4'-demethylepipodophyllotoxin compounds and use thereof as anticancer agent
A technology for demethylepipodophyllotoxins and compounds, which is applied in the field of novel 4′-demethylepodophyllotoxins and can solve the problems of poor water solubility, easy metabolic inactivation, toxic side effects, and insufficient drug efficacy.
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[0078] The preparation of general formula compound I:
[0079]
[0080] a: MeSO 3 H / NaI; CH 2 Cl 2 , then p-nitroaniline, BaCO 3 , THF; b: Pb-C, H 2 ;c: HATU, DIEA, DCM
[0081] Dissolve norepipodophyllotoxin SM (4.000g, 10mmol) in 150ml of anhydrous dichloromethane, add NaI (2.235mg, 15mmol), dissolve in 150ml of anhydrous CH 2 Cl 2 , stirred for about 10min, added methanesulfonic acid (10ml, 15mmol) under ice-water bath conditions, stirred at room temperature for 2h, filtered, the filtrate was concentrated under reduced pressure, and directly added BaCO 3 (3.950g, 20mmol), p-nitroaniline (2.070mg, 15mmol), dissolved in 150ml of anhydrous dichloromethane, stirred at room temperature under nitrogen protection for 8h, filtered, the filtrate was concentrated under reduced pressure, extracted with ethyl acetate, saturated thiosulfuric acid Sodium solution and saturated brine were washed successively, dried over anhydrous sodium sulfate, and separated by silica gel colum...
Embodiment 1
[0089] MS(ESI): 576[M+H] +
[0090] 1 H-NMR (300MHz, CDCl 3): 8.93 (s, 1H, -NH-CO-), 7.43 (d, J=8.7, 2H, ArH), 6.75 (s, 1H, 5-H), 6.51-6.54 (m, 3H, 8-H , ArH), 6.33 (s, 2H, 2', 6'-H), 5.96 (d, J=4.5, 2H, -OCH 2 O-), 5.46(s, 1H, -OH), 4.58-4.65(m, 2H, 1-H, 4-H), 4.38(t, J=7.8, 1H, 11-H), 4.12(t, J=9.0,1H,11-H), 3.79(s,6H,3',5'-OCH 3 ), 3.12, (dd, J=5.1, 13.8, 1H, 2-H), 3.06 (s, 2H, - CH 2 -N(CH 3 ) 2 ), 2.37(s, 6H, -N(CH 3 ) 2 )
Embodiment 2
[0092] MS(ESI):638[M+H] +
[0093] 1 H-NMR (300MHz, CDCl 3 ): 7.57 (d, J=8.7, 2H, ArH), 7.61 (s, 1H, -NH-CO-), 7.45 (d, J=8.4, 2H, ArH), 6.69-6.77 (m, 3H, ArH , 5-H), 6.50-6.56 (m, 3H, ArH, 8-H), 6.33 (s, 2H, 2', 6'-H), 5.96 (d, J=6.0, 2H, OCH 2 O-), 5.30(s, 1H, -OH), 4.57-4.65(m, 2H, 1-H, 4-H), 4.39(t, J=7.5, 1H, 11-H), 4.02(t, J=10.2,1H,11-H), 3.78(s,6H,3',5'-OCH 3 ), 3.16(dd, J=4.8, 14.1, 1H, 2-H), 3.04(s, 6H, -N(CH 3 ) 2 ), 2.88-3.01(m, 1H, 3-H)
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