반응 #1017403

ord-ad328b90562c4ab58653bfdc5affeedd

용매

반응 조건

온도
85°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타Step 2 In a sealed tube was combined
  2. 2
    기타The flask was sealed
  3. 3
    온도The reaction mixture was cooled to RT
  4. 4
    기타purified by flash chromatography (5% MeOH/dichloromethane)

실험 절차

To a stirred solution of (E)-3-(2-(4-methoxybenzylamino)-6-bromoquinolin-3-yl)-N-(cyclohexylmethyl)acrylamide (representative compound 10; 3.7 g, 7.3 mmol) in DME (100 mL) was added 4-methylbenzenesulfonohydrazide (13.6 g, 72.8 mmol). The mixture was brought to reflux at 86° C. and then via addition funnel was added dropwise a solution of sodium acetate (10.4 g, 127 mmol) in water (60 mL) over 1.5 h. Once the addition was complete, the reaction was refluxed for an additional 30 min, and then cooled to RT and concentrated to remove organic solvent. The crude material was dissolved in DCM (150 mL) and washed sequentially with 1N NaOH, 1N HCl, and then water. The organic layer was dried over MgSO4, filtered and concentrated to give a yellow oil. Purification via flash chromatography (5% EtOAc/dichloromethane) afforded 3-(2-(4-methoxybenzylamino)-6-bromoquinolin-3-yl)-N-(cyclohexylmethyl)propanamide (representative compound 11). Step 2 In a sealed tube was combined 3-(2-(4-methoxybenzylamino)-6-bromoquinolin-3-yl)-N-(cyclohexylmethyl)propanamide (0.16 g, 0.31 mmol), 2-chlorophenylboronic acid (0.074 g, 0.47 mmol), bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (0.0044 g, 0.0063 mmol), potassium acetate (0.062 g, 0.63 mmol), EtOH (6.0 ml) and water (0.41 mL). The flask was sealed and heated in an oil bath at 85° C. for 16 h. The reaction mixture was cooled to RT, adsorbed onto silica and purified by flash chromatography (5% MeOH/dichloromethane) to afford 3-(2-(4-methoxybenzylamino)-6-(2-chlorophenyl)quinolin-3-yl)-N-(cyclohexylmethyl)propanamide. Step: 3 Following the same procedure as in Step 9 of Scheme II, 3-(2-amino-6-(2-chlorophenyl)quinolin-3-yl)-N-(cyclohexylmethyl)propanamide (representative compound 6) was obtained after 3 hours of refluxing in TFA. MS (ESI, pos. ion) m/z: 422 (M+1).

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US09296698B2uspto-grants-2016_03