Potassium Carbonate → 1-(5-benzenesulfonyl-2-(S)-oxiranylmethoxy-phenyl)-ethanone

HRID 2221301ノート

反応式

HRID 2221301 の反応式
[CH2:1]([C@@H:3]1[O:5][CH2:4]1)Cl.[C:6]1([S:12]([C:15]2[CH:16]=[CH:17][C:18]([OH:24])=[C:19]([C:21](=[O:23])[CH3:22])[CH:20]=2)(=[O:14])=[O:13])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.C(OCC)(=O)C>[C:6]1([S:12]([C:15]2[CH:16]=[CH:17][C:18]([O:24][CH2:1][C@@H:3]3[CH2:4][O:5]3)=[C:19]([C:21](=[O:23])[CH3:22])[CH:20]=2)(=[O:14])=[O:13])[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 2734062(-)-EpichlorohydrinHCID 189877381-(5-Benzenesulfonyl-2-hydroxy-phenyl)-ethanone

生成物 1

HCID 866015571-(5-benzenesulfonyl-2-(S)-oxiranylmethoxy-phenyl)-ethanone

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

(R)-(−)Epichlorhydrin (1.93 g; 0.021 mol) was added to a suspension of 1-(5-benzenesulfonyl-2-hydroxy-phenyl)-ethanone (1.92 g; 0.007 mol) and potassium carbonate (1.44 g; 0.011 mol) in acetonitrile (5 mL). The mixture was heated under reflux for 18 hours. After cooling to ambient temperature, the mixture was diluted with ethyl acetate, filtered, washed with water and saturated sodium bicarbonate, dried (Na2SO4) and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel (hexane-ethyl acetate; 7:3) to give 1-(5-benzene sulfonyl-2-(S)-oxiranylmethoxy-phenyl)-ethanone as a white solid (1.456 g; 63%). A sample was recrystallized from diethyl ether-hexane: M. p. 115.1-116.8° C. Similarly, but replacing (R)-(−)epichlorhydrin with (S)-(+)epichlorhydrin, 1-(5-benzene sulfonyl-2-(R)-oxiranylmethoxy-phenyl)-ethanone was prepared. M. p. 111.9-113.5° C. Similarly, but replacing 1-(5-benzenesulfonyl-2-hydroxy-phenyl)-ethanone with 1-[5-(3-fluoro-benzenesulfonyl)-2-hydroxy-phenyl]-ethanone, the above procedure gave 1-[5-(3-fluoro-benzenesulfonyl)-2-(S)-oxiranylmethoxy-phenyl]-ethanone: M. p. 112.7-114.9° C. Replacing 1-(5-benzenesulfonyl-2-hydroxy-phenyl)-ethanone with 1-[5-(3-Fluoro-benzenesulfonyl)-2-hydroxy-phenyl]-ethanone and replacing (R)-(−)epichlorhydrin with (S)-(+)epichlorhydrin gave 1-[5-(3-Fluoro-benzenesulfonyl)-2-(R)-oxiranylmethoxy-phenyl]-ethanone. M. p. 118.3-120.5° C.

後処理

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 18 hours
  3. filtrationfiltered
  4. washwashed with water and saturated sodium bicarbonate
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified by flash chromatography on silica gel (hexane-ethyl acetate; 7:3)

出典と根拠

ORDレコード
ord-54ceaf446b4a49ef9ccd615e22eabadc
出典データセット
uspto-grants-2008_05
特許番号
US07368567B2

反応ノート

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