Potassium hydroxy sulfite → (R)-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1lambda6-thiomorpholin-3-one

HRID 920156ノート

反応式

HRID 920156 の反応式
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:27])=[C:6]([C@@:8]2([CH3:26])[N:13]([CH2:14][C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][C:16]=3[O:23][CH3:24])[C:12](=[O:25])[CH2:11]S[CH2:9]2)[CH:7]=1.O[O:29][S:30]([O-:32])=O.[K+]>CO>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([F:27])=[C:6]([C@@:8]2([CH3:26])[N:13]([CH2:14][C:15]3[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][C:16]=3[O:23][CH3:24])[C:12](=[O:25])[CH2:11][S:30](=[O:32])(=[O:29])[CH2:9]2)[CH:7]=1

参加物

4

反応物 2

HCID 23707502Potassium hydroxy sulfiteHCID 90016345(R)-5-(5-bromo-2-fluorophenyl)-4-(2,4-dimethoxybenzyl)-5-methylthiomorpholin-3-one

生成物 1

HCID 90067087(R)-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1lambda6-thiomorpholin-3-one収率 95%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
23 °C

実験手順

To a solution of (R)-5-(5-bromo-2-fluorophenyl)-4-(2,4-dimethoxybenzyl)-5-methylthiomorpholin-3-one (2.95 g, 6.49 mmol, Eq: 1.00) in methanol (100 ml) was added at 23° C. Oxone® (7.98 g, 13.0 mmol, Eq: 2.00). The reaction mixture was stirred at 23° C. for 16 hours. The reaction mixture was carefully quenched by addition of water at 0° C., then 10 ml of a diluted NaHSO3-solution, sat. NaHCO3-solution and ethyl acetate were added. Vigorous stirring was continued for 10 min. The organic layer was separated and washed with water, then dried over Na2SO4, filtered and evaporated to give a yellow oil which was chromatographed on 20 g silica gel with 0-50% ethyl acetate in heptane to give (R)-5-(5-bromo-2-fluoro-phenyl)-4-(2,4-dimethoxy-benzyl)-5-methyl-1,1-dioxo-1λ6-thiomorpholin-3-one (3 g, 6.17 mmol, 95.0% yield) as a white foam. MS (ISP): m/z=486.2 [M+H]+ and 488.1 [M+2+H]+.

後処理

  1. customThe reaction mixture was carefully quenched by addition of water at 0° C.
  2. addition10 ml of a diluted NaHSO3-solution, sat. NaHCO3-solution and ethyl acetate were added
  3. stirringVigorous stirring
  4. waitwas continued for 10 min
  5. customThe organic layer was separated
  6. washwashed with water
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customevaporated
  10. customto give a yellow oil which
  11. customwas chromatographed on 20 g silica gel with 0-50% ethyl acetate in heptane

出典と根拠

ORDレコード
ord-d6045364a194485bb373245e1c9e07a1
出典データセット
uspto-grants-2016_03
特許番号
US09273042B2

反応ノート

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