Novel crystal of (3S)-3-[2-(6-amino-2-fluoropyridine-3-yl)-4-fluoro-1h-imidazole-5-yl]-7-[5-chloro-2-(1h-tetrazole-1-yl)phenyl]-2,3-dihydroindolizine-5(1H)-one
A technology of indolinazine and fluoropyridine, applied in (3S)-3-[2-(6-amino-2-fluoropyridin-3-yl)-4-fluoro-1H-imidazol-5-yl Novel crystal field of ]-7-[5-chloro-2-(1H-tetrazol-1-yl)phenyl]-2,3-dihydroindorazin-5(1H)-one capable of resolving bleeding complications Symptoms are the problem, the drug does not show sufficient antithrombotic effect, etc.
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[0169] The present invention will be described in detail by referring to the following examples, but the present invention is not limited to the examples.
[0170] Regarding chromatographic separation or TLC, solvents in parentheses correspond to employed elution solvents or developing solvents, and ratios are expressed by volume ratios.
[0171] Regarding NMR, solvents in parentheses correspond to solvents used for measurement.
[0172] Compound names used in this specification are usually named according to IUPAC rules using the computer program ACD / Name (registered trademark) given by Advanced Chemistry Development, or by IUPAC nomenclature.
[0173] The measurement times, solvents and column conditions used for LC / MS analysis in the following examples are shown below. At the same time, t R Indicates the retention time.
[0174] Condition a. Column YMC-Triart C18, 2.0mm×30mm, 1.9μm; column temperature 30°C; mobile phase (liquid A) 0.1% trifluoroacetic acid aqueous soluti...
Embodiment 1
[0177] Example 1(1): 6-fluoro-5-iodo-2-pyridinamine
[0178] Under ice cooling, N-iodosuccinimide (56.5 g) was added in multiple portions (3 parts) to 6-fluoro-2-pyridinamine (25.6 g) in N,N-dimethylformamide (200 mL ) in the solution. The mixture was stirred at room temperature for 3 hours, and tap water (0.5 L) was added to the reaction solution. The mixture was extracted 3 times with ethyl acetate / hexane (1 / 1, 300 mL), and the organic layer was washed with saturated aqueous sulfurous acid (0.5 L), saturated aqueous sodium carbonate (0.5 L, twice), tap water (0.5 L ) and saturated brine (0.5 L), dried, and concentrated. To the obtained residue was added hexane / ethyl acetate (3 / 1, 150 mL), and the slurry was washed at room temperature, and filtered. The obtained solid was dried to obtain the title compound (36.7 g) having the following physical properties.
[0179] TLC: Rf 0.56 (ethyl acetate:hexane=1:2).
[0180] Example 1(2): Bis(2-methyl-2-propenyl)(6-fluoro-5-iod...
Embodiment 2
[0240] Example 2: (3R)-3-[2-(6-amino-2-fluoropyridin-3-yl)-4-fluoro-1H-imidazol-5-yl]-7-[5-chloro- 2-(1H-tetrazol-1-yl)phenyl]-2,3-indolinazin-5(1H)-one-3,5-dihydroxybenzoic acid (2 / 1)
[0241] To the compound of Example 1(13) (20 mg) were added 3,5-dihydroxybenzoic acid (2.83 mg) and acetonitrile (100 μL). The resulting mixture was stirred at 25°C for 1 day to obtain a precipitate. The precipitate was filtered off, and then dried in air to obtain a crystal of the title compound having the following physical property values.
[0242] 1 H-NMR (DMSO-d6): 11.70, 9.65, 9.13, 7.86-7.75, 7.14-7.13, 6.96-6.92, 6.78-6.75, 6.40-6.36, 6.00, 5.92, 5.71, 5.68, 3.32, 3.20-2.93, 2.27 -2.20.
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![Novel crystal of (3S)-3-[2-(6-amino-2-fluoropyridine-3-yl)-4-fluoro-1h-imidazole-5-yl]-7-[5-chloro-2-(1h-tetrazole-1-yl)phenyl]-2,3-dihydroindolizine-5(1H)-one](https://images-eureka.patsnap.com/patent_img/105793d0-b9c8-4d4a-acfb-e4173ecfedf1/HDA0003092990510000011.png)
![Novel crystal of (3S)-3-[2-(6-amino-2-fluoropyridine-3-yl)-4-fluoro-1h-imidazole-5-yl]-7-[5-chloro-2-(1h-tetrazole-1-yl)phenyl]-2,3-dihydroindolizine-5(1H)-one](https://images-eureka.patsnap.com/patent_img/105793d0-b9c8-4d4a-acfb-e4173ecfedf1/HDA0003092990510000021.png)
![Novel crystal of (3S)-3-[2-(6-amino-2-fluoropyridine-3-yl)-4-fluoro-1h-imidazole-5-yl]-7-[5-chloro-2-(1h-tetrazole-1-yl)phenyl]-2,3-dihydroindolizine-5(1H)-one](https://images-eureka.patsnap.com/patent_img/105793d0-b9c8-4d4a-acfb-e4173ecfedf1/HDA0003092990510000031.png)