m-Chloroperbenzoic acid → HCID 69506693, compound

HRID 2366728Notes

Reaction equation

HRID 2366728 reaction equation
[CH2:1]([C:5]1[N:6]([CH2:18][C:19]([CH3:26])([CH3:25])[C:20]([O:22][CH2:23]C)=[O:21])[C:7]2[C:16]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[N:10]=[CH:9][C:8]=2[N:17]=1)[CH2:2][CH2:3][CH3:4].C1C=C(Cl)C=C(C(OO)=O)C=1.ClC(Cl)(Cl)C([N:42]=C=O)=O.[N-]=C=O>CO>[NH2:42][C:9]1[C:8]2[N:17]=[C:5]([CH2:1][CH2:2][CH2:3][CH3:4])[N:6]([CH2:18][C:19]([CH3:26])([CH3:25])[C:20]([O:22][CH3:23])=[O:21])[C:7]=2[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[N:10]=1

Participants

6

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 76400Trichloroacetyl isocyanate3×HCID 105034IsocyanateHCID 69506740HCID 69506740, compound

Product 1

HCID 69506693HCID 69506693, compoundYield 103.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A modification of the methods described in Part B of Example 60 was used to treat ethyl 3-(2-butyl-1H-imidazo[4,5-c]quinolin-1-yl)-2,2-dimethylpropanoate (11.0 g, 31 mmol) with mCPBA (13.6 g of 77% pure material), followed by trichloroacetyl isocyanate (4.4 mL, 37 mmol). The reaction with the isocyanate was stirred for 1.5 hours before the addition of additional trichloroacetyl isocyanate (4.4 mL) and stirring for three days. Additional trichloroacetyl isocyanate (0.5 mL) was added, and the reaction was stirred for four hours. After the addition of methanol (50 mL), the solution was stirred overnight, and then the solvent was removed under reduced pressure. The residue was dissolved in dichloromethane (150 mL), and the solution was washed with saturated aqueous sodium bicarbonate (2×35 mL), dried over potassium carbonate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (eluting with 5% methanol in dichloromethane containing 2 mL ammonium hydroxide per liter of eluent) to provide 11.4 g of methyl 3-(4-amino-2-butyl-1H-imidazo[4,5-c]quinolin-1-yl)-2,2-dimethylpropanoate as a semi-solid.

Workup

  1. stirringthe reaction was stirred for four hours
  2. stirringthe solution was stirred overnight
  3. customthe solvent was removed under reduced pressure
  4. dissolutionThe residue was dissolved in dichloromethane (150 mL)
  5. washthe solution was washed with saturated aqueous sodium bicarbonate (2×35 mL)
  6. dry with materialdried over potassium carbonate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified by column chromatography on silica gel (eluting with 5% methanol in dichloromethane containing 2 mL ammonium hydroxide per liter of eluent)

Sources & evidence

ORD record
ord-e2b80a57cd3d411cb630d72cf9b38146
Source dataset
uspto-grants-2014_04
Patent number
US08697873B2

Reaction notes

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