Sodium Cyanide → Ethyl 6-cyano-4-hydroxycinnolin-3-yl carboxylate

HRID 442338Notes

Reaction equation

HRID 442338 reaction equation
N[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[N:7][C:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:5]2[OH:17].N([O-])=O.[Na+].[C-:22]#[N:23].[Na+]>O.Cl>[C:22]([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[N:7][C:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:5]2[OH:17])#[N:23]

Participants

6

Reactant 3

HCID 8929Sodium CyanideHCID 23668193Sodium NitriteHCID 178470447HCID 178470447, compound

Product 1

HCID 178470443Ethyl 6-cyano-4-hydroxycinnolin-3-yl carboxylate

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent3×

Conditions

Temperature
0 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-f6cb46640c2a4da89c6b435ac2fdf341
Source dataset
uspto-grants-1977_08
Patent number
US04045439

Reaction notes

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