2-methoxyphenoxy pyrimidine antitumor compound as well as preparation method and application thereof
A technology of methoxyphenoxypyrimidine and methoxyphenoxy is applied in the field of 2-methoxyphenoxypyrimidine anti-tumor compounds and their preparation, and the preparation method is simple and feasible, with high yield and easy The effect of mass production
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Embodiment 1
[0045]Example 1 Preparation of 2-((6-amino-5-(2-methoxyphenoxy)-2-phenylpyrimidin-4-yl)oxy)ethan-1-ol (A1).
[0046] a. Preparation of diethyl 2-bromomalonate.
[0047] Put diethyl malonate (30.00g, 187.30mmol), NBS (35.00g, 196.67mmol) and 100ml of chloroform into a 250ml flask, and then add two drops of concentrated sulfuric acid as a catalyst. The reaction was carried out at 50° C. for 12 hours, and the progress of the reaction was monitored by thin-layer chromatography. After the reaction was completed, wash the reaction solution with saturated sodium sulfite solution, then wash the reaction solution with saturated sodium chloride solution, then dry the reaction solution with anhydrous sodium sulfate, evaporate the solvent under reduced pressure, and obtain 43.65 g of a colorless transparent liquid product. Yield 97.48%.
[0048] b. Preparation of diethyl 2-(2-methoxyphenoxy)malonate.
[0049] Diethyl 2-bromomalonate (43.65g, 182.59mmol), guaiacol (22.67g, 182.59mmol), ...
Embodiment 2
[0061] Example 2 Preparation of 2-((6-amino-5-(2-methoxyphenoxy)-2-(m-tolyl)pyrimidin-4-yl)oxy)ethan-1-ol (A2) .
[0062] Using diethyl malonate as a raw material, according to the steps of Example 1a, 1b, 2-(2-methoxyphenoxy) diethyl malonate was obtained, and then using m-toluonitrile as a raw material, according to Example 1c , 1d, 1e, 1f steps make 6-chloro-5-(2-methoxyphenoxy)-2-(m-tolyl)pyrimidin-4-amine, according to the steps of Example 1g, make 2-(( 6-Amino-5-(2-methoxyphenoxy)-2-(m-tolyl)pyrimidin-4-yl)oxy)ethan-1-ol (A2), white solid, yield: 61.37% .
[0063] 1 H NMR (500MHz, DMSO-d 6 )δ8.16–8.01(m, 2H), 7.36(t, J=7.0Hz, 1H), 7.28(d, J=6.8Hz, 1H), 7.07(d, J=7.6Hz, 1H), 6.99( t,J=7.1Hz,1H),6.81(t,J=7.1Hz,1H),6.67(d,J=7.9Hz,1H),6.56(s,2H),4.71(t,J=4.9Hz, 1H), 4.39(t, J=5.0Hz, 2H), 3.86(s, 3H), 3.60(d, J=5.1Hz, 2H), 2.38(s, 3H).
Embodiment 3
[0064] Example 3 2-((6-amino-5-(2-methoxyphenoxy)-2-(p-tolyl)pyrimidin-4-yl)oxy)ethan-1-ol (A3) preparation.
[0065] Using diethyl malonate as a raw material, according to the steps of Example 1a, 1b to prepare 2-(2-methoxyphenoxy) diethyl malonate, and then using p-toluonitrile as a raw material, according to Example 1c , 1d, 1e, 1f steps make 6-chloro-5-(2-methoxyphenoxy)-2-(p-tolyl)pyrimidin-4-amine, according to the steps of Example 1g, make 2-(( 6-Amino-5-(2-methoxyphenoxy)-2-(p-tolyl)pyrimidin-4-yl)oxy)ethan-1-ol (A3), white solid, yield: 57.19 %.
[0066] 1 H NMR (500MHz, DMSO-d 6 )δ8.17(d, J=7.8Hz, 2H), 7.28(d, J=7.8Hz, 2H), 7.07(d, J=8.0Hz, 1H), 6.98(t, J=7.7Hz, 1H) ,6.80(t,J=7.6Hz,1H),6.67(d,J=8.0Hz,1H),6.52(s,2H),4.70(t,J=4.9Hz,1H),4.39(t,J= 5.2Hz, 2H), 3.86(s, 3H), 3.60(d, J=5.2Hz, 2H), 2.37(s, 3H).
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