HCID 19610455, compound → HCID 67652043, compound

HRID 1857992Notes

Reaction equation

HRID 1857992 reaction equation
[ClH:1].Cl.[N:3]1([C:8]2[CH:14]=[CH:13][C:11]([NH2:12])=[CH:10][CH:9]=2)[CH:7]=[CH:6][N:5]=[CH:4]1.[N:15]([O-])=O.[Na+]>Cl.O>[ClH:1].[ClH:1].[N:3]1([C:8]2[CH:14]=[CH:13][C:11]([NH:12][NH2:15])=[CH:10][CH:9]=2)[CH:7]=[CH:6][N:5]=[CH:4]1

Participants

5

Reactant 2

HCID 19610455HCID 19610455, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 67652043HCID 67652043, compoundYield 119.2%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Conditions

Temperature
-15 °C

Procedure

To a cooled (-15° C.) and stirred suspension of 4-(imidazol-1-yl)aniline, dihydrochloride (20 g, 86.2 mmol) in concentrated hydrochloric acid (100 ml) was added dropwise, over 1 hour, a solution of sodium nitrite (6.25 g, 90.6 mmol) in water (40 ml). After a further 10 minutes of stirring at -12° C., the mixture was quickly filtered to remove a solid, and the filtrate was added portionwise to a cooled (-20° C.) and stirred solution of tin (II) chloride dihydrate (100 g) in concentrated hydrochloric acid (50 ml) at such a rate as to maintain the internal temperature below -10° C. (15 minutes). The mixture was allowed to warm to 5° C. over 30 minutes, and the solid was collected and washed with diethyl ether (4×100 ml). The above solid was suspended in water (200 ml) and basified with 4N sodium hydroxide solution and extracted with ethyl acetate (5×500 ml). The combined organic solutions were dried (Na2SO4) and filtered. The filtrate was vigorously stirred while hydrogen chloride was being bubbled through the solution until a deep red mixture was obtained. Stirring was continued for a further 20 minutes to give a cream solid which was collected by filtration and dried over phosphorus pentoxide-potassium hydroxide under high vacuum to leave 12.7 g (60%) of the title compound; δH (360 MHz, DMSO-d6) 7.20 (2H, d, J=9.0 Hz), 7.73 (2H, d, J=9.0 Hz), 7.91 (1H, t, J=1.5 Hz), 8.23 (1H, t, J=1.7 Hz), 9.71 (1H, t, J=1.3 Hz).

Workup

  1. additionwas added dropwise, over 1 hour
  2. stirringAfter a further 10 minutes of stirring at -12° C.
  3. filtrationthe mixture was quickly filtered
  4. customto remove a solid
  5. additionthe filtrate was added portionwise to
  6. temperaturea cooled (-20° C.)
  7. stirringstirred solution of tin (II) chloride dihydrate (100 g) in concentrated hydrochloric acid (50 ml) at such a rate as
  8. temperatureto maintain the internal temperature below -10° C. (15 minutes)
  9. temperatureto warm to 5° C. over 30 minutes
  10. customthe solid was collected
  11. washwashed with diethyl ether (4×100 ml)
  12. extractionextracted with ethyl acetate (5×500 ml)
  13. dry with materialThe combined organic solutions were dried (Na2SO4)
  14. filtrationfiltered
  15. stirringThe filtrate was vigorously stirred while hydrogen chloride
  16. customwas being bubbled through the solution until a deep red mixture
  17. customwas obtained
  18. stirringStirring
  19. customto give a cream solid which
  20. filtrationwas collected by filtration
  21. dry with materialdried over phosphorus pentoxide-potassium hydroxide under high vacuum

Sources & evidence

ORD record
ord-c7204c484d704c28b00336f19b4276b3
Source dataset
uspto-grants-2000_11
Patent number
US06150391

Reaction notes

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