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

HRID 1926088Notes

Reaction equation

HRID 1926088 reaction equation
C(S[CH2:6][CH2:7][O:8][CH2:9][CH2:10][N:11]1[C:19]2[C:18]([NH:20][C:21]3[CH:26]=[CH:25][C:24]([O:27][C:28]4[CH:33]=[CH:32][CH:31]=[C:30]([C:34]([F:37])([F:36])[F:35])[CH:29]=4)=[C:23]([Cl:38])[CH:22]=3)=[N:17][CH:16]=[N:15][C:14]=2[CH:13]=[CH:12]1)(C)(C)C.CO.[C:41](OO)([CH3:44])([CH3:43])[CH3:42].[S:47]([O-:51])([O-])(=[O:49])=S.[Na+].[Na+]>ClCCl.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[C:41]([S:47]([CH2:6][CH2:7][O:8][CH2:9][CH2:10][N:11]1[C:19]2[C:18]([NH:20][C:21]3[CH:26]=[CH:25][C:24]([O:27][C:28]4[CH:33]=[CH:32][CH:31]=[C:30]([C:34]([F:35])([F:37])[F:36])[CH:29]=4)=[C:23]([Cl:38])[CH:22]=3)=[N:17][CH:16]=[N:15][C:14]=2[CH:13]=[CH:12]1)(=[O:51])=[O:49])([CH3:44])([CH3:43])[CH3:42]

Participants

7

Reactant 4

HCID 887MethanolHCID 6410tert-Butyl hydroperoxideHCID 24477Sodium ThiosulfateHCID 675211475-{2-[2-(tert-butylthio)ethoxy]ethyl}-N-{3-chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine

Product 1

HCID 575971905-{2-[2-(tert-butylsulfonyl)ethoxy]ethyl}-N-{3-chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 6344DichloromethaneSolvent

Procedure

5-{2-[2-(tert-Butylthio)ethoxy]ethyl}-N-{3-chloro-4-[3-(trifluoromethyl)phenoxy]phenyl}-5H-pyrrolo[3,2-d]pyrimidin-4-amine (140 mg) was dissolved in dichloromethane (5.0 mL), titanium tetraisopropoxide (0.90 mL), methanol (0.20 mL) and 70% aqueous tert-butyl hydroperoxide solution (7.0 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 (10.6 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-bf31995303ba4f13a0a641e03e8fbde4
Source dataset
uspto-grants-2012_05
Patent number
US08178543B2

Reaction notes

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