Oxalyl chloride → 1-(3-Methoxy-4-nitrophenyl)piperidin-4-one

HRID 419358ノート

反応式

HRID 419358 の反応式
C(Cl)(=O)C(Cl)=O.[CH3:7][O:8][C:9]1[CH:10]=[C:11]([N:18]2[CH2:23][CH2:22][CH:21]([OH:24])[CH2:20][CH2:19]2)[CH:12]=[CH:13][C:14]=1[N+:15]([O-:17])=[O:16]>C(Cl)Cl.CS(C)=O>[CH3:7][O:8][C:9]1[CH:10]=[C:11]([N:18]2[CH2:23][CH2:22][C:21](=[O:24])[CH2:20][CH2:19]2)[CH:12]=[CH:13][C:14]=1[N+:15]([O-:17])=[O:16]

参加物

5

反応物 2

HCID 65578Oxalyl chlorideHCID 259188601-(3-Methoxy-4-nitrophenyl)piperidin-4-ol

生成物 1

HCID 259188571-(3-Methoxy-4-nitrophenyl)piperidin-4-one収率 98.3%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒2 回HCID 6344Dichloromethane溶媒3 回

反応条件

温度
-78 °C

実験手順

Oxalyl chloride (11.9 mL, 23.78 mmol) was dissolved in DCM (200 mL) and cooled to −78° C. DMSO (3.4 mL, 47.58 mmol) in DCM (15 mL) was added to the solution dropwise via an addition funnel. Upon completion of addition, the reaction was allowed to stir 10 min. 1-[3-(methyloxy)-4-nitrophenyl]-4-piperidinol (4.04 g, 15.86 mmol) in DMSO (6 mL) and DCM (15 mL) was added dropwise via addition funnel. Upon completion of addition, the reaction was allowed to stir 15 minutes. TEA (11.0 mL, 79.3 mmol) was then added dropwise via addition funnel. Upon completion of addition, the bath was removed and the reaction was allowed to warm to rt. The reaction was stirred until alcohol was consumed as indicated by TLC. The solvent was removed in vacuo and the residue was taken up in EtOAc. The suspension was washed twice with H2O, followed by brine. The organic layer was dried with MgSO4, filtered and concentrated to provide the title compound of step B (3.91 g, 15.59 mmol, 97%) as a bright yellow solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.47-2.51 (m, 4H), 3.82 (t, J=6.2 Hz, 4H), 3.91 (s, 3H), 6.52 (d, J=2.6 Hz, 1H), 6.61 (dd, J=9.5, 2.6 Hz, 1H), 7.91 (d, J=9.5 Hz, 1H).

後処理

  1. additionUpon completion of addition
  2. additionUpon completion of addition
  3. stirringto stir 15 minutes
  4. additionUpon completion of addition
  5. customthe bath was removed
  6. temperatureto warm to rt
  7. stirringThe reaction was stirred until alcohol
  8. customwas consumed
  9. customThe solvent was removed in vacuo
  10. washThe suspension was washed twice with H2O
  11. dry with materialThe organic layer was dried with MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated

出典と根拠

ORDレコード
ord-3d06461a6c4b427d83cde11c13ecca4b
出典データセット
uspto-grants-2012_01
特許番号
US08093239B2

反応ノート

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