Ammonium Chloride → HCID 86713636、化合物

HRID 1430482ノート

反応式

HRID 1430482 の反応式
[F:1][C:2]1[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[CH:12][C:3]=1[CH2:4][N:5]1[CH2:10][CH2:9][N:8]([CH3:11])[CH2:7][CH2:6]1.[NH4+].[Cl-]>CCO.[Fe]>[F:1][C:2]1[CH:15]=[CH:14][C:13]([NH2:16])=[CH:12][C:3]=1[CH2:4][N:5]1[CH2:10][CH2:9][N:8]([CH3:11])[CH2:7][CH2:6]1

参加物

5

反応物 2

HCID 25517Ammonium ChlorideHCID 86713635HCID 86713635、化合物

生成物 1

HCID 86713636HCID 86713636、化合物収率 75.1%

試薬・触媒・溶媒 2

HCID 23925Iron触媒HCID 702Ethanol溶媒

反応条件

温度
55 °C

実験手順

A solution of 1-(2-fluoro-5-nitrobenzyl)-4-methylpiperazine (0.577 g, 2.278 mmol) in EtOH (7 mL) was treated with satd. NH4Cl (4.75 mL, 22.78 mmol) followed by iron (powder) (1.272 g, 22.78 mmol) and the mixture heated at 55° C. overnight. The mixture was cooled to RT and gravity-filtered through filter paper, rinsing well with MeOH and DCM. The filtrate was concentrated to dryness. The residue was treated with EtOAc and water, then concentrated to dryness again. The resulting material was treated with THF (20 mL), sonicated for several hours and the solvent decanted from the solids. The solids were treated with additional THF (20 mL), sonicated again and the solvent decanted. The solids were treated with THF (20 mL) for a third time, stirred vigorously overnight, then the liquid was decanted. The combined decanted liquids were concentrated to dryness, treated with DCM, filtered to remove solids and concentrated to dryness to afford very hydroscopic 4-fluoro-3-((4-methylpiperazin-1-yl)methyl)aniline (382 mg, 75% yield). 1H NMR (400 MHz, DMSO-d6): δ 6.81 (m, 1H), 6.49 (m, 2H), 4.99 (s, 2H), 3.44 (s, 2H), 3.32 (s, 8H), 2.69 (s, 3H); MS (ESI) m/z: 224.2 [M+H]+.

後処理

  1. temperatureThe mixture was cooled to RT
  2. filtrationgravity-filtered
  3. filtrationthrough filter paper
  4. washrinsing well with MeOH and DCM
  5. concentrationThe filtrate was concentrated to dryness
  6. additionThe residue was treated with EtOAc and water
  7. concentrationconcentrated to dryness again
  8. additionThe resulting material was treated with THF (20 mL)
  9. customsonicated for several hours
  10. customthe solvent decanted from the solids
  11. additionThe solids were treated with additional THF (20 mL)
  12. customsonicated again
  13. customthe solvent decanted
  14. additionThe solids were treated with THF (20 mL) for a third time
  15. customthe liquid was decanted
  16. customThe combined decanted liquids
  17. concentrationwere concentrated to dryness
  18. additiontreated with DCM
  19. filtrationfiltered
  20. customto remove solids
  21. concentrationconcentrated to dryness

出典と根拠

ORDレコード
ord-b1c4aa1ffa694cfd99dc27d8d1b326e5
出典データセット
uspto-grants-2015_01
特許番号
US08940756B2

反応ノート

読み込み中…