Reaktion #59991

Reaktionsgleichung

cumene hydroperoxide

2-(((4-((2,2-dimethyl-1,3-dioxan-5-yl)methoxy)-3,5-dimethylpyridin-2-yl)methyl)thio)-1H-benzimidazole

sodium hydrogen carbonate

sodium thiosulfate

N,N-diisopropylethylamine

→

title compound

Ausbeute 40.0%

2-(((4-((2,2-dimethyl-1,3-dioxan-5-yl)methoxy)-3,5-dimethylpyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole

Ausbeute 40.0%

Lösungsmittel

toluene

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.DISSOLUTIONwas dissolved
2. 2
   TemperaturAfter the reaction mixture was cooled to room temperature
3. 3
   workup.ADDITIONwas added dropwise to the mixture
4. 4
   workup.STIRRINGthe mixture was stirred at room temperature for 22 hours
5. 5
   Extraktionthe mixture was extracted with ethyl acetate
6. 6
   TrocknenThe organic layer was dried over anhydrous sodium sulfate
7. 7
   Filtrationfiltrated
8. 8
   Einengenconcentrated
9. 9
   SonstigeThe residue was purified by silica gel column chromatography (NH silica gel: 30 g, elution solvent: ethyl acetate, ethyl acetate/methanol 7:3, 1;1 gradient)
10. 10
    workup.ADDITIONThe fractions containing the title compound
11. 11
    Sonstigewere collected with ethyl acetate
12. 12
    Einengenconcentrated

Vorschrift

A mixture of 2-(((4-((2,2-dimethyl-1,3-dioxan-5-yl)methoxy)-3,5-dimethylpyridin-2-yl)methyl)thio)-1H-benzimidazole (500 mg, 1.21 mmol) and N,N,N′,N′-(−)-tetramethyl-(D)-tartaramide (396 mg, 1.94 mmol) in toluene (4 ml) was dissolved by heating at 40° C. for 10 minutes in a nitrogen atmosphere. Hafnium tetrabutoxide (315 μL, 0.78 mmol) was added to the mixture and further stirred at the same temperature for one hour. After the reaction mixture was cooled to room temperature, N,N-diisopropylethylamine (90 μl, 0.52 mmol) was added and subsequently, cumene hydroperoxide (267 μl, 1.46 mmol as the content was regarded as 80%) was added dropwise to the mixture and then the mixture was stirred at room temperature for 22 hours. After a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium thiosulfate solution were added, the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, filtrated, and concentrated. The residue was purified by silica gel column chromatography (NH silica gel: 30 g, elution solvent: ethyl acetate, ethyl acetate/methanol 7:3, 1;1 gradient). The fractions containing the title compound were collected with ethyl acetate and concentrated to obtain the title compound (206 mg, yield: 40%) as a colorless foam.

Quelle