Cesium carbonate → 1-tert-Butoxycarbonyl-4-[(4-hydroxyphenyl)sulfanyl]piperidine

HRID 605781ノート

反応式

HRID 605781 の反応式
CS(Cl)(=O)=O.O[CH:7]1[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]1.C(=O)([O-])[O-].[Cs+].[Cs+].[SH:26][C:27]1[CH:32]=[CH:31][C:30]([OH:33])=[CH:29][CH:28]=1>CC(N(C)C)=O.O.CCOC(C)=O.C1COCC1>[OH:33][C:30]1[CH:31]=[CH:32][C:27]([S:26][CH:7]2[CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]2)=[CH:28][CH:29]=1

参加物

9

反応物 4

HCID 10796Cesium carbonateHCID 31297Methanesulfonyl chlorideHCID 2401474-MercaptophenolHCID 643502Tert-butyl 4-hydroxypiperidine-1-carboxylate

生成物 1

HCID 185387571-tert-Butoxycarbonyl-4-[(4-hydroxyphenyl)sulfanyl]piperidine収率 73.4%

試薬・触媒・溶媒 4

HCID 962Water溶媒2 回HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒HCID 31374Dimethylacetamide溶媒

実験手順

TEA (2.30 ml) and methanesulfonyl chloride (1.22 ml) were dropwise added to a THF (40 ml) solution containing tert-butyl 4-hydroxypiperidine-1-carboxylate (3.02 g) at 0° C., followed by stirring at room temperature for 1 hour. EtOAc (50 ml) and water (50 ml) were added to the reaction solution. The organic layer was washed with aqueous 5% citric acid solution, an aqueous saturated sodium hydrogencarbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain a pale orange oil. The resulting oil was dissolved in DMA (25 ml), and cesium carbonate (5.38 g) and 4-sulfanylphenol (1.89 g) were added thereto, followed by heating at 50° C. for 2 hours. The reaction solution was cooled, water was added thereto, followed by extraction with EtOAc. The organic layer was washed with an aqueous 1 M hydrochloric acid solution and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: hexane:EtOAc=4:1 (v/v)) to obtain tert-butyl 4-[(4-hydroxyphenyl)sulfanyl]piperidine-1-carboxylate (3.40 g) as colorless powder.

後処理

  1. washThe organic layer was washed with aqueous 5% citric acid solution
  2. dry with materialan aqueous saturated sodium hydrogencarbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate
  3. customThe solvent was evaporated under reduced pressure
  4. customto obtain a pale orange oil
  5. temperatureby heating at 50° C. for 2 hours
  6. temperatureThe reaction solution was cooled
  7. extractionfollowed by extraction with EtOAc
  8. washThe organic layer was washed with an aqueous 1 M hydrochloric acid solution and saturated brine in that order
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe solvent was evaporated under reduced pressure
  11. customthe residue was purified by silica gel column chromatography (eluent: hexane:EtOAc=4:1 (v/v))

出典と根拠

ORDレコード
ord-6903be5b41e0492281b85d855b51d090
出典データセット
uspto-grants-2011_03
特許番号
US07915261B2

反応ノート

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