of 18.6 g (270 mmol) of sodium nitrite in 50 mL of water was added to this dropwise with cooling and stirring. After a short time the reaction mixture was added dropwise with stirring at ambient temperature to a solution of 46.5 g (484 mmol) of cupric sulfate and 60.0 g (1.03 mol) of sodium chloride in 200 mL of water. When the addition was complete, the mixture was heated to 50° C. with stirring for 1 hr. A solid formed. The mixture was extracted with methylene chloride and the extract was washed with water, dried over magnesium sulfate, and concentrated by evaporation under reduced pressure to obtain an impure solid. This was dried and recrystallized from ethanol to obtain 24.8 g of the title compound as a white solid melting at 76°-77° C.

1. customwas prepared
2. temperaturewith cooling
3. additionAfter a short time the reaction mixture was added dropwise
4. additionWhen the addition
5. temperaturethe mixture was heated to 50° C.
6. stirringwith stirring for 1 hr
7. customA solid formed
8. extractionThe mixture was extracted with methylene chloride
9. washthe extract was washed with water
10. dry with materialdried over magnesium sulfate
11. concentrationconcentrated by evaporation under reduced pressure
12. customto obtain an impure solid
13. customThis was dried
14. customrecrystallized from ethanol

ORD record

ord-4f0f11d539db41da91a979523d4ea08e

Source dataset

uspto-grants-1993_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05201938