Diisopropylamine → [[(Ethylsulfinyl)-1-tosylimidazol-5-ylmethyl]thio]ethane

HRID 27615ノート

反応式

HRID 27615 の反応式
[CH2:1]([S:3]([CH2:5][S:6][CH2:7][CH3:8])=[O:4])[CH3:2].C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.C(OC[C:34]1[N:38]([S:39]([C:42]2[CH:48]=[CH:47][C:45]([CH3:46])=[CH:44][CH:43]=2)(=[O:41])=[O:40])[CH:37]=[N:36][CH:35]=1)(=O)C>O1CCCC1.CCCCCC>[CH2:1]([S:3]([CH:5]([C:34]1[N:38]([S:39]([C:42]2[CH:48]=[CH:47][C:45]([CH3:46])=[CH:44][CH:43]=2)(=[O:41])=[O:40])[CH:37]=[N:36][CH:35]=1)[S:6][CH2:7][CH3:8])=[O:4])[CH3:2]

参加物

8

反応物 5

HCID 7912DiisopropylamineHCID 382152(1-((4-Methylphenyl)sulfonyl)-1H-imidazol-5-yl)methyl acetateHCID 2724682Lithium diisopropylamideHCID 3015888Ethyl (ethylthio)methyl sulphoxideHCID 178418339Butyllithium

生成物 1

HCID 23343207[[(Ethylsulfinyl)-1-tosylimidazol-5-ylmethyl]thio]ethane

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒

反応条件

温度
25 °C

実験手順

A solution of 10 mmole of [[(ethylsulfinyl)methyl]thio]ethane in 20 ml of dry tetrahydrofuran is heated at 0° C. with 10 mmole of lithium diisopropylamide, prepared from a solution of diisopropylamine M in tetrahydrofuran and butyllithium 2 M in hexane. After 30 minutes at 0° C. a solution of 12 mmole of 5-acetyloxymethyl-1-tosylimidazole in 10 ml of tetrahydrofuran is added. The reaction mixture is stirred at 25° C. overnight then is quenched with brine and extracted with ether. The organic phase is washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to give [[(ethylsulfinyl)-1-tosylimidazol-5-ylmethyl]thio]ethane. To a solution of 20 mmole of [[(ethylsulfinyl)-1-tosylimidazol-5-ylmethyl]thio]ethane in 20 ml of dry tetrahydrofuran is added at 0° C. and under nitrogen a solution of 20 mmole of lithium diisopropylamide prepared from a solution of diisopropylamine M in tetrahydrofuran and butyl lithium 2 M in hexane. Stirring is continued for 30 minutes at 25° C. after which a stream of chlorodifluoromethane is bubbled into the reaction mixture for 1/2 hour. The reaction mixture is maintained at 40° C. for 3 hours then quenched with brine and extracted with ether. The organic phase is separated, washed with brine, dried over magnesium sulfate and concentrated under reduced pressure to afford [[(ethylsulfinyl)((difluoromethyl)-1-tosylimidazol-5-ylmethyl)]thio]ethane. To a solution of 30 ml of [[(ethylsulfinyl)((difluoromethyl)-1-tosylimidazol-5-ylmethyl)]thio]ethane in 33 ml of acetonitrile is added at 0° C. a 70% aqueous solution of perchloric acid (1.1 ml). After stirring for 2 hours at 0° C. the reaction mixture is poured into 60 ml of water then extracted with difluoromethane. The organic phase is washed with sodium bicarbonate then water, dried over magnesium sulfate and concentrated under reduced pressure to afford difluoromethyl 5-imidazolylmethyl ketone.

後処理

  1. customthen is quenched with brine
  2. extractionextracted with ether
  3. washThe organic phase is washed with brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-2e1f28c0771a44b3a1a135255e726141
出典データセット
uspto-grants-1980_09
特許番号
US04221914

反応ノート

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