Amide derivatives, and preparation method and application thereof to medicines
A compound, selected technology, applied in the direction of pharmaceutical formulations, drug combinations, medical preparations containing active ingredients, etc.
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[0135] Example 1
[0136] (R)-1-(4-((S)-1-(3,5-Dimethyl-4-(4-(trifluoromethyl)-1H-pyrazol-1-yl)phenoxy) (Butyl)benzoyl)piperidine-3-carboxylic acid
[0137]
[0138] first step
[0139] Methyl 4-(1-hydroxybutyl)benzoate
[0140] Methyl p-formylbenzoate 1a (10.0 g, 60.92 mmol) was dissolved in 100 mL of tetrahydrofuran, and propyl magnesium bromide (33.5 mL, 67.0 mmol) was added at -78°C, and reacted at room temperature for 3 hours. 300mL ethyl acetate was added, washed with saturated ammonium chloride solution (200mL) and saturated sodium chloride solution (200mL), the organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue obtained was subjected to silica gel column chromatography ( Eluent: petroleum ether: ethyl acetate system) to obtain methyl 4-(1-hydroxybutyl)benzoate 1b (8.66g, colorless liquid), yield: 68.0%
[0141] MS m / z(ESI): 209.0[M+1]
[0142] Second step
[0143] Methyl 4-butyryl benzoate
[0144] Dissolve methyl 4-(1-hyd...
Example Embodiment
[0167] Example 2
[0168] (R)-1-(4-((S)-1-(3,5-Dimethyl-4-(4-(trifluoromethyl)-1H-pyrazol-1-yl)phenoxy) (Butyl)-2-fluorobenzoyl)piperidine-3-carboxylic acid
[0169]
[0170] first step
[0171] Methyl 2-fluoro-4-(1-hydroxybutyl)benzoate
[0172] Methyl 2-fluoro-4-formylbenzoate 2a (3.0g, 16.5mmol) was dissolved in 60mL of tetrahydrofuran, and under nitrogen protection, while stirring at -78°C, propylmagnesium bromide (8.6mL, 17.3mmol) was slowly added , React at room temperature for 2 hours. The reaction solution was cooled to 0°C, saturated ammonium chloride solution (30 mL) was slowly added, and the mixture was extracted with ethyl acetate (20 mL x 3). The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue obtained was subjected to silica gel column chromatography Purification method (eluent: petroleum ether: ethyl acetate system) to obtain methyl 2-fluoro-4-(1-hydroxybutyl)benzoate 2b (850mg, colorless liquid), yield: 23.0...
Example Embodiment
[0199] Example 3
[0200] (S)-1-(4-((S)-1-(3,5-Dimethyl-4-(4-(trifluoromethyl)-1H-pyrazol-1-yl)phenoxy) (Butyl)-2-fluorobenzoyl)piperidine-3-carboxylic acid
[0201]
[0202] first step
[0203] (S)-1-(2-Fluoro-4-(R)-1-hydroxybutyl)benzoylpiperidinyl)-3-carboxylic acid ethyl ester
[0204] The (R)-2-fluoro-4-(1-hydroxybutyl)benzoic acid 2e (150mg, 0.71mmol), (S)-piperidine-3-carboxylic acid ethyl ester 3a (142uL, 0.92mmol), double ( 2-oxo-3-oxazolidinyl) hypophosphorous oxychloride (270mg, 1.06mmol) and N,N-diisopropylethylamine (0.50mL, 2.82mmol) were dissolved in 5mL tetrahydrofuran, and the reaction solution was at room temperature React for 2 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (developing solvent: petroleum ether: ethyl acetate system) to obtain (S)-1-(2-fluoro-4-(R)-1 -Hydroxybutyl)benzoylpiperidinyl)-3-carboxylic acid ethyl ester 3b (250 mg, colorless liquid), yield: ...
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