4-Toluenesulfonyl chloride → Tert-butyl [4-(4-amino-7-bromo-2-ethoxymethyl-1h-imidazo[4,5-c]quinolin-1-ylmethyl)benzyl]carbamate

HRID 1818238Notes

Reaction equation

HRID 1818238 reaction equation
ClC1C=C(C=CC=1)C(OO)=O.[Br:12][C:13]1[CH:14]=[CH:15][C:16]2[C:17]3[N:25]([CH2:26][C:27]4[CH:41]=[CH:40][C:30]([CH2:31][NH:32][C:33](=[O:39])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[CH:29][CH:28]=4)[C:24]([CH2:42][O:43][CH2:44][CH3:45])=[N:23][C:18]=3[CH:19]=[N:20][C:21]=2[CH:22]=1.[OH-].[NH4+:47].C1(C)C=CC(S(Cl)(=O)=O)=CC=1>C(Cl)(Cl)Cl>[NH2:47][C:19]1[C:18]2[N:23]=[C:24]([CH2:42][O:43][CH2:44][CH3:45])[N:25]([CH2:26][C:27]3[CH:41]=[CH:40][C:30]([CH2:31][NH:32][C:33](=[O:39])[O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[CH:29][CH:28]=3)[C:17]=2[C:16]2[CH:15]=[CH:14][C:13]([Br:12])=[CH:22][C:21]=2[N:20]=1

Participants

6

Reactant 4

HCID 73974-Toluenesulfonyl chlorideHCID 14923Ammonium HydroxideHCID 70297m-Chloroperbenzoic acidHCID 86593767tert-butyl [4-(7-bromo-2-ethoxymethyl-1H-imidazo[4,5-c]quinolin-1-ylmethyl)benzyl]carbamate

Product 1

HCID 86593768Tert-butyl [4-(4-amino-7-bromo-2-ethoxymethyl-1h-imidazo[4,5-c]quinolin-1-ylmethyl)benzyl]carbamate

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

3-Chloroperoxybenzoic acid (2.91 g, 9.3 mmol, 55% pure) was added to a solution of tert-butyl [4-(7-bromo-2-ethoxymethyl-1H-imidazo[4,5-c]quinolin-1-ylmethyl)benzyl]carbamate (3.2 g, 6.1 mmol) in chloroform (60 mL). The reaction was stirred for 1 hour and then cooled with an ice bath. Ammonium hydroxide (40 mL) was added and the reaction was stirred for 10 minutes. p-Toluenesulfonyl chloride (1.16 g, 6.1 mmol) was added in two portions. The cooling bath was removed and the mixture was stirred for an additional 16 hours. The layers were separated and the aqueous fraction was extracted with dichloromethane. The combined organic fractions were washed sequentially with water and saturated aqueous sodium chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification of the residue by flash column chromatography (CMA/chloroform) and subsequent recrystallization from acetonitrile yielded 1.15 g of tert-butyl [4-(4-amino-7-bromo-2-ethoxymethyl-1H-imidazo [4,5-c]quinolin-1-ylmethyl)benzyl]carbamate as a tan solid.

Workup

  1. temperaturecooled with an ice bath
  2. stirringthe reaction was stirred for 10 minutes
  3. customThe cooling bath was removed
  4. stirringthe mixture was stirred for an additional 16 hours
  5. customThe layers were separated
  6. extractionthe aqueous fraction was extracted with dichloromethane
  7. washThe combined organic fractions were washed sequentially with water and saturated aqueous sodium chloride
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customPurification of the residue
  12. customby flash column chromatography (CMA/chloroform) and subsequent recrystallization from acetonitrile

Sources & evidence

ORD record
ord-7623f6d6f21049629f612a6d4152b04f
Source dataset
uspto-grants-2009_10
Patent number
US07598382B2

Reaction notes

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