Benzenesulfonyl chloride → [4-amino-7-bromo-1-(tetrahydro-2H-pyran-4-ylmethyl)-1H-imidazo[4,5-c]quinolin-2-yl]methanol

HRID 1694585Notes

Reaction equation

HRID 1694585 reaction equation
C([O:4][CH2:5][C:6]1[N:7]([CH2:20][CH:21]2[CH2:26][CH2:25][O:24][CH2:23][CH2:22]2)[C:8]2[C:17]3[CH:16]=[CH:15][C:14]([Br:18])=[CH:13][C:12]=3[N:11]=[CH:10][C:9]=2[N:19]=1)(=O)C.C(=O)(O)[O-].[Na+].[OH-].[NH4+:33].C1(S(Cl)(=O)=O)C=CC=CC=1>O.C(Cl)(Cl)Cl>[NH2:33][C:10]1[C:9]2[N:19]=[C:6]([CH2:5][OH:4])[N:7]([CH2:20][CH:21]3[CH2:26][CH2:25][O:24][CH2:23][CH2:22]3)[C:8]=2[C:17]2[CH:16]=[CH:15][C:14]([Br:18])=[CH:13][C:12]=2[N:11]=1

Participants

7

Reactant 4

HCID 7369Benzenesulfonyl chloride2×HCID 14923Ammonium Hydroxide2×HCID 516892Sodium Bicarbonate2×HCID 67281006[7-bromo-1-(tetrahydro-2H-pyran-4-ylmethyl)-1H-imidazo[4,5-c]quinolin-2-yl]methyl acetate

Product 1

HCID 67281118[4-amino-7-bromo-1-(tetrahydro-2H-pyran-4-ylmethyl)-1H-imidazo[4,5-c]quinolin-2-yl]methanolYield 52.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

3-Chloroperoxybenozic acid (2.4 g, 50% pure, 7.0 mmol) was added to a mixture of [7-bromo-1-(tetrahydro-2H-pyran-4-ylmethyl)-1H-imidazo[4,5-c]quinolin-2-yl]methyl acetate (2.3 g, 5.4 mmol) and chloroform (27 mL) at ambient temperature. The reaction was stirred at this temperature for 18 hours. Saturated aqueous sodium bicarbonate (50 mL) and water (50 mL) were then added to the reaction and the layers were separated. The aqueous layer was extracted with additional dichloromethane. The organic layers were combined, dried over sodium sulfate, and concentrated under reduced pressure to a dark oil. This oil was dissolved in methanol (27 mL) and to this solution was added 15 M ammonium hydroxide (3.6 mL, 54 mmol) and benzene sulfonyl chloride (2.9 mL, 23 mmol). The resulting reaction mixture was stirred at ambient temperature for 2 hours before adding additional 15 M ammonium hydroxide (3.6 mL, 54 mmol) and benzene sulfonyl chloride (2.9 mL, 23 mmol). The reaction was stirred 18 hours. The reaction was then concentrated under reduced pressure and diluted with saturated aqueous sodium bicarbonate and chloroform. A suspension resulted that was filtered to afford a solid that was stirred with saturated aqueous sodium bicarbonate and filtered to give 1.1 g of [4-amino-7-bromo-1-(tetrahydro-2H-pyran-4-ylmethyl)-1H-imidazo[4,5-c]quinolin-2-yl]methanol as a white solid.

Workup

  1. customthe layers were separated
  2. extractionThe aqueous layer was extracted with additional dichloromethane
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated under reduced pressure to a dark oil
  5. dissolutionThis oil was dissolved in methanol (27 mL) and to this solution
  6. customThe resulting reaction mixture
  7. stirringwas stirred at ambient temperature for 2 hours
  8. stirringThe reaction was stirred 18 hours
  9. concentrationThe reaction was then concentrated under reduced pressure
  10. additiondiluted with saturated aqueous sodium bicarbonate and chloroform
  11. customA suspension resulted
  12. filtrationthat was filtered
  13. customto afford a solid
  14. filtrationfiltered

Sources & evidence

ORD record
ord-85886e2a4e04465e89491c55c2ee51dc
Source dataset
uspto-grants-2012_04
Patent number
US08158794B2

Reaction notes

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