Acetic Acid → 1-[(6-Chloropyridin-3-yl)methyl]-4-methylpiperazine

HRID 1431142Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1431142
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][N:3]=1.[CH3:10][N:11]1[CH2:16][CH2:15][NH:14][CH2:13][CH2:12]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl.O>[Cl:1][C:2]1[N:3]=[CH:4][C:5]([CH2:6][N:14]2[CH2:15][CH2:16][N:11]([CH3:10])[CH2:12][CH2:13]2)=[CH:8][CH:9]=1

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 531671-MethylpiperazineHCID 27640536-Chloropyridine-3-carbaldehydeHCID 5049666Sodium triacetoxyborohydride

Produkt 1

HCID 14735211-[(6-Chloropyridin-3-yl)methyl]-4-methylpiperazineAusbeute 84,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

6-Chloronicotinaldehyde (10 g, 70.6 mmol, Eq: 1.00) was suspended in 700 ml DCM. 1-Methylpiperazine (8.84 g, 88.3 mmol, Eq: 1.25) and acetic acid (8.48 g, 8.09 ml, 141 mmol, Eq: 2.0) were added. Sodium triacetoxyborohydride (22.5 g, 106 mmol, Eq: 1.5) was added in portions over several minutes. The reaction mixture stirred at room temperature. After 3.5 hrs, there was no sign of starting material. LCMS showed product plus a little reduced starting material. Water was added, followed by DCM and the layers were separated. The DCM layer was washed with saturated ammonium chloride and the aqueous layer was combined with the initial aqueous layer. The aqueous extractions were bacidified with 1M NaOH. The resulting aqueous layer was extracted 3 times with DCM, and then dried, and concentrated to give 13.5 grams of a light yellow oil (84.7%) which was used without further purification.

Aufarbeitung

  1. customthe layers were separated
  2. washThe DCM layer was washed with saturated ammonium chloride
  3. extractionThe aqueous extractions
  4. extractionThe resulting aqueous layer was extracted 3 times with DCM
  5. customdried
  6. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-7dfe59dce7784cc8a400c1cee87268aa
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08940741B2

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