Bicyclic heterocyclic derivatives
A technology of compounds and mixtures, applied in drug combination, organic active ingredients, organic chemistry, etc., can solve problems such as hyperglycemia
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Embodiment 1
[0261] (2R)-1-[1-(4-chlorophenyl)-6,7-dihydro-4H-pyrazolo[4,3-c]pyridin-5-yl]-3,3,3-tri Fluoro-2-hydroxy-2-methyl-propan-1-one ("A1")
[0262]
[0263] 1.1 tert-butyl 1-(4-chloro-phenyl)-1,4,6,7-tetrahydro-pyrazolo[4,3-c]pyridine-5-carboxylate
[0264] 3-[1-Dimethylamino-methyl-(E)-ylidene]-4-oxo-piperidine-1-carboxylic acid tert-butyl ester (200 mg, 0.786 mmol) and 4-chlorophenylhydrazine hydrochloride The salt (155 mg, 0.865 mmol) was suspended in methanol (4 mL) and water (1 mL). While stirring, glacial acetic acid (0.23 mL, 3.932 mmol) was added and an orange solution formed after a few minutes. The mixture was stirred at room temperature for 1 h, diluted with ethyl acetate, water, saturated NaHCO 3 solution and brine, washed with Na 2 SO 4 Dry, filter and evaporate to dryness. The oily residue was purified by flash chromatography (Companion RF, 40 g Si50 silica gel column). Yield: 145.5 mg brown oil; LC / MS, Rt: 2.61 min; (M+H) 334.1.
[0265] 1.2 1-(4-Chloro-ph...
Embodiment 2
[0271] (2R)-1-[2-(4-chlorophenyl)-6,7-dihydro-4H-pyrazolo[4,3-c]pyridin-5-yl]-3,3,3-tri Fluoro-2-hydroxy-2-methyl-propan-1-one ("A2")
[0272] "A2" as the isomeric cyclization product of step 1.1 was isolated in step 1.3 by preparative HPLC (Agilent 1260, column: Waters SunFire C18, 5 μm, 30×150 mm). Yield: 7mg (4%) colorless powder; LC / MS, Rt: 2.26min; (M+H) 374.1; 1 H NMR (500MHz, DMSO-d 6 ) δ 8.33 (s, 1H), 7.82-7.76(m, 2H), 7.55-7.50 (m, 2H), 7.21 (s, 1H), 5.16-4.94 (m, 1H), 4.69-4.50 (m,1H ), 4.28-4.02 (m, 1H), 3.94-3.68 (m, 1H), 2.93-2.68 (m, 2H), 1.66-1.45 (m, 3H).
Embodiment 3
[0274] (R)-3,3,3-Trifluoro-2-hydroxy-2-methyl-1-(1-phenyl-1,4,6,7-tetrahydro-pyrazolo[4,3-c ]pyridin-5-yl)-propan-1-one ("A3")
[0275]
[0276] Prepare as described in Example 1 (steps 1.1-1.3). Yield: 142mg (62%) colorless solid; LC / MS, Rt: 1.97min; (M+H) 340.1; 1 H NMR (400MHz, DMSO-d 6 ) δ 7.58-7.52 (m, 3H), 7.52-7.45(m, 2H), 7.38-7.31 (m, 1H), 6.87 (s, 1H), 4.73 (s, 2H), 4.09-3.90 (m, 2H ),2.91 (t, J =5.8Hz, 2H), 1.58 (s, 3H).
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