Fused heterocycle derivative and application thereof
A compound, heteroaryl technology
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Embodiment 1
[0195] Embodiment 1: the preparation of compound 1
[0196]
[0197] Preparation of (Z)-ethyl-3-hydroxy-2-phenylacrylate
[0198] Place 28g of ethyl phenylacetate and 230mL of ethyl formate in a 1L three-necked flask in an ice bath. Weigh 20g of NaH and slowly add it into the three-necked bottle, a large amount of gas will come out, and the adding time is about 30 minutes. After the addition, stir at room temperature for 5 hours to stop the reaction, add the reaction solution to an appropriate amount of water, adjust the pH to be acidic, extract the organic layer with an appropriate amount of ethyl acetate, combine, dry, and spin off the organic solvent to obtain 32 g of an oily product.
[0199] Preparation of (Z)-ethyl-3-((2-chloropyridin-4-yl)amino)-2-phenylacrylate
[0200] Add ethyl-3-hydroxy-2-phenylacrylate (19g, 1eq), 2-chloro-4-aminopyridine (12.7g, 1eq), ethanol (300mL), concentrated hydrochloric acid (0.5mL) into the reaction flask, Mix well and heat up to 85°...
Embodiment 2
[0206] Embodiment 2: the preparation of compound 2
[0207]
[0208] 3-Chloro-4-(2-fluoro-4-((4-oxo-3-phenyl-1,4-dihydro-1,6-naphthyridin-5-yl)amino)phenoxy)-2 - Preparation of amidopyridines
[0209] Add 5-chloro-3-phenyl-1,6-naphthyridin-4(1H)-one (150mg, 1eq), 4-(4-amino-2-fluorophenoxy)-3- Chloro-2-amidopyridine (162mg, 1eq), concentrated hydrochloric acid (3 drops), and isopropanol (130mL) were mixed, stirred electromagnetically, heated to 50°C and reacted for 3 hours, filtered off insoluble matter, and the filter cake was washed with isopropanol After vacuum drying, 3-chloro-4-(2-fluoro-4-((4-oxo-3-phenyl-1,4-dihydro-1,6-naphthyridin-5-yl)amino)benzene Oxy)-2-amidopyridine (68 mg). 5-((4-((2-amino-3-chloropyridin-4-yl)oxy)-3-fluorophenyl)amino)-3-phenyl-1,6-naphthyridine-4(1H)- Preparation of ketones
[0210] 3-chloro-4-(2-fluoro-4-((4-oxo-3-phenyl-1,4-dihydro-1,6-naphthyridin-5-yl)amino)phenoxy )-2-amidopyridine (65mg, 1eq), acetonitrile (35mL), ethyl acetate (...
Embodiment 3
[0212] Embodiment 3: the preparation of compound 3
[0213]
[0214] Preparation of 4-(4-amino-2-fluorophenoxy)-3-iodo-2-pyridinamide
[0215] Add 3-iodo-4-chloro-2-pyridinamide (281mg, 1.0eq), 2-fluoro-4-aminophenol (127mg, 1.0eq), potassium tert-butoxide (145.6mg, 1.3eq ), anhydrous DMF (25mL), heated to 90 ° C for 4 hours, the plate reaction was complete, the reaction was stopped, the solvent was recovered under reduced pressure, and the crude residue was obtained by silica gel column chromatography to obtain 4-(4-amino-2-fluorobenzene) - 3-iodo-2-pyridineamide (300 mg).
[0216] 4-(2-fluoro-4-((4-oxo-3-phenyl-1,4-dihydro-1,6-naphthyridin-5-yl)amino)phenoxy)-3-iodo-2 - Preparation of amidopyridines
[0217] To a 100mL round bottom flask was added 4-(4-amino-2-fluorophenoxy)-3-iodo-2-pyridineamide (580mg, 1.0eq), 5-chloro-3-(4-fluorophenyl )-1,6-naphthyridin-4(1H)-one (426mg, 1eq), isopropanol 100mL, concentrated hydrochloric acid 0.1mL, heated to 50°C for 6 hours, st...
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