Hydrochloric Acid → HCID 21469301, compound

HRID 1938353Notes

Reaction equation

HRID 1938353 reaction equation
N[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[C:7]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[CH:6]=2.[ClH:20].N([O-])=O.[Na+].[C:25]([O:29][CH3:30])(=[O:28])[CH:26]=[CH2:27]>CC(C)=O.O>[CH2:13]([O:12][C:7]1[CH:6]=[C:5]2[C:10]([CH:11]=[C:2]([CH2:27][CH:26]([Cl:20])[C:25]([O:29][CH3:30])=[O:28])[CH:3]=[N:4]2)=[CH:9][CH:8]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7294Methyl AcrylateHCID 21469268HCID 21469268, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 21469301HCID 21469301, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Conditions

Temperature
5 °C

Procedure

The above 3-amino-7-benzyloxyquinoline (2.3 g, 9.2 mmol.) was dissolved in a mixture of acetone and water (25 mL and 6 mL). Under chilling with ice, to the solution was added concentrated hydrochloric acid (2.5 mL). The reaction temperature was set to a temperature of lower than 5° C. The reaction mixture was stirred at 5° C. for 20 minutes after addition of aqueous sodium nitrite solution (833 mg (12 mmol.)/1.6 mL) for 5 minutes. After the stirring was complete, methyl acrylate (6 mL, 67.5 mmol.) was added for 5 minutes. Then, cuprous oxide (120 mg) was gradually added, and the reaction temperature was set to 37° C. Under the condition, the reaction mixture was vigorously stirred. After the completion of reaction was confirmed, acetone was distilled off. To the residue were added ethyl acetate and concentrated aqueous ammonia, so that the aqueous portion reached pH 7. The organic portion was recovered, washed with water, and dried over anhydrous sodium sulfate. The dried mixture was filtered, and the filtrate was placed under reduced pressure to distill off ethyl acetate. The residue was purified by column chromatography (hexane/ethyl acetate=2/1), to give 1.65 g of the desired compound as a pale yellowish white crystalline product (yield 51%).

Workup

  1. temperatureUnder chilling with ice, to the solution
  2. customlower than 5° C
  3. customwas set to 37° C
  4. stirringUnder the condition, the reaction mixture was vigorously stirred
  5. customAfter the completion of reaction
  6. distillationacetone was distilled off
  7. additionTo the residue were added ethyl acetate and concentrated aqueous ammonia
  8. customThe organic portion was recovered
  9. washwashed with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. filtrationThe dried mixture was filtered
  12. distillationto distill off ethyl acetate
  13. customThe residue was purified by column chromatography (hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-cda063f2c1c945a38f3eade2b51981b0
Source dataset
uspto-grants-1997_12
Patent number
US05693651

Reaction notes

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