Application of a Class of Fusidic Acid Derivatives in Reversal of Tumor Drug Resistance
A fusidic acid and drug resistance reversal technology, a new application in tumor drug resistance reversal, the field of fusidic acid derivatives
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Embodiment 1
[0057] Benzyl 21-fusidate
[0058] Take a 500mL eggplant-shaped bottle, dissolve fusidic acid (10.01g, 0.019mol) in acetone (200mL), stir and add potassium carbonate (5.36g, 0.039mol), benzyl bromide (2.78mL, 0.023mol), 30°C React for 5-7 hours. Suction filtration, concentration, dilution with ethyl acetate (50mL), washing with 10% hydrochloric acid until acidic, washing with water, washing with saturated brine, drying over anhydrous sodium sulfate, filtering, distilling off the solvent under reduced pressure, silica gel column chromatography (V 氯仿 :V 甲醇 =210:1-190:1), to obtain benzyl 21-fusidate (8.86 g, 75.4%) as a white solid. 1 H-NMR (CDCl 3 ,400MHz)δ:7.30-7.37(m,5H,Ar-H),5.87(d,J=8.36Hz,1H,16-H),5.20(d,J=12.20Hz,1H,CHAr),5.06( t,J=7.12Hz,1H,24-H), 4.92(d,J=12.20Hz,1H,CHAr),4.33(s,1H,11-H),3.70(d,J=2.00Hz,1H, 3-OH), 3.04(d, J=11.20Hz, 1H, 13-H), 2.37-2.50(m, 2H, 2×22-H), 2.28-2.31(m, 1H, 12-H), 2.08 -2.20(m,5H,1-H,5-H,15-H and 2×23-H),1.92(s,3H,OCOCH 3),1.76-1.84(m...
Embodiment 2
[0060] 3-(6-Nitrooxy-hexanoyl)-21-fusidic acid benzyl ester
[0061] Take a 25mL eggplant-shaped bottle, dissolve benzyl 21-fusidate (0.12mmol) in anhydrous dichloromethane (10mL), stir and add bromohexanoic acid (0.18mmol), DMAP (0.37mmol), EDCI ( 0.38mmol), 5 drops of triethylamine, and react at room temperature for 7-10 hours. Wash with 10% hydrochloric acid until acidic, wash with water, wash with saturated brine, dry over anhydrous sodium sulfate, filter, evaporate the solvent under reduced pressure, and perform silica gel column chromatography (V 石油醚 :V 乙酸乙酯 =50:1-20:1) to obtain benzyl 3-(6-bromohexanoyl)-21-fusidate as a white solid.
[0062] Take a 25mL eggplant-shaped bottle, dissolve 3-(6-bromohexanoyl)-21-fusidic acid benzyl ester (0.069mmol) in 8mL of anhydrous acetonitrile, stir and add silver nitrate (0.18mmol), 70°C in the dark React for 18 hours. Filter, concentrate, dissolve in ethyl acetate, wash with water successively, wash with saturated brine, dry ov...
Embodiment 3
[0064] 3,11-dicarbonyl-21-fusidic acid benzyl ester
[0065] Take a 25mL eggplant-shaped bottle, dissolve benzyl 21-fusidate (60mg, 0.099mmol) in 10mL of dichloromethane, add freshly prepared PCC (64mg, 0.30mmol) with stirring, and stir at room temperature for 4-8 hours. Remove the solvent under reduced pressure, dilute with ethyl acetate (10mL), wash with water, wash with saturated brine, dry over anhydrous sodium sulfate, filter, evaporate the solvent under reduced pressure, perform silica gel column chromatography (V 石油醚 :V 乙酸乙酯 =10:1-6:1), a pale yellow solid (40 mg, 66.7%) was obtained. 1 H-NMR (CDCl 3 ,400MHz)δ:7.32-7.37(m,5H,5×Ar-H),5.93(d,J=8.22Hz,1H,16-H),5.21(d,J=11.95Hz,1H,CHAr), 5.04(t, J=7.18Hz, 1H, 24-H), 4.95(d, J=12.13Hz, 1H, CHAr), 2.85-2.93(m, 1H, 13-H), 2.65-2.78(m, 2H ,2×22-H),2.47-2.54(m,1H,12-H),2.33-2.42(m,3H,15-H and 2×23-H),2.14-2.26(m,2H,1- H and5-H),1.97-2.11(m,3H,2×2-H and 7-H),1.95(s,3H,OCOCH 3 ), 1.81(t, J=11.88Hz, 1H, 12-H), 1.63(s, 3H, 27-...
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