Aminopyridine derivatives and uses thereof
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reference example 1
[0345] Reference Example 1: 5-Methyl-1-[5-(trifluoromethyl)pyridin-2-yl]-1H-pyrazole-4-carbonyl chloride
[0346] (1) Add 2-chloro-5-(trifluoromethyl)pyridine (25g) and hydrazine hydrate (100%) (100ml) to ethanol (60ml), stir at 100°C for 3 hours, and remove The reaction solution was concentrated, chloroform and water were added to the residue, the organic layer was separated, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and a 4N hydrochloric acid-ethanol solution was added to the residue to obtain 5-(three Fluoromethyl)pyridin-2-ylhydrazine hydrochloride (15.4 g). MS(ESI)m / z: 178(M+H) + .
[0347] (2) Next, ethyl 2-ethoxymethylene acetoacetate (6.1 g) synthesized according to the method described in J. Chem. Soc. Perkin trans. I), page 1875 (1988) and the above The 5-(trifluoromethyl)pyridin-2-ylhydrazine hydrochloride (7.0g) was added to a mixed solvent of water (40ml) and ethanol (40ml), stirred at reflux temperature for 3 hours, a...
reference example 2
[0349] Reference example 2: 1-(5-chloropyridin-2-yl)-5-methyl-1H-pyrazole-4-carboxylic acid
[0350] In Reference Example 1, 2,5-dichloropyridine was used instead of 2-chloro-5-(trifluoromethyl)pyridine, and the title compound was obtained by the same reaction and treatment as (1) and (2). MS(ESI)m / z: 238(M+H) + .
reference example 3
[0351] Reference Example 3: 1-(3,5-Dichloropyridin-2-yl)-5-methyl-1H-pyrazole-4-carboxylic acid
[0352] (1) Add 2,3,5-trichloropyridine (25g) and hydrazine monohydrate (109.8g) to ethanol (20ml), stir at 100°C, and then cool to room temperature. The resulting solid was collected by filtration to obtain 3,5-dichloropyridin-2-ylhydrazine (24.07 g).
[0353] (2) Next, 1N was added to ethyl 2-ethoxymethylene acetoacetate (25.1g) synthesized according to the method described in J.Chem.Soc.Perkin trans.I, page 1875 (1988) The aqueous solution of hydrochloric acid (135 ml) and the above-mentioned 3,5-dichloropyridin-2-ylhydrazine (24.02 g) in ethanol (135 ml) were stirred at reflux temperature for 3 hours and then cooled to room temperature. Water was added to the reaction solution, the resulting solid was filtered out, and purified with a mixed solvent of ethyl acetate / n-hexane to obtain 1-(3,5-dichloropyridin-2-yl)-5-methyl-1H -Ethyl pyrazole-4-carboxylate.
[0354] (3) Add 4N sodium ...
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