Glycyrrhetinic acid derivative and application thereof as antitumor medicament
Technology of an anti-tumor drug, glycyrrhetinic acid, applied in the field of medicine
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Embodiment 1
[0032] 5-[4-(2-bromoethoxy)phenyl]-3H-1,2-dithiole-3-thione ( 5a ) preparation
[0033] ADT-OH (0.325g, 1.4mmol), 1,2-dibromoethane (0.50mL, 5.8mmol), anhydrous K 2 CO 3 (0.396g, 2.8mmol), dissolved in 10mL dry DMF, reacted at 120°C for 2h. After cooling, add 20mL ethyl acetate to dilute, wash with water (3×20mL), anhydrous Na 2 SO 4 dry. Filter, evaporate to dryness under reduced pressure, and recrystallize from acetone-water to obtain 0.388 g of dark brown product, yield 81.5%, mp: 126.0~127.0°C. 1 H NMR (400MHz, CDCl 3 ), δ(ppm): 7.59(d, 2H, J =8.9Hz, ArH), 7.36(s, 1H, =CH), 6.96 (d, 2H, J =8.9Hz, ArH), 4.33(t, 2H, J =6.1Hz,CH 2 ), 3.65(t, 2H, J = 6.1 Hz, CH 2 ); 13 C NMR (400MHz, CDCl 3 ), δ(ppm): 212.554, 170.180, 158.775, 132.260, 126.120, 122.226, 113.014, 65.455, 26.026.
[0034] Above-mentioned identification data proves that gained compound is 5-[4-(2-bromoethoxy) phenyl]-3H-1,2-dithiole-3-thione ( 5a ), its structural formula is: .
[0035] Comp...
Embodiment 2
[0039] 5-[4-(3-bromopropoxy)phenyl]-3H-1,2-dithiole-3-thione ( 5b ) preparation
[0040] With 1,3-dibromopropane as raw material, refer to 5a prepared by the method, yield 83.2%, mp: 79.0~80.0℃. 1 H NMR (400MHz, CDCl 3 ), δ(ppm): 7.62(d, 2H, J = 8.8Hz, ArH), 7.40(s, 1H, =CH), 7.00(d, 2H, J = 8.7Hz, ArH), 4.19(t, 2H, J = 5.8 Hz, CH 2 ), 3.62(t, 2H, J = 6.3Hz, CH 2 ), 2.36(p, 2H, J =6.0 Hz, CH 2 ); 13 C NMR (400MHz, CDCl 3 ), δ(ppm): 212.460, 170.437, 159.454, 132.073, 126.065, 121.751, 112.886, 63.118, 29.453, 27.178. The above identification data prove that the obtained compound is 5-[4-(3-bromopropoxy)phenyl]-3H-1,2-dithio-3-thione ( 5b ), its structural formula is: .
[0041] Compound I 2 preparation of
[0042] Take GA and 5b as raw material, refer to Ⅰ 1 Prepared by the synthetic method of , red solid, yield 86.6%, mp: 79.1~80.7℃. 1 H NMR (400MHz, CDCl 3 ), δ(ppm): 7.54 (d, 2H, J= 8.8 Hz, ArH), 7.31 (s, 1H, =CH), 6.91 (d, 2H, J= 8.8 Hz, ArH), 5.5...
Embodiment 3
[0045] 5-[4-(4-bromobutoxy)phenyl]-3H-1,2-dithiole-3-thione ( 5c ) preparation
[0046] With 1,4-dibromobutane as raw material, refer to 5a prepared by the method, yield 79.4%, mp: 70.0~71.0℃. 1 H NMR (400MHz, CDCl 3 ), δ(ppm): 7.60(d, 2H, J = 8.7Hz, ArH), 7.38(s, 1H, =CH), 6.96(d, 2H, J =8.7Hz, ArH), 4.07(t, 2H, J =5.9Hz,CH 2 ), 3.50(t, 2H, J =6.4Hz,CH 2 ), 2.08(m, 2H, CH 2 ), 1.99(m, 2H, CH 2 ); 13 C NMR (400MHz, CDCl 3 ), δ(ppm): 212.439, 170.554, 159.670, 132.006, 126.057, 121.553, 112.834, 64.759, 30.795, 26.729, 25.133. The above identification data prove that the compound obtained is 5-[4-(4-bromobutoxy)phenyl]-3H-1,2-dithiole-3-thione ( 5c ), its structural formula is: .
[0047] Compound I 3 preparation of
[0048] Take GA and 5c as raw material, refer to Ⅰ 1 Prepared by the synthetic method of , red solid, yield 89.2%, mp: 138.2~139.2℃. 1 H NMR (400MHz, CDCl 3 ), δ(ppm): 7.60 (d, 2H, J= 8.8Hz,), 7.39 (s, 1H, =CH), 6.98(d, 2H, J= 8.8 Hz, Ar...
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