Toluene → 2-(((4-(2-(8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)ethoxy)-3-methylpyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole

HRID 31585Notes

Reaction equation

HRID 31585 reaction equation
C1(C)C=CC=CC=1.[CH2:8]([C:10]1([CH2:20][CH2:21][O:22][C:23]2[CH:28]=[CH:27][N:26]=[C:25]([CH2:29][S:30][C:31]3[NH:35][C:34]4[CH:36]=[CH:37][CH:38]=[CH:39][C:33]=4[N:32]=3)[C:24]=2[CH3:40])[O:19][CH2:18][C:13]2([O:17][CH2:16][CH2:15][O:14]2)[CH2:12][O:11]1)[CH3:9].ClC1C=CC=C(C(OO)=[O:49])C=1>CO>[CH2:8]([C:10]1([CH2:20][CH2:21][O:22][C:23]2[CH:28]=[CH:27][N:26]=[C:25]([CH2:29][S:30]([C:31]3[NH:35][C:34]4[CH:36]=[CH:37][CH:38]=[CH:39][C:33]=4[N:32]=3)=[O:49])[C:24]=2[CH3:40])[O:19][CH2:18][C:13]2([O:14][CH2:15][CH2:16][O:17]2)[CH2:12][O:11]1)[CH3:9]

Participants

5

Reactant 3

HCID 1140Toluene2×HCID 70297m-Chloroperbenzoic acidHCID 597925652-(((4-(2-(8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)ethoxy)-3-methylpyridin-2-yl)methyl)thio)-1H-benzimidazole

Product 1

HCID 120031242-(((4-(2-(8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)ethoxy)-3-methylpyridin-2-yl)methyl)sulfinyl)-1H-benzimidazoleYield 47.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

To a toluene (10.8 ml) and methanol (1.2 ml) solution of the 2-(((4-(2-(8-ethyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)ethoxy)-3-methylpyridin-2-yl)methyl)thio)-1H-benzimidazole (380 mg, 0.81 mmol) obtained in the step (4h), a toluene (2.7 ml) and methanol (0.3 ml) solution of 3-chloroperbenzoic acid (192 mg, 0.73 mmol as the content was regarded as 65%) was added dropwise at −70 to −60° C. for 10 minutes in a nitrogen atmosphere. The mixture was stirred for one hour in the same conditions. The reaction was terminated by adding a saturated aqueous solution (15 ml) of sodium hydrogen carbonate at the same temperature. The mixture was extracted with chloroform (50 ml) twice and the organic layer was dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by silica gel column chromatography (NH silica gel: elusion solvent: ethyl acetate/methanol=1/0-4/1 gradient) and desired fractions were concentrated. The obtained foamy product was re-precipitated with chloroform and diethyl ether and filtered. The operation was repeated four times and the obtained solid was washed with diethyl ether and then dried to obtain the title compound (188 mg, 47.9% yield) as a white solid.

Workup

  1. additionwas added dropwise at −70 to −60° C. for 10 minutes in a nitrogen atmosphere
  2. customThe reaction was terminated
  3. additionby adding a saturated aqueous solution (15 ml) of sodium hydrogen carbonate at the same temperature
  4. extractionThe mixture was extracted with chloroform (50 ml) twice
  5. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customThe obtained crude product
  8. customwas purified by silica gel column chromatography (NH silica gel: elusion solvent: ethyl acetate/methanol=1/0-4/1 gradient)
  9. concentrationdesired fractions were concentrated
  10. customThe obtained foamy product was re-precipitated with chloroform and diethyl ether
  11. filtrationfiltered
  12. washthe obtained solid was washed with diethyl ether
  13. customdried

Sources & evidence

ORD record
ord-08397371a41c43d287a817bfea55d25d
Source dataset
uspto-grants-2008_09
Patent number
US07425634B2

Reaction notes

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