Podophyllotoxin-indirubin ramification, preparation method and medical application thereof
A technology of podophyllotoxin and indirubin, which can be used in drug combination, antitumor drugs, organic chemistry, etc., can solve the problems that restrict the clinical application of podophyllotoxin in antitumor.
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Embodiment 1
[0032] Example 1: Indirubin-N 1 - Preparation of Acetate-4-podophyllotoxin (I-1)
[0033] Podophyllotoxin (0.12g, 0.28mmol) was added to anhydrous dichloromethane (5mL), then triethylamine (0.2mL, 1.4mmol) was added, the above reaction solution was cooled to 0°C, and bromo Acetyl chloride (2.5eq). After dropping, the reaction solution was raised to 30°C for 1-2 hours. The reaction was quenched with ammonium chloride solution, extracted three times with dichloromethane, the organic layers were combined, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain intermediate III-1. The above crude product, indirubin (1 g), cesium carbonate (2.5 eq) and catalytic amount of potassium iodide were added into anhydrous DMF, and stirred at 25° C. for 0.5-1 hour. Quench the reaction with brine, extract three times with dichloromethane, combine the organic layers, wash with saturated brine, dry over anhydrous magnesium sulfate, filter to...
Embodiment 2
[0035] Example 2: Indirubin-N 1 - Preparation of propionate-4-podophyllotoxin (I-2)
[0036] Bromopropionyl chloride is replaced by bromoacetyl chloride, according to the method described in Example 1, the rest of the required raw materials and reagents are the same as in Example 1, to obtain purple solid indirubin-N 1 -Propionate-4-podophyllotoxin (I-2), yield 70%.
[0037] 1 H NMR (400MHz, DMSO-d6) δ11.03(s, 1H), 8.79(d, J=7.2Hz, 1H), 7.65(d, J=7.2Hz, 1H), 7.58(t, J=6.4Hz ,1H),7.40(d,J=7.6Hz,1H),7.30(t,J=6.8Hz,1H),7.07(s,2H),7.01(t,J=6.8Hz,1H),6.75(s ,1H),6.50(s,2H),5.89(s,2H),5.74(s,1H),5.66(s,1H),4.36(t,J=7.2Hz,1H),4.25(s,2H) ,4.03(d,J=5.6Hz,2H),3.66(s,6H),3.61(d,J=7.2Hz,2H),3.54(s,3H),2.64-2.73(m,2H); 13C NMR(100MHz,DMSO-d6)δ188.98,177.69,171.17,169.40,153.10,152.87,147.80,146.64,141.07,139.22,138.76,137.65,136.45,132.70,129.47,127.05,124.88,122.32,121.91,121.18,119.50 ,113.92,109.31,109.05,108.22,106.04,105.58,101.60,72.83,70.81,60.27,56.28,55.36,44.07,43.76,35.76,...
Embodiment 3
[0038] Example 3: Indirubin-N 1 - Preparation of butyrate-4-podophyllotoxin (I-3)
[0039] Bromobutyryl chloride is replaced by bromoacetyl chloride, according to the method described in Example 1, the rest of the required raw materials and reagents are the same as in Example 1, to obtain a purple solid indirubin-N 1 -Butyrate-4-podophyllotoxin (I-3), yield 60%.
[0040] 1 H NMR (400MHz, DMSO-d6) δ11.03(s, 1H), 8.80(d, J=8.0Hz, 1H), 7.65(d, J=6.8Hz, 1H), 7.57(t, J=6.8Hz ,1H),7.38(d,J=7.6Hz,1H),7.29(t,J=6.8Hz,1H),7.08(s,2H),7.01(t,J=7.2Hz,1H),6.85(s ,1H),6.50(s,3H),5.95(s,2H),5.67(s,1H),4.39(t,J=7.6Hz,1H),4.29(d,J=14.0Hz,2H),3.81 (s,2H),3.65(s,6H),3.58(s,3H),3.55(d,J=9.2Hz,1H),2.93(s,1H),2.26-2.40(m,2H),1.86( s,2H); 13 C NMR(100MHz,DMSO-d6)δ188.98,177.72,172.67,169.56,153.11,152.86,147.82,146.72,141.55,139.12,138.81,137.67,136.47,132.63,129.59,127.28,124.91,122.25,121.89,121.20,119.48 ,113.88,109.27,108.87,108.26,106.11,105.80,101.64,72.53,70.99,60.34,56.26,44.24,43.77,3...
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