Tyrosine kinase inhibitor and pharmaceutical application thereof
A technology of tyrosine kinases and inhibitors, which can be used in drug combinations, antineoplastic drugs, organic chemistry, etc., and can solve the problems that gefitinib cannot be combined with it, the selectivity is not good enough, and it is easy to cause drug resistance.
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Embodiment 1
[0026] Preparation of 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-(N-bromoacetyl)aminoquinazoline, the steps are as follows:
[0027] (1) Preparation of 4-chloro-7-fluoro-6-nitroquinazoline.
[0028] 8.5 g of 4-hydroxy-7-fluoro-6-nitroquinazoline and 150 ml of phosphorus oxychloride were added to a 250 ml round bottom bottle, and the mixture was heated to reflux for 6 hours with stirring. Rotary evaporation removes excess phosphorus oxychloride, then washes with 10:1 petroleum ether / ethyl acetate to obtain 8 grams of solid 4-chloro-7-fluoro-6 nitroquinazoline, MS (m / z) :227.78(M+1) + .
[0029] (2) Preparation of 4-(4-fluoro-3-chloroanilino)-7-fluoro-6-nitroquinazoline.
[0030] 2.3 grams of 4-chloro-7-fluoro-6-nitroquinazoline, 1.6 grams of 4-fluoro-3-chloroaniline, and 1.73 grams of potassium carbonate were added to 30 ml of N, N dimethylformamide, and the mixture was stirred and heated to 50 degrees After 10 hours, the solvent was removed under reduced pressure distillatio...
Embodiment 2
[0042] Preparation of 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-(N-chloroacetyl) aminoquinazoline, the steps are as follows:
[0043] 160 mg of 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-aminoquinazoline and 129 mg of triethylamine were dissolved in 50 ml of dichloromethane, then cooled to 0 degrees, slowly Add 68 mg of chloroacetyl chloride dropwise, stir for 5 hours, add 10 ml of water, separate the dichloromethane and dry it with anhydrous magnesium sulfate, filter and concentrate to obtain a crude product, and further column purification to obtain 120 mg of the product, MS (m / z): 394.68(M+1) + .
Embodiment 3
[0045] Preparation of 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-(N-3'-chloropropionyl) aminoquinazoline, the steps are as follows:
[0046] 160 mg of 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-aminoquinazoline and 60 mg of p-dimethylaminopyridine were dissolved in 10 ml of N,N-dimethylformamide, Add 125 mg of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, 70 mg of 3-chloropropionic acid and 129 mg of N,N-diisopropylethylamine, and stir After 15 hours, 20 ml of water was added, extracted with 100 ml of ethyl acetate, and the ethyl acetate was separated and dried over magnesium sulfate. Concentrate by filtration, and the residue is separated by column separation with dichloromethane / methanol to obtain the product 4-(4-fluoro-3-chloroanilino)-7-methoxy-6-(N-3'-chloropropionyl)amino Quinazoline 55 mg, MS (m / z): 408.68 (M+1) + .
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