Novel aminopyridine derivatives having aurora a selective inhibitory action
a technology of aminopyridine and selective inhibitory action, which is applied in the direction of heterocyclic compound active ingredients, biocide, drug compositions, etc., can solve the problems of difficult development of subtype-selective drugs, and achieve the effect of improving the activity of natural killer cells
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[0449]In a thin-layer chromatography of Examples and Referential Examples, Silica gel60F254 (Merck) was used as a plate and a UV detector was used as a detecting method. As silica gel for the column, Biotage FLASH column (SI, NH) was used. In a reversed phase preparative liquid chromatography, XBridge Prep C18 (Waters) was used as a column and a 0.1% aqueous trifluoroacetic acid solution and a 0.1% solution of trifluoroacetic acid in acetonitrile were used in a mobile phase. MS spectra were measured using Waters micromass ZQ2000 (ESI, ESCi). NMR spectra were measured using a spectrometer in the type of JEOL JNM-AL400 (400 MHz) or Varian MERCURY400 (400 MHz) and all δ values are represented in ppm. Melting points were measured under a 1° C. / min raise condition using a combination of Mettler Toledo FP82HT Hot Stage and NIKON Eclipse E600 POL.
[0450]Meanings of abbreviations are as follows.[0451]s: singlet[0452]d: doublet[0453]dd: double doublet[0454]t: triplet[0455]dt: double triplet[0...
example 1
Synthesis of trans-4-(3-chloro-2-fluorophenoxy)-1-((6-(1,3-thiazol-2-ylamino)pyridin-2-yl)methyl)cyclohexanecarboxylic acid hydrochloride
[0468]
(1) Synthesis of 2-bromo-6-(((tert-butyl(dimethyl)silyl)oxy)methyl)pyridine
[0469]
[0470]To a solution of 10 g of (6-bromo-pyridin-2-yl)methanol in 50 ml of N,N-dimethylformamide were successively added 4 g of imidazole and 8.4 g of tert-butyldimethylsilyl chloride at room temperature, followed by stirring the reaction mixture at room temperature for 2 hours. After adding water to the reaction mixture, the mixture was extracted with n-hexane. The resulting hexane solution was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give the title compound as colorless oil.
(2) Synthesis of 6-(((tert-butyl(dimethyl)silyl)oxy)methyl)-N-((2Z)-3-(methoxymethyl)-1,3-thiazol-2(3H)-ylidene)pyridin-2-amine
[0471]
[0472]A mixture of 15.92 g of 2-bromo-6-(((tert-butyl(dimethyl)silyl)oxy)methyl)pyridine, 5.53 g of 2-amin...
example 2
Synthesis of trans-4-(3-chloro-2-fluorophenoxy)-1-(6-(1,3-thiazol-2-ylamino)pyridin-2-yl)methyl)cyclohexanecarboxylic acid
[0489]
[Method A]
[0490]To a 47.9 mg of trans-4-(3-chloro-2-fluorophenoxy)-1-(6-(1,3-thiazol-2-ylamino)pyridin-2-yl)methyl)cyclohexanecarboxylic acid hydrochloride as obtained in Example 1 were successively added 4 ml of water and 4 ml of ethanol, followed by stirring the reaction mixture at room temperature for 12 hours. The resulting precipitate was collected by filtration and washed with water to give the title compound as a colorless needle (mp: 202-222° C.).
[0491]1H-NMR (DMSO-d6) δ: 1.60-1.92 (8H, m), 2.98 (2H, s), 4.61 (1H, brs), 6.71 (1H, d, J=7.2 Hz), 6.90 (1H, d, J=8.2 Hz), 6.98 (1H, d, J=3.5 Hz), 7.10-7.22 (3H, m), 7.38 (1H, d, J=3.5 Hz), 7.60 (1H, t, J=7.6 Hz).
[0492]mass: 462,464 (M+1)+
[Method B]
[0493]To 460 mg of trans-4-(3-chloro-2-fluorophenoxy)-1-(6-(1,3-thiazol-2-ylamino)pyridin-2-yl)methyl)cyclohexanecarboxylic acid hydrochloride as obtained in Exa...
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