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

HRID 1645530노트

반응식

HRID 1645530 반응식
C1(C)C=CC=CC=1.[CH3:8][C:9]1[C:10]([CH2:28][S:29][C:30]2[NH:34][C:33]3[CH:35]=[CH:36][CH:37]=[CH:38][C:32]=3[N:31]=2)=[N:11][CH:12]=[CH:13][C:14]=1[O:15][CH2:16][C:17]1([CH3:27])[O:26][CH2:25][C:20]2([O:24][CH2:23][CH2:22][O:21]2)[CH2:19][O:18]1.ClC1C=CC=C(C(OO)=[O:47])C=1>CO>[CH3:8][C:9]1[C:10]([CH2:28][S:29]([C:30]2[NH:31][C:32]3[CH:38]=[CH:37][CH:36]=[CH:35][C:33]=3[N:34]=2)=[O:47])=[N:11][CH:12]=[CH:13][C:14]=1[O:15][CH2:16][C:17]1([CH3:27])[O:18][CH2:19][C:20]2([O:21][CH2:22][CH2:23][O:24]2)[CH2:25][O:26]1

참가 물질

5

반응물 3

HCID 1140Toluene2회HCID 70297m-Chloroperbenzoic acidHCID 597925332-(((3-methyl-4-((8-methyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)methoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole

생성물 1

HCID 120031192-(((3-methyl-4-((8-methyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)methoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzimidazole수율 38.4%

시약·촉매·용매 1

HCID 887Methanol용매2회

실험 절차

To a toluene (8.1 ml) and methanol (0.9 ml) solution of the 2-(((3-methyl-4-((8-methyl-1,4,7,9-tetraoxaspiro[4.5]dec-8-yl)methoxy)pyridin-2-yl)methyl)thio)-1H-benzimidazole (372 mg, 0.84 mmol) obtained in the step (5f), a toluene (2.7 ml) and methanol (0.3 ml) solution of 3-chloroperbenzoic acid (200 mg, 0.76 mmol as the content was regarded as 65%) was added dropwise at −55° C. to −50° C. for 10 minutes in a nitrogen atmosphere. The mixture was stirred at −60° C. to −50° C. for 1.5 hours. The reaction was terminated by adding 12 ml of a saturated aqueous solution of sodium hydrogen carbonate at the same temperature. The mixture was extracted with 50 ml of chloroform twice, and then, 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, elution solvent: ethyl acetate/methanol=1/0-4/1 gradient) and desired fractions were concentrated. The obtained white foam was re-precipitated with chloroform and diethyl ether and filtered. The operation was repeated twice to obtain the title compound (148 mg, 38.4% yield) as a white solid.

후처리

  1. additionwas added dropwise at −55° C. to −50° C. for 10 minutes in a nitrogen atmosphere
  2. customThe reaction was terminated
  3. additionby adding 12 ml of a saturated aqueous solution of sodium hydrogen carbonate at the same temperature
  4. extractionThe mixture was extracted with 50 ml of chloroform 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, elution solvent: ethyl acetate/methanol=1/0-4/1 gradient)
  9. concentrationdesired fractions were concentrated
  10. customThe obtained white foam was re-precipitated with chloroform and diethyl ether
  11. filtrationfiltered

출처 및 근거

ORD 기록
ord-d63f8187eb4b4870acd2d1cc970b71bc
출처 데이터셋
uspto-grants-2012_02
특허 번호
US08124780B2

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