Sulfuric Acid → 4-Iodophthalonitrile

HRID 1706851Notes

Reaction equation

HRID 1706851 reaction equation
N[C:2]1[CH:3]=[C:4]([C:10]#[N:11])[C:5](=[CH:8][CH:9]=1)[C:6]#[N:7].S(=O)(=O)(O)O.N([O-])=O.[Na+].NC(N)=O.[I-:25].[K+].COC1C=CC(O)=CC=1>O>[I:25][C:2]1[CH:3]=[C:4]([C:10]#[N:11])[C:5](=[CH:8][CH:9]=1)[C:6]#[N:7]

Participants

8

Reactant 6

HCID 1118Sulfuric AcidHCID 1176UreaHCID 4875Potassium IodideHCID 90154-MethoxyphenolHCID 925291,2-Benzenedicarbonitrile, 4-amino-HCID 23668193Sodium Nitrite2×

Product 1

HCID 41200244-IodophthalonitrileYield 72%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

4-Aminophthalonitrile (40 g, 0.28 mol) was slowly added to 80 ml of concentrated sulfuric acid and the mixture was stirred with cooling (below 25° C.) until dissolution was complete. After cooling below 15° C., ice water (175 ml) was slowly added to precipitate the amine bisulfate. A solution of sodium nitrite (20 g, 0.29 mol) in 40 ml of water was then added at such a rate as to maintain the temperature at 0°-10° C. After stirring the solution for an additional 15 minutes, a few crystals of urea were added to decompose any excess sodium nitrite. The homogeneous solution was then poured into a breaker containing potassium iodide (75 g, 0.45 mol) dissolved in 150 ml of water. After the evolution of nitrogen had ceased and a negative test with alkaline p-methoxyphenol indicated that the reaction was complete, the brown precipitate was collected by suction filtration and washed with 10% sodium bisulfite, with saturated sodium bicarbonate and finally with water. Recrystallization from ethanol-water afforded 51 g (72%) of the desired product, m.p. 141°-142° C.

Workup

  1. temperaturewith cooling (below 25° C.)
  2. dissolutionuntil dissolution
  3. temperatureAfter cooling below 15° C.
  4. customto precipitate the amine bisulfate
  5. temperatureto maintain the temperature at 0°-10° C
  6. stirringAfter stirring the solution for an additional 15 minutes
  7. additionThe homogeneous solution was then poured into a breaker
  8. filtrationthe brown precipitate was collected by suction filtration
  9. washwashed with 10% sodium bisulfite, with saturated sodium bicarbonate and finally with water
  10. customRecrystallization from ethanol-water

Sources & evidence

ORD record
ord-486ef788c1f4429f9a9d8fbe5167b50b
Source dataset
uspto-grants-1980_06
Patent number
US04209458

Reaction notes

Loading…