Sodium borohydride → Phenylmethyl 4-[(4-amino-3-methylphenyl)oxy]-1-piperidinecarboxylate

HRID 419314ノート

反応式

HRID 419314 の反応式
[CH3:1][C:2]1[CH:3]=[C:4]([O:11][CH:12]2[CH2:17][CH2:16][N:15]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[CH2:14][CH2:13]2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-])=O.[BH4-].[Na+]>CO.O.O.O.O.O.O.[Ni](Cl)Cl>[NH2:8][C:7]1[CH:6]=[CH:5][C:4]([O:11][CH:12]2[CH2:13][CH2:14][N:15]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[CH2:16][CH2:17]2)=[CH:3][C:2]=1[CH3:1]

参加物

5

反応物 2

HCID 4311764Sodium borohydride2 回HCID 59452627Phenylmethyl 4-[(3-methyl-4-nitrophenyl)oxy]-1-piperidinecarboxylate

生成物 1

HCID 59452998Phenylmethyl 4-[(4-amino-3-methylphenyl)oxy]-1-piperidinecarboxylate収率 78%

試薬・触媒・溶媒 2

HCID 11791229Dichloronickel;hexahydrate触媒HCID 887Methanol溶媒

反応条件

温度
0 °C

実験手順

Phenylmethyl 4-[(3-methyl-4-nitrophenyl)oxy]-1-piperidinecarboxylate (0.798 g, 2.15 mmol) was dissolved in 20 mL of MeOH with stirring. Nickel(II) chloride hexahydrate (0.256 g, 1.08 mmol) was added and the mixture was cooled to 0° C. Sodium borohydride (0.163 g, 4.31 mmol) was added, and the mixture was stirred for 20 min. Additional sodium borohydride (˜20 to 30 mg) was added, and the mixture was stirred for 10 min more. The reaction was quenched by the addition of approximately 15 mL of 2N sodium hydroxide solution. The mixture was poured into EtOAc and H2O, and the layers were separated. The organic layer was washed with brine, and the combined aqueous layers were extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography to afford 0.568 g (78%) of the title compound. 1H NMR (400 MHz, DMSO-d6) δ 7.40-7.23 (m, 5H), 6.61-6.43 (m, 3H), 5.04 (s, 2H), 4.37 (s, 2H), 4.27-4.17 (m, 1H), 3.74-3.57 (m, 2H), 3.27-3.12 (m, 2H), 1.97 (s, 3H), 1.86-1.73 (m, 2H), 1.52-1.39 (m, 2H).

後処理

  1. stirringthe mixture was stirred for 20 min
  2. stirringthe mixture was stirred for 10 min more
  3. customThe reaction was quenched by the addition of approximately 15 mL of 2N sodium hydroxide solution
  4. additionThe mixture was poured into EtOAc and H2O
  5. customthe layers were separated
  6. washThe organic layer was washed with brine
  7. extractionthe combined aqueous layers were extracted with EtOAc
  8. dry with materialThe combined organic layers were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-33c24dd0a3ba4109acc3d8039899090e
出典データセット
uspto-grants-2012_01
特許番号
US08093239B2

反応ノート

読み込み中…