Sarsasapogenin-structure-modified derivatives, pharmaceutical compositions thereof and applications of the compositions
A technology of timogenin and derivatives, applied in the field of timogenin structurally modified derivatives, which can solve the problems of scarcity of derivatives and immature research on timogenin structurally modified derivatives
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Embodiment 1
[0080] The preparation method of timogenin AA is as follows:
[0081] The anemarrhena rhizome medicine is refluxed and extracted three times according to the weight ratio of 50%-90% ethanol at 1:2-1:4, filtered, and the ethanol is evaporated to dryness. The ethanol crude extract was dispersed in 5% H 2 SO 4 , heated and hydrolyzed for 4-10 hours, the acid hydrolyzed product was extracted with DCM several times, and the DCM was removed to obtain the crude product of timogenin. The crude product was eluted with petroleum ether-acetone (20:1) to obtain timogenin AA.
[0082] Timogenin AA
[0083] 1 H NMR (400MHz, CDCl 3 )δ4.42(m,1H,H-20),4.12(s,1H,H-3),3.97(d,J=11.0Hz,1H,H-26),3.31(d,J=11.0Hz, 1H,H-26),2.07–0.98(m,37H),0.77(s,3H). 13 C NMR (100MHz, CDCl 3 )δ109.75, 81.02, 67.08, 65.14, 62.08, 56.47, 42.11, 40.67, 40.31, 39.85, 36.52, 35.27 (2C), 33.53, 31.74, 29.95, 27.81, 27.08, 26.56, 26.54, 25.97 20.90,16.50,16.05,14.34.MS(ESI):m / z 416.45[M+H] + ;HRMS(ESI):m / z[M+H] ...
Embodiment 2
[0085] Preparation method of timogenin derivative ZM1:
[0086] At room temperature, mix timogenin AA with acetic anhydride and ammonium chloride, then heat the reaction to 50-150°C for 4-24 hours, then add 2%-10% methanol-sodium hydroxide solution, and react at room temperature After 4-24 hours, the mother sapogenin derivative ZM1 was obtained by extraction and column chromatography.
[0087] Timogenin Derivative ZM1
[0088] 1H NMR (400MHz, CDCl 3 )δ4.73(ddd, J=16.2, 7.1Hz, 1H), 4.11(s, 1H), 3.47(d, J=21.0Hz, 2H), 2.47(d, J=10.0Hz, 1H), 1.28- 1.93(m,30H),0.98(s,3H),0.92(d,3H),0.67(s,3H).13C-NMR(101MHz,CDCl 3 )δ151.59,103.80,84.40,68.05,67.07,64.39,54.97,43.72,39.98,39.82,36.51,35.35,35.26,35.07,34.05,33.53,30.38,29.96,27.84,26.69,26.54,23.90,23.15,21.04,16.43 ,14.20,11.66,ESI-MS m / z 417.4[M+H] + .
Embodiment 3
[0090] Preparation method of timogenin derivative ZM13:
[0091] Under the protection of argon, react the timogenin derivative ZM1 with p-toluenesulfonyl chloride for 1-10 hours, then add sodium azide, and raise the temperature to 40-100°C, react for 1-10 hours, then add triphenyl After 1-10 hours of reaction at room temperature, the mother sapogenin derivative ZM13 was obtained by extraction and column chromatography. Wherein, the molar ratio of ZM1 to toluenesulfonyl chloride, sodium azide and triphenylphosphine is 1:1:1:1 to 1:10:10:10.
[0092] Timogenin Derivative ZM13
[0093] 1H NMR (400MHz, CDCl 3 )δ4.71(m, 1H), 4.32(d, J=5.6Hz, 1H), 4.11(s, 1H), 3.03(dd, J=13.6, 6.8Hz, 2H), 2.46(d, J=10.0 Hz, 1H), 1.32-1.83(m, 30H), 0.98(s, 3H), 0.91(d, J=6.6Hz, 3H), 0.65(s, 3H), ESI-MS: m / z 416.3[M +H] + .
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