反应详情

温度

0 °C

A suspension of ethyl 6-amino-4-hydroxycinnolin-3-yl carboxylate (1.164 g.) in water (10 ml.) and concentrated hydrochloric acid (1.0 ml.) was stirred at 0° C. in an ice-salt bath, and a solution of sodium nitrite (0.5 g.) in water (3 ml.) was added during 5 minutes, maintaining the temperature at 0°-5° C. The mixture was stirred at 0° C. for 10 minutes, and this mixture was then added dropwise to a stirred solution of cuprous cyanide (0.54 g.) and sodium cyanide (0.6 g.) in water (4 ml.), heated at 60°-70° C. on a steam bath. The mixture was heated under reflux for 30 minutes. The brown solid which was precipitated was filtered off, washed thoroughly with water and dried as much as possible on the filter. The crude product was extracted with boiling ethanol (2 × 100 ml.), and the combined extracts were filtered and the filtrate evaporated under reduced pressure. The residue was applied to a column of silica (30 g., Kieselgel 60). Elution with a mixture containing 15% v/v of ethanol and 85% v/v of chloroform yielded ethyl 6-cyano-4-hydroxycinnolin-3-yl carboxylate, m.p. 259°-261° C.

1. temperaturemaintaining the temperature at 0°-5° C
2. stirringThe mixture was stirred at 0° C. for 10 minutes
3. temperatureheated at 60°-70° C. on a steam bath
4. temperatureThe mixture was heated
5. temperatureunder reflux for 30 minutes
6. customThe brown solid which was precipitated
7. filtrationwas filtered off
8. washwashed thoroughly with water
9. customdried as much as possible on the filter
10. extractionThe crude product was extracted with boiling ethanol (2 × 100 ml.)
11. filtrationthe combined extracts were filtered
12. customthe filtrate evaporated under reduced pressure
13. washElution with a mixture
14. additioncontaining 15% v/v of ethanol and 85% v/v of chloroform