Methanol → N-{3-chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5-{2-[2-(methylsulfonyl)ethoxy]ethyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine

HRID 1786997Notes

Reaction equation

HRID 1786997 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH:19][C:20]2[C:21]3[N:28]([CH2:29][CH2:30][O:31][CH2:32][CH2:33]SC)[CH:27]=[CH:26][C:22]=3[N:23]=[CH:24][N:25]=2)[CH:5]=[CH:6][C:7]=1[O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=1.CO.[C:38](OO)(C)(C)C.[S:44]([O-:48])([O-])(=[O:46])=S.[Na+].[Na+]>ClCCl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[Cl:1][C:2]1[CH:3]=[C:4]([NH:19][C:20]2[C:21]3[N:28]([CH2:29][CH2:30][O:31][CH2:32][CH2:33][S:44]([CH3:38])(=[O:48])=[O:46])[CH:27]=[CH:26][C:22]=3[N:23]=[CH:24][N:25]=2)[CH:5]=[CH:6][C:7]=1[O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=1

Participants

7

Reactant 4

HCID 887MethanolHCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 67520384N-{3-Chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5-{2-[2-(methylthio)ethoxy]ethyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine

Product 1

HCID 57597132N-{3-chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5-{2-[2-(methylsulfonyl)ethoxy]ethyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 6344DichloromethaneSolvent

Procedure

N-{3-Chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5-{2-[2-(methylthio)ethoxy]ethyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine (70.0 mg) was dissolved in dichloromethane (5.0 mL), titanium tetraisopropoxide (0.10 mL), methanol (0.50 mL) and 70% aqueous tert-butyl hydroperoxide solution (8.0 mL) were added, and the mixture was stirred at room temperature for 1 hr. Saturated aqueous sodium thiosulfate solution was added to the reaction mixture under ice-cooling, and the mixture was stirred at room temperature for 1 hr and extracted with dichloromethane. The extract was dried over magnesium sulfate and concentrated, and the residue was separated and purified by silica gel column chromatography (eluent, ethyl acetate:methanol=100:0→ethyl acetate:methanol=90:10). Crystallization from diethyl ether/ethyl acetate/hexane gave the title compound (62.5 mg).

Workup

  1. temperaturecooling
  2. stirringthe mixture was stirred at room temperature for 1 hr
  3. extractionextracted with dichloromethane
  4. dry with materialThe extract was dried over magnesium sulfate
  5. concentrationconcentrated
  6. customthe residue was separated
  7. custompurified by silica gel column chromatography (eluent, ethyl acetate:methanol=100:0→ethyl acetate:methanol=90:10)
  8. customCrystallization from diethyl ether/ethyl acetate/hexane

Sources & evidence

ORD record
ord-dacf341508f24341899bb9c208a16e3c
Source dataset
uspto-grants-2009_03
Patent number
US07507740B2

Reaction notes

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