(S)-4-methylbenzenesulfinamide → (R)-4-methylbenzenesulfinic acid [2-(4-chlorophenyl)-2-methylpropyliden]-amide

HRID 1192383ノート

反応式

HRID 1192383 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([CH3:12])([CH3:11])[CH:9]=O)=[CH:4][CH:3]=1.[CH3:13][C:14]1[CH:19]=[CH:18][C:17]([S@@:20]([NH2:22])=[O:21])=[CH:16][CH:15]=1>C(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([CH3:12])([CH3:11])[CH:9]=[N:22][S@@:20]([C:17]2[CH:18]=[CH:19][C:14]([CH3:13])=[CH:15][CH:16]=2)=[O:21])=[CH:4][CH:3]=1

参加物

4

反応物 2

HCID 11116285(S)-4-methylbenzenesulfinamideHCID 114353342-(4-Chlorophenyl)-2-methylpropanal

生成物 1

HCID 69790886(R)-4-methylbenzenesulfinic acid [2-(4-chlorophenyl)-2-methylpropyliden]-amide

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

The 2-(4-chlorophenyl)-2-methylpropionaldehyde (5.60 g, 30.7 mmol) and (S)-4-methyl-benzenesulfinic acid amide (5.00 g, 32.2 mmol) were dissolved in 300 mL of DCM and treated with Ti(OEt)4 (32.1 mL, 153 mmol). The mixture was heated to reflux under nitrogen for four hours. The solution was cooled in an ice bath and quenched with the dropwise-addition of 200 mL of water. The resulting precipitate (Ti salts) were removed by filtration through a plug of celite and washed with DCM. The resulting filtrate was separated, and the aqueous was extracted with more DCM. The combined organic was dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by filtration through a plug of silica gel (hexanes:ethyl acetate, 1:1) to afford the (R)-4-methylbenzenesulfinic acid [2-(4-chlorophenyl)-2-methylpropyliden]-amide as a colorless oil, which solidified upon standing to give a white solid (9.28 g, 95%). 1H NMR (CDCl3, 400 MHz) δ 8.14 (s, 1H), 7.54 (d, J=8.4 Hz, 2H), 7.31 (d, J=8.8 Hz, 2H), 7.27 (d, J=8.8 Hz, 2H), 7.14 (m, 2H), 2.42 (s, 3H), 1.52 (s, 3H), 1.47 (s, 3H).

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux under nitrogen for four hours
  3. temperatureThe solution was cooled in an ice bath
  4. customquenched with the dropwise-addition of 200 mL of water
  5. customThe resulting precipitate (Ti salts) were removed by filtration through a plug of celite
  6. washwashed with DCM
  7. customThe resulting filtrate was separated
  8. extractionthe aqueous was extracted with more DCM
  9. dry with materialThe combined organic was dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. filtrationThe residue was purified by filtration through a plug of silica gel (hexanes:ethyl acetate, 1:1)

出典と根拠

ORDレコード
ord-18cbe83a10e44007b92aad33a2e346eb
出典データセット
uspto-grants-2014_03
特許番号
US08680114B2

反応ノート

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