Hydrochloric Acid → HCID 66665502, compound

HRID 522432Notes

Reaction equation

HRID 522432 reaction equation
Cl.Cl.[CH3:3][C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[N:7]=[C:6]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[NH2:20])[CH:5]=1.N([O-])=O.[Na+].[N-]=[N+]=[N-].[Na+].C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.O>[CH3:3][C:4]1[C:13]2[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=2[N:7]2[N:20]=[C:15]3[C:14]([CH:19]=[CH:18][CH:17]=[CH:16]3)=[C:6]2[CH:5]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 33557Sodium AzideHCID 16242249HCID 16242249, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 66665502HCID 66665502, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

9 ml of conc. hydrochloric acid are added to a suspension, cooled to 0° C., of 90.5 g (332 mmol) of 2-(4-methylquinolin-2-yl)phenylamine hydrochloride in 1300 ml of ice-water and 1000 ml of toluene in an open 10 l beaker, and a solution of 24.1 g (352 mmol) of sodium nitrite in 100 ml of water is then added dropwise, during which the temperature is kept below +5° C. When the addition is complete, the mixture is stirred for a further 20 min., a solution of 24.9 g (382 mmol) of sodium azide in 500 ml of ice-water is then allowed to run in slowly with vigorous stirring (note: evolution of gas, foaming!), and the mixture is then stirred further until the evolution of gas is complete. After warming to room temperature, the reaction mixture is rendered slightly alkaline using saturated sodium carbonate solution, the organic phase is separated off, washed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution, dried over a mixture of sodium carbonate and magnesium sulfate, the desiccant is filtered off, and the filtrate is slowly heated to reflux under argon (care: evolution of gas from about 80° C.). After 8 h under reflux, the mixture is allowed to cool, filtered through 800 g of alumina (basic, activity grade 1), rinsed with 2000 ml of toluene, and the filtrate is then evaporated to dryness in vacuo. The yellow oil obtained in this way is recrystallised twice from about 300 ml of ethanol. The solid obtained in this way is freed from readily volatile and non-volatile secondary components by fractional sublimation (p about 1×10−5 mbar, T about 180° C.). Yield: 48.8 g (210 mmol), 63%, purity: about 99.5% (NMR).

Workup

  1. customis kept below +5° C
  2. additionWhen the addition
  3. stirringwith vigorous stirring (note: evolution of gas, foaming!)
  4. stirringthe mixture is then stirred further until the evolution of gas
  5. customthe organic phase is separated off
  6. washwashed once with 500 ml of water and once with 500 ml of saturated sodium chloride solution
  7. dry with materialdried over a mixture of sodium carbonate and magnesium sulfate
  8. filtrationthe desiccant is filtered off
  9. temperaturethe filtrate is slowly heated
  10. temperatureto reflux under argon (care: evolution of gas from about 80° C.)
  11. temperatureAfter 8 h under reflux
  12. temperatureto cool
  13. filtrationfiltered through 800 g of alumina (basic, activity grade 1)
  14. washrinsed with 2000 ml of toluene
  15. customthe filtrate is then evaporated to dryness in vacuo
  16. customThe yellow oil obtained in this way
  17. customis recrystallised twice from about 300 ml of ethanol
  18. customThe solid obtained in this way
  19. customby fractional sublimation (p about 1×10−5 mbar, T about 180° C.)

Sources & evidence

ORD record
ord-aaf1ab62499c4ad48ce0ea1c927f198e
Source dataset
uspto-grants-2016_05
Patent number
US09331290B2

Reaction notes

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