Hydrochloric Acid → 5-Hydrazinoquinoline dihydrochloride

HRID 353448Notes

Reaction equation

HRID 353448 reaction equation
[ClH:1].[NH2:2][C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][CH:7]=[N:8]2.[N:13]([O-])=O.[Na+].O=C1O[C@H]([C@H](CO)O)C(O)=C1O.C(O)(=O)C(O)=O>O>[ClH:1].[ClH:1].[NH:2]([C:3]1[CH:12]=[CH:11][CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][CH:7]=[N:8]2)[NH2:13]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 971Oxalic AcidHCID 119115-AminoquinolineHCID 23668193Sodium NitriteHCID 54670067L-Ascorbic Acid

Product 1

HCID 123341075-Hydrazinoquinoline dihydrochlorideYield 66.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
-1 °C

Procedure

To a 1 L flask under a nitrogen atmosphere, concentrated HCl (300 ml, 32%, 3.05 moles) was charged and cooled to −2 to 0° C. 5-Aminoquinoline (50 g, 0.347 moles) was then added all at once as a solid. An increase in temperature of 25° C. was observed. The suspension was again cooled to −2 to 0° C. Aqueous sodium nitrite (29 g, 0.420 moles) dissolved in water (50 ml) was added dropwise to the acidic solution through an addition funnel over a period of 1 hour at −2 to 0° C. The resulting mixture (dark-brown solution) was stirred for 1 hour at −2 to 0° C. L-Ascorbic acid (64 g, 0.363 moles) was then added in portions as a solid over a period of 1 hour at (−)2-0° C. The reaction was allowed to come to room temperature (18-20° C.) over a period of 45 minutes, then heated at 80° C. and stirred 20 minutes at this temperature. The resultant orange suspension was cooled to room temperature (18-20° C.) and water (100 ml) was added. The slurry was stirred overnight (16-17 hours) at 18-20° C., cooled to 0° C. for 1.5 hours, filtered and washed with methanol (150 ml). The product was dried to constant weight in an air tray drier at 40° C. to afford 53.8 g of 5-hydrazinoquinoline dihydrochloride as a green-brown solid (HPLC purity calculated as area percent: 98.6%, with 1.3% of oxalic acid intermediate; 66% molar yield).

Workup

  1. temperatureAn increase in temperature of 25° C.
  2. temperatureThe suspension was again cooled to −2 to 0° C
  3. additionwas added dropwise to the acidic solution through an addition funnel over a period of 1 hour at −2 to 0° C
  4. customto come to room temperature
  5. custom(18-20° C.)
  6. customof 45 minutes
  7. temperatureheated at 80° C.
  8. stirringstirred 20 minutes at this temperature
  9. additionwas added
  10. stirringThe slurry was stirred overnight (16-17 hours) at 18-20° C.
  11. temperaturecooled to 0° C. for 1.5 hours
  12. filtrationfiltered
  13. washwashed with methanol (150 ml)
  14. customThe product was dried to constant weight in an air tray drier at 40° C.
  15. customto afford

Sources & evidence

ORD record
ord-6ff1b6a72609442a81a1932b68515134
Source dataset
uspto-grants-2004_06
Patent number
US06753334B2

Reaction notes

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