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

HRID 1372339노트

반응식

HRID 1372339 반응식
[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

참가 물질

7

반응물 3

HCID 313Hydrochloric Acid2회HCID 210699164-Fluoro-2-pyrazol-1-yl-benzonitrileHCID 178418361HCID 178418361, 화합물

생성물 1

HCID 210699174-Fluoro-2-pyrazol-1-yl-benzylamine hydrochloride수율 58.6%

시약·촉매·용매 3

HCID 23938Palladium촉매2회HCID 702Ethanol용매HCID 8857Ethyl Acetate용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-940d75488da74fa28213d56427632a61
출처 데이터셋
uspto-grants-2007_01
특허 번호
US07157447B2

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