Methane, dichloromethoxy- → HCID 21931734, compound

HRID 1243986Notes

Reaction equation

HRID 1243986 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[CH3:5][O:6][C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[N:13]([CH3:17])[C:12](=[O:18])[CH2:11][C:10]2([CH3:20])[CH3:19].[CH3:21][O:22]C(Cl)Cl>C(Cl)Cl>[CH3:5][O:6][C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][C:16]=1[CH:21]=[O:22])[N:13]([CH3:17])[C:12](=[O:18])[CH2:11][C:10]2([CH3:20])[CH3:19]

Participants

5

Reactant 3

HCID 21004Methane, dichloromethoxy-HCID 6451240Aluminum(III) ChlorideHCID 21931766HCID 21931766, compound

Product 1

HCID 21931734HCID 21931734, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a flame dried round bottom flask equipped with a nitrogen cap was added 89 mg (66 mmol) aluminum chloride and 5 ml of methylene chloride (CHCl2). The mixture was stirred at ambient temperature for 0.25 hour and then cooled to 0° C. followed by the addition of 75 mg (0.34 mmol) 6-methoxy-1,4,4-trimethyl-3,4-dihydro-1H-quinolin-2-one. The reaction mixture was stirred for 10 minutes at this temperature and was then treated with 84 μl (0.93 mmol) of α,α-dichloromethyl methyl ether before allowing the reaction to slowly warm to room temperature over 16 hours. The reaction mixture was quenched with 30 ml of 2M HCl and extracted with ethyl acetate (3×30 ml). The combined organics were then washed with saturated aqueous bicarbonate solution and brine followed by drying over sodium sulfate and evaporation in vacuo. The crude residue was purified on silica gel eluting with 1:1 ethyl acetate/hexane to afford two products. The more polar material was identified as the desired product: Mass spectrum APCI m/e 248 (p+1). The less polar product was identified as 7-Dichloromethyl-6-methoxy-1-methyl-3,4-dihydro-1H-quinolin-2-one (Mass spectrum APCI m/e 302 (p+1)) from which the desire product was isolated after a brief stirring in pH 7 phosphate buffer. Total yield 56 mg (66%).

Workup

  1. customTo a flame dried round bottom flask
  2. customequipped with a nitrogen
  3. customcap
  4. temperaturecooled to 0° C.
  5. stirringThe reaction mixture was stirred for 10 minutes at this temperature
  6. customthe reaction
  7. temperatureto slowly warm to room temperature over 16 hours
  8. customThe reaction mixture was quenched with 30 ml of 2M HCl
  9. extractionextracted with ethyl acetate (3×30 ml)
  10. washThe combined organics were then washed with saturated aqueous bicarbonate solution and brine
  11. dry with materialby drying over sodium sulfate and evaporation in vacuo
  12. customThe crude residue was purified on silica gel eluting with 1:1 ethyl acetate/hexane
  13. customto afford two products

Sources & evidence

ORD record
ord-c6e48086659e4d0fb4830919735e9531
Source dataset
uspto-grants-2006_10
Patent number
US07119207B2

Reaction notes

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