Sodium Thiosulfate → 2-(4-(2,2-Dimethyl-1,3-dioxan-5-yl)methoxy-3,5-dimethylpyridin-2-yl)methylsulfinyl-1H-benzimidazole

HRID 1645659Notes

Reaction equation

HRID 1645659 reaction equation
[CH3:1][C:2]1([CH3:29])[O:7][CH2:6][CH:5]([CH2:8][O:9][C:10]2[C:15]([CH3:16])=[CH:14][N:13]=[C:12]([CH2:17][S:18][C:19]3[NH:23][C:22]4[CH:24]=[CH:25][CH:26]=[CH:27][C:21]=4[N:20]=3)[C:11]=2[CH3:28])[CH2:4][O:3]1.C(N(CC)C(C)C)(C)C.[O-]O.C1(C(C)C)C=CC=CC=1.C(=O)([O-])[OH:51].[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:29])[O:3][CH2:4][CH:5]([CH2:8][O:9][C:10]2[C:15]([CH3:16])=[CH:14][N:13]=[C:12]([CH2:17][S:18]([C:19]3[NH:20][C:21]4[CH:27]=[CH:26][CH:25]=[CH:24][C:22]=4[N:23]=3)=[O:51])[C:11]=2[CH3:28])[CH2:6][O:7]1

Participants

7

Reactant 5

HCID 24477Sodium ThiosulfateHCID 81531DiisopropylethylamineHCID 516892Sodium BicarbonateHCID 248807801H-Benzimidazole, 2-[[[4-[(2,2-dimethyl-1,3-dioxan-5-yl)methoxy]-3,5-dimethyl-2-pyridinyl]methyl]thio]-HCID 53627471Cumen hydroperoxide

Product 1

HCID 120032122-(4-(2,2-Dimethyl-1,3-dioxan-5-yl)methoxy-3,5-dimethylpyridin-2-yl)methylsulfinyl-1H-benzimidazoleYield 63%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A toluene (4 ml) solution 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), zirconium(IV) isopropoxide isopropanol complex (295 mg, 0.76 mmol) and N,N,N′,N′-(−)-tetramethyl-(D)-tartaramide (396 mg, 1.94 mmol) was stirred in a nitrogen atmosphere at 40° C. for one hour. After the solution was cooled to room temperature, N,N-diisopropylethylamine (91 μl, 0.52 mmol) was added and subsequently, cumene hydroperoxide (243 μl, 1.32 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 (328 mg, yield: 63%) as a colorless foam.

Workup

  1. additionwas added dropwise to the mixture
  2. extractionthe mixture was extracted with ethyl acetate
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. filtrationfiltrated
  5. concentrationconcentrated
  6. customThe 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)
  7. additionThe fractions containing the title compound
  8. customwere collected with ethyl acetate
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-0e31c5cba0ac465a9d0852d991d39131
Source dataset
uspto-grants-2012_02
Patent number
US08124780B2

Reaction notes

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