Hydrochloric Acid → 4-Fluoro-2-pyrazol-1-yl-benzylamine hydrochloride

HRID 1726668Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1726668
[F:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([N:10]2[CH:14]=[CH:13][CH:12]=[N:11]2)[CH:3]=1.[ClH:15].[H][H]>CCO.CCOC(C)=O.[Pd]>[ClH:15].[F:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][NH2:7])=[C:4]([N:10]2[CH:14]=[CH:13][CH:12]=[N:11]2)[CH:3]=1

Komponenten

7

Edukt 3

HCID 313Hydrochloric Acid2×HCID 210699164-Fluoro-2-pyrazol-1-yl-benzonitrileHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 210699174-Fluoro-2-pyrazol-1-yl-benzylamine hydrochlorideAusbeute 58,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23938PalladiumKatalysator2×HCID 702EthanolLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a solution of 4-fluoro-2-pyrazol-1-yl-benzonitrile (500 mg, 2.67 mmol) in EtOH (10 mL) and EtOAc (10 mL) was added conc-HCl (0.25 mL, 3 mmol) and 10% Pd—C (100 mg). The mixture was hydrogenated at 1 atmosphere hydrogen for 20 h. To the mixture was added additional conc-HCl (0.15 mL) and 10% Pd—C (100 mg) and the mixture was further hydrogenated for additional 20 h. The mixture was filtered over Celite, washed with EtOH, and the combined filtrate and washings were concentrated in vacuo. The residual material was triturated with EtOH to obtain 356 mg of the title compound as the hydrochloride salt as an off-white crystalline solid: HPLC rt=1.01 min. LC/MS m/z 192 (M+H); 1H NMR (DMSO-d6, 500 MHz) δ ppm 3.99 (2H, s, 7-CH2), 6.63 (1H, t, J=2 Hz, 9-CH), 7.40 (1H, dt, J=8.5, 2.5 Hz, 5-CH), 7.54 (1H, dd, J=10, 2.5 Hz, 3-CH) 7.81 (1H, dd, J=8.5, 6 Hz, 6-CH), 7.86 (1H, d, J=1.5 Hz, 10-CH) 8.35 (1H, d, J=2 Hz, 8-CH), 8.54 (3H, br.s, NH3+); 13C NMR (DMSO-d6, 125.8 Hz) δ ppm 38.8 (7-CH2), 107.7 (9-CH2), 111.6 (d, J=25 Hz, 3-CH), 114.6 (d, J=21 Hz, 5-CH), 123.7 (d, J=3 Hz, 1-C), 131.7 (8-CH), 134.0 (d, J=9 Hz, 6-CH), 140.4 (d, J=11 Hz, 2-C), 141.5 (10-CH), 161.9 (d, J=247 Hz, 6-CF); HRMS (ESI) calcd for C10H11FN3 (M+H) 192.0937, found 192.0930 (δ-3.6 ppm).

Aufarbeitung

  1. filtrationThe mixture was filtered over Celite
  2. washwashed with EtOH
  3. concentrationthe combined filtrate and washings were concentrated in vacuo
  4. customThe residual material was triturated with EtOH

Quellen und Nachweise

ORD-Eintrag
ord-d7861d1c99f547519139941d09362673
Quelldatensatz
uspto-grants-2009_02
Patentnummer
US07491819B1

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