Irreversible EGFR inhibitors containing a zinc-binding group
An alkyl and hydroxyl technology, which is applied in the field of preparing medicines for treating and/or preventing tumors, can solve the problems of difficulty in EGF receptor tyrosine kinase inhibitors and the like
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Embodiment 1
[0206] Example 17 Preparation of-(6-acrylamido-4-(3-chloro-4-fluoroanilino)quinazolin-7-yloxy)-N-hydroxyheptanamide (compound 1)
[0207] (1) Preparation of methyl 7-chloroheptanoate
[0208]
[0209] With stirring, methyl 7-hydroxyheptanoate (48 g, 300 mmol) was dissolved in SOCl 2 (120mL), DMF (5mL) was added, and the resulting thick suspension was heated to obtain a transparent yellow solution, which was refluxed for 18 hours, and excess SOCl was distilled off under reduced pressure. 2 To get a brown syrup, add toluene to azeotrope twice to remove excess SOCl 2 A brown solid was obtained, which was dissolved in a small amount of dichloromethane, quickly filtered through silica gel, and then rinsed with dichloromethane quickly, and the obtained yellow filtrate was concentrated under reduced pressure to obtain the target product (45 g, 84%).
[0210] (2) Preparation of 4-(3-chloro-4-fluoroanilino)-6-nitroquinazolin-7-ol
[0211]
[0212] Dissolve N-(3-chloro-4-fluoro...
Embodiment 2
[0233] Preparation of Example 26-(6-acrylamido-4-(3-chloro-4-fluoroanilino)quinazolin-7-yloxy)-N-hydroxycaproamide (compound 2)
[0234] (1) Preparation of ethyl 6-(4-(3-chloro-4-fluoroanilino)-6-nitroquinazolin-7-yloxy)hexanoate
[0235]
[0236] N-(3-Chloro-4-fluorophenyl)-7-fluoro-6-nitroquinazolin-4-amine (10.08 g, 33 mmol) was dissolved in 1,4-dioxane (100 mL) , join K 2 CO 3 (20.7g, 150mmol), ethyl 6-hydroxyhexanoate (14.4g, 90mmol), heated to 100 ° C for 72 hours, the reaction solution was concentrated under reduced pressure to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain the target product (10.5g ,67%).
[0237] (2) Preparation of ethyl 6-(6-amino-4-(3-chloro-4-fluoroanilino)quinazolin-7-yloxy)hexanoate
[0238]
[0239] 6-(4-(3-Chloro-4-fluoroanilino)-6-nitroquinazolin-7-yloxy)ethyl hexanoate (10.5g, 22mmol) was dissolved in THF (100mL), added Catalyst RaneyNi (1.2g), feed H 2 Reduction reaction, fi...
Embodiment 38
[0254] Example 38 Preparation of-(6-acrylamido-4-(3-chloro-4-fluoroanilino)quinazolin-7-yloxy)-N-hydroxyoctylamide (compound 3)
[0255] (1) Preparation of methyl 8-(4-(3-chloro-4-fluoroanilino)-6-nitroquinazolin-7-yloxy)octanoate
[0256]
[0257] N-(3-Chloro-4-fluorophenyl)-7-fluoro-6-nitroquinazolin-4-amine (11.08 g, 33 mmol) was dissolved in 1,4-dioxane (100 mL) , join K 2 CO 3 (20.7g, 150mmol), methyl 8-hydroxyoctanoate (24g, 138mmol), heated to 100 ° C for 72 hours, the reaction solution was concentrated under reduced pressure to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain the target product (5.8g, 36 %).
[0258] (2) Preparation of methyl 8-(6-amino-4-(3-chloro-4-fluoroanilino)quinazolin-7-yloxy)octanoate
[0259]
[0260] 8-(4-(3-Chloro-4-fluoroanilino)-6-nitroquinazolin-7-yloxy)octanoic acid methyl ester (5.8g, 12mmol) was dissolved in THF (100mL), and the catalyst was added RaneyNi (1.2g), pass int...
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