Pharmaceutical salt of novel EGRF (Epidermal Growth factor Receptor) kinase inhibitor as well as preparation method and application of pharmaceutical salt
An amino, ethyl technology, applied in the preparation of carboxylate, sulfonate, pharmaceutical formulations and other directions
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Embodiment 1
[0022] Example 1: N-(2-((2-(dimethylamino)ethyl)(methyl)amino)-4-methoxy-5-((4-(6,7,8,9- Tetrahydropyrido[1,2-a]indol-10-yl)-pyrimidin-2-yl)amino)phenyl)acrylamide
[0023]
[0024] Step a Synthesis of 1-(4-bromobutyl)-1H-indole
[0025]
[0026] In a 100mL reaction flask, add NaH (60% content, 1.23g, 30.73mmol) and DMF (10mL) in sequence, stir at room temperature for 5min and cool to 0-4°C, slowly add 10mL of dissolved indole (3g, 25.61mmol) DMF solution, after the addition was completed, raised to room temperature and reacted for 20 minutes to obtain an indole activation solution.
[0027] Another 250mL reaction flask was taken, and 1,4-dibromobutane (16.59g, 76.82mmol) and DMF (50mL) were added. Slowly add the indole activation solution prepared above dropwise at 0-4°C, and react at room temperature for 0.5 h after the drop is complete. After the reaction, quenched by adding water (100 mL), extracted with ethyl acetate, combined the ethyl acetate layers, dried over...
Embodiment 2
[0058] Example 2: N-(2-((2-(dimethylamino)ethyl)(methyl)amino)-4-methoxy-5-((4-(6,7,8,9- Tetrahydropyrido[1,2-a]indol-10-yl)-pyrimidin-2-yl)amino)phenyl)acrylamide methanesulfonate
[0059] Weigh compound (I) (148.5mg, 0.28mmol) and dissolve it in 1.49mL of 95% acetone. The solid dissolves at 55°C. Dilute methanesulfonic acid (29.11mg, 0.30mmol) with 1mL of acetone. The acetone solution of sulfonic acid was added to the acetone solution of the above compound (I), reacted for 2 hours, filtered, washed with acetone, and dried under vacuum at room temperature to obtain 155 mg of mesylate.
[0060] 1 H NMR (500MHz, DMSO-d 6 ):δ9.56(s,1H,disappear after heavy water exchange),9.20(s,1H,disappear after heavy water exchange),8.50(s,1H,),8.36(d,1H),8.09(d,1H), 7.91(s,1H,disappeared after heavy water exchange),7.43(d,1H),7.16(t,1H),7.12(t,1H),7.05(d,1H),6.97(s,1H,),6.63( dd,1H,),6.29(dd,1H),5.78(d,1H),4.11(t,2H),3.90(s,3H),3.33-3.31(m,2H),3.26-3.21(m,4H ), 2.81(s,6H), 2.62(s,3H), 2...
Embodiment 3
[0062] Example 3: N-(2-((2-(dimethylamino)ethyl)(methyl)amino)-4-methoxy-5-((4-(6,7,8,9- Tetrahydropyrido[1,2-a]indol-10-yl)-pyrimidin-2-yl)amino)phenyl)acrylamide maleate
[0063] Weigh compound (I) (148.5mg, 0.28mmol) and dissolve in 8.25mL isopropanol, dissolve clear maleic acid (35.16mg, 0.30mmol) with 2mL isopropanol, and dissolve maleic acid in isopropanol at room temperature The solution was added to the above-mentioned compound (I) in isopropanol, reacted for 2 hours, filtered, washed with isopropanol, and dried under vacuum at room temperature to obtain 100 mg of maleate.
[0064] 1 H NMR (500MHz, DMSO-d 6 ): δ9.64(s,1H),9.13(s,1H),8.47(s,1H),8.36(d,1H),8.10(d,1H),7.97(s,1H),7.45(d, 1H),7.16(t,1H),7.12(t,1H),7.05(d,1H),6.98(s,1H),6.57(dd,10.2Hz,1H),6.31(dd,1H),6.09( s,2H),5.81(d,1H),4.12(t,2H),3.90(s,3H),3.29-3.18(m,6H),2.80(s,6H),2.61(s,3H),2.03 -2.02(m,2H),1.84-1.82(m,2H).
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