반응 #59900

반응 방정식

( 10d )

2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole

N,N-diisopropylethylamine

cumene hydroperoxide

water

2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole

sodium hydrogen carbonate

→

title compound

수율 82.4%

2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole

수율 82.4%

용매

toluene

반응 조건

후처리

1. 1
   workup.ADDITIONwas added
2. 2
   workup.ADDITIONwas added
3. 3
   workup.ADDITIONwas added dropwise in a nitrogen atmosphere
4. 4
   workup.STIRRINGthe mixture was stirred at 0° C. to room temperature for 5.5 hours
5. 5
   추출the reaction mixture was extracted with ethyl acetate
6. 6
   건조The organic layer was dried over sodium sulfate
7. 7
   workup.DISTILLATIONthe solvent was distilled off under reduced pressure
8. 8
   기타The obtained residue was purified by silica gel column chromatography (NH silica gel, elution solvent: ethyl acetate/methanol)

실험 절차

To a toluene (dehydrated)(1.5 ml)-water (1.47 μl, 81.5 μmol) solution of the 2-(((3-methyl-4-(1,5,9-trioxaspiro[5.5]undec-3-ylmethoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole (300 mg, 679 mmol) separately obtained in the same manner as described in the steps (10a) to (10d) of Example 10, L-(+)-diethyl tartrate (51.2 μl, 299 μmol) was added and the mixture was stirred at 50° C. for 5 minutes in a nitrogen atmosphere. Titanium (IV) isopropoxide (40.1 μl, 136 μmol) was added and the resultant mixture was stirred for further one hour. After cooled on ice and N,N-diisopropylethylamine (37.8 μl, 217 μmol) was added, and cumene hydroperoxide (376 μl, 2.04 mmol as the content was regarded as 80%) was added dropwise in a nitrogen atmosphere, the mixture was stirred at 0° C. to room temperature for 5.5 hours. After a saturated aqueous solution of sodium hydrogen carbonate was added, the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (NH silica gel, elution solvent: ethyl acetate/methanol) to obtain the title compound (256 mg, yield: 82.4%) as a light yellow foam.

출처