Camptothecin derivatives with antitumor activity
A technology of camptothecin and analogs, applied in the field of camptothecin derivatives, can solve the problems of poor tumor effect, affecting tissue/plasma distribution ratio, etc.
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Embodiment 17
[0077] The preparation of embodiment 17-ethyl-10-boronic acid camptothecin (HD-302)
[0078] 1a, Synthesis of 7-ethyl-10-trifluoromethylsulfonyloxycamptothecin
[0079] Suspend SN-38 (0.1g, 0.255mmol) in anhydrous N,N-dimethylformamide (2.5ml) under nitrogen protection, and add triethylamine (52mg, 0.51mmol) to the resulting suspension . Under stirring, N-phenylbis(trifluoromethanesulfonyl)imide (137mg, 0.383mmol) was added thereto, and reacted at room temperature for 16 hours (TLC controlled the complete reaction of the main material). After the reaction was complete, dichloromethane (5ml) and water (2×10ml) were added, stirred and washed, the organic phase was collected, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to obtain an off-white solid (134mg, 0.255mmol).
[0080] 1b, Synthesis of 7-ethyl-10-trifluoromethylsulfonyloxy-16-O-triethylsilylcamptothecin
[0081] Under nitrogen protection, 7-ethyl-10-trifluoromethylsulfonyloxycamptothecin (0.1...
Embodiment 2
[0088] 2a, Synthesis of 7-tert-butoxyiminomethyl-10-hydroxycamptothecin
[0089] Add 10-hydroxy-7-formylcamptothecin (50mg) into ethanol (10ml) and pyridine (1.5ml), then add O-tert-butylhydroxylamine hydrochloride (55mg) under stirring, reflux for 5h, reduce Concentrate under reduced pressure, and purify through column (dichloromethane: methanol) to obtain 30 mg of yellow solid.
[0090] 1 HNMR (400MHz, CD 3 OD):δ0.88(t,H3-18E+H3-18Z,J=7.35Hz),1.35(s,t-BuZ),1.45(s,t-BuE),1.80-1.90(m,H2-19E +H2-19Z),5.10-5.40(m,H2-5E+H2-5Z+H2-17E+H2-17Z),6.53(s,OH),7.25-7.50(m,H-14E+H-14Z+ H-11E+H-11Z+H-9Z),7.70(d,.H-9E,J=2.57Hz)8.05(d,H-12E+H-12Z,J=9.19Hz),8.25(s,CH =NZ), 9.0 (s, CH=NE) 10.35 (s, 10-OH).
[0091] 2b, Synthesis of 7-tert-butoxyiminomethyl-10-trifluoromethylsulfonyloxycamptothecin
[0092] Suspend 7-tert-butoxyiminomethyl-10-hydroxycamptothecin (140mg) in anhydrous N,N-dimethylformamide (2.5ml) under nitrogen protection to obtain a suspension Add triethylamine (52 mg, 0....
Embodiment 3
[0100] 3a, Synthesis of 7-(2'-trimethylsilyl)ethyl-10-hydroxycamptothecin
[0101] Add ferric sulfate heptahydrate (2g) and 30% sulfuric acid (12.5ml) into a 100ml three-necked flask, stir at room temperature for 20min, add trimethylsilyl propanol (4.8g), glycol (50ml) dropwise into the reaction flask and stir 15min. Add this reaction solution dropwise into a reaction bottle containing SN-38 (2.5g), 30% sulfuric acid (137.5ml), and 30% hydrogen peroxide (0.81ml) (about 30min), stir at room temperature for 1h, and then add hydrogen peroxide dropwise (2.43ml), stirred overnight.
[0102] Wash the reaction solution with n-hexane (3×25ml), discard the n-hexane layer, extract the reaction solution with dichloromethane (3×125ml), combine the organic phases, concentrate under reduced pressure at low temperature (below 40°C) to obtain the crude product, add N, N -Dimethylformamide (80ml), heated to 120°C, dissolved and clarified, crystallized at 25°C, filtered with suction, and drie...
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