Methyl vinyl ketone → 7-Chloro-4-methylquinoline

HRID 2234226

Reaction equation

HRID 2234226 reaction equation
Cl.[Cl:2][C:3]1[CH:4]=[C:5]([CH:7]=[CH:8][CH:9]=1)[NH2:6].[CH:10]([C:12]([CH3:14])=O)=[CH2:11].[OH-].[Na+]>[Cl-].[Zn+2].[Cl-].C(O)C>[CH3:14][C:12]1[C:7]2[C:5](=[CH:4][C:3]([Cl:2])=[CH:9][CH:8]=2)[N:6]=[CH:11][CH:10]=1

Participants

6

Reactant 3

HCID 6570Methyl vinyl ketoneHCID 14798Sodium HydroxideHCID 67336Benzenamine, 3-chloro-, hydrochloride (1:1)

Product 1

HCID 1704377-Chloro-4-methylquinoline

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

32.8 g. (0.2 mol) 3-chloroaniline hydrochloride, 81 g. ferric trichloride hexahydrate (0.3 mol), 3.0 g. redried anhydrous zinc chloride and 150 mL 95% ethanol were added into a 500 mL 3-neck flask equipped with a reflux condenser, a magnetic stirrer with heating, a thermometer and a constant-pressure dropping funnel, and the mixture was stirred and heated to 60° C. 12.6 g. (0.18 mol) methyl vinyl ketone was added slowly through the constant-pressure dropping funnel while maintaining the temperature at 60-70° C., followed by raising the temperature to reflux for 2 hours. After cooling, the mixed solution was added with 25% aqueous sodium hydroxide until alkaline. The solvent was then distilled off under reduced pressure until dry. The resulting solids were removed and repeatedly extracted with anhydrous ethyl ether. The extracts were collected, dried over anhydrous potassium carbonate and filtered. After removing the solvent, the residue was purified in a silica column using hexane/ethyl acetate (3:1) as the mobile phase to afford 11.38 g. of product.

Workup

  1. customequipped with a reflux condenser, a magnetic stirrer
  2. temperaturewith heating
  3. temperaturewhile maintaining the temperature at 60-70° C.
  4. temperatureby raising the temperature
  5. temperatureto reflux for 2 hours
  6. temperatureAfter cooling
  7. distillationThe solvent was then distilled off under reduced pressure
  8. customuntil dry
  9. customThe resulting solids were removed
  10. extractionrepeatedly extracted with anhydrous ethyl ether
  11. customThe extracts were collected
  12. dry with materialdried over anhydrous potassium carbonate
  13. filtrationfiltered
  14. customAfter removing the solvent
  15. customthe residue was purified in a silica column
  16. customto afford 11.38 g

Sources & evidence

ORD record
ord-5ff7f23daf544bd983658a9dfac439fb
Source dataset
uspto-grants-2010_05
Patent number
US07709653B2

Linked notes

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