Preparation method and application of irreversible alkyne heterocyclic compound FGFR inhibitor
A compound and solvate technology, applied in the field of irreversible alkyne heterocyclic compounds FGFR inhibitors
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Embodiment 1
[0085] Example 1: (S)-1-(1-acryloylpyrrolidin-3-yl)-3-(3,5-dimethoxy-2,6-difluorophenylethynyl)-4-amino- Preparation of 7-Hydroxy-1H-pyrrole[2,3-d]pyridazine (Compound 1)
[0086]
[0087] Step 1: Synthesis of Compound 1b
[0088] Add compound 3-cyano-1H-pyrrole-2-carboxylate ethyl ester 1a (1.64g, 10.0mmol), hydrazine hydrate 5mL, and ethanol 50mL into the reaction flask, heat up to reflux reaction overnight with stirring. After cooling to room temperature, the solvent was evaporated to dryness under reduced pressure. The residue was purified by column chromatography to obtain compound 1b (0.64 g, 43% yield) as a white solid. LC / MS(ESI):m / z=151.1[M+H] + .
[0089] Step 2: Synthesis of Compound 1c
[0090] Add compound 1b (0.6g, 4.0mmol) and 10mL of N,N-dimethylformamide to the reaction flask, add NBS (1.07g, 6.0mmol) in batches, and react at 50°C for 4 hours under stirring. After cooling to room temperature, the reaction solution was poured into 50 mL of water and ex...
Embodiment 2
[0099] Example 2: (S)-1-(1-but-2-ynoylpyrrolidin-3-yl)-3-(3,5-dimethoxy-2,6-difluorophenylethynyl)- Preparation of 4-amino-7-hydroxy-1H-pyrrole[2,3-d]pyridazine (compound 2)
[0100]
[0101] Compound 2 (112 mg, yield 52%) was obtained as a yellow solid by a method similar to that of Example 1 (the intermediate was replaced by but-2-ynoyl chloride). LC / MS(ESI):m / z=482.0[M+H] + .
Embodiment 3
[0102] Example 3: (S)-1-(1-acryloylpyrrolidin-3-yl)-3-(3,5-dimethoxy-2,6-dichlorophenylethynyl)-4-amino- Preparation of 7-Hydroxy-1H-pyrrole[2,3-d]pyridazine (Compound 3)
[0103]
[0104] Compound 3 (95 mg, yield 41%) was obtained as an off-white solid by a method similar to that of Example 1 (the intermediate was replaced with 3,5-dimethoxy-2,6-dichlorophenylacetylene). LC / MS(ESI):m / z=503.0[M+H] + .
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