JAK inhibitor compound and application thereof
A compound and isomer mixture technology, applied in the field of novel compounds, can solve problems such as unsatisfactory efficacy or safety of JAK inhibitors
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Embodiment 1
[0509] Example 1: (2-(6-(2-ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)-4,6-dihydropyrrolo [3,4-d]imidazol-5(1H)-yl)(5-(piperidin-1-yl)pyrazin-2-yl)methanone (MDI-2)
[0510]
[0511] The synthetic route of target compound 8 (that is, MDI-2):
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[0513] Synthetic route of intermediate 10
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[0515] Synthetic route of intermediate 16
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[0517] Synthetic route of intermediate 20
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[0519] resolve resolution:
[0520] Synthetic intermediate 1: 6-bromo1H-indazole-3-carbaldehyde
[0521] Sodium nitrite (14.00g, 200mmol) was dissolved in 75ml DMF and 100ml water, cooled to 0°C, under nitrogen protection, 3N HCl (23ml, 68.9mmol) was slowly added dropwise, and the reaction was completed for 10 minutes. At 0°C, a solution of 6-bromoindole (5.00 g, 25.5 mmol) in DMF (35 ml) was slowly added dropwise to the reaction solution, and after the addition was complete, the reaction was carried out overnight at room temperature. Extracted 3...
Embodiment 2
[0578] Example 2: (2-(6-(2-ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)--4,6-dihydropyrrolo [3,4-d]imidazol-5(1H)-yl)(5-morpholinepyrazin-2-yl)methanone (MDI-201)
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[0580] The synthetic route of MDI-201:
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[0582] resolve resolution:
[0583] Synthetic intermediate MDI-201-1: methyl 5-morpholinepyrazine-2-carboxylate
[0584] Dissolve 5-chloro-pyrazine-2-carboxylic acid methyl ester (1.5g, 8.7mmol) in 10ml DMF, add N,N-diisopropylethylamine (3.0ml, 17.4mmol) and morpholine (0.91g , 10.4mmol), stirred at room temperature overnight, under vigorous stirring, water was added, solids were precipitated, filtered, washed with water, and dried to obtain intermediate MDI-201-1 with a yield of 72.2%.
[0585] Synthetic intermediate MDI-201-2: 5-morpholine pyrazine-2-carboxylic acid
[0586] Dissolve the intermediate MDI-201-1 (1.4g, 6.27mmol) in 20ml of tetrahydrofuran and 20ml of water, add lithium hydroxide (0.32g, 7.53mmol), react at room temperature...
Embodiment 3
[0597] Example 3: (2-(6-(2-ethyl-5-fluoro-4-hydroxyphenyl)-1H-indazol-3-yl)--4,6-dihydropyrrolo [3,4-d]imidazol-5(1H)-yl)(1-methyl-1H-pyrazol-4-yl)methanone (MDI-202)
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[0599] The synthetic route of MDI-202:
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[0601] resolve resolution:
[0602] Synthetic intermediate MDI-202-1: (2-(6-bromo 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazol-3-yl)-1-( (2-(Trimethylsilyl)ethoxy)methyl)-4,6-dihydropyrrolo[3,4-d]imidazol-5(1H)-yl)(1-methyl-1H- Pyrazol-4-yl)methanone
[0603] The intermediate 1-methyl-1H-pyrazole-4-carboxylic acid (16.5mg, 0.13mmol) and N,N-diisopropylethylamine (46.0mg, 0.36mmol) were dissolved in DMF, and HATU (67.8 mg, 0.18mmol), react at room temperature for 10 minutes. Intermediate 2-(6-bromo1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazol-3-yl)-1-((2-(trimethylsilyl Base)ethoxy)methyl)-4,6-dihydropyrrolo[3,4-d]imidazole-5(1H)-tert-butyl carboxylate (80mg, 0.12mmol) was dissolved in 5ml of dichloromethane, Add 1ml of trifluoroacet...
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