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

HRID 1192383노트

반응식

HRID 1192383 반응식
[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

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-18cbe83a10e44007b92aad33a2e346eb
출처 데이터셋
uspto-grants-2014_03
특허 번호
US08680114B2

반응 노트

불러오는 중…