Synthesis method and anti-tumor application of a kind of phenanthridine derivatives
A synthesis method and derivative technology, which can be used in antitumor drugs, drug combinations, steroids, etc., and can solve the problems of poor water solubility, unfavorable research needs and clinical use, and low bioavailability.
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Embodiment 18
[0045] Example 1.8, Preparation of 9-dimethoxy-5-(4-methoxybenzyl)-1,2,3,4-tetrahydrobenzo[c]phenanthridin-6-one (3)
[0046] 1) Preparation of intermediate (1)
[0047] Add 15 mL of thionyl chloride to 2-bromo-4,5-dimethoxybenzoic acid (1.50 g, 5.74 mmol), heat to reflux at 65° C. for 1 h, and remove the solvent by rotary evaporation to obtain acid chloride as a white solid. Dissolve m-aminoanisole (0.930g, 6.32mmol) in 3mL of dichloromethane, add 7mL of N,N-diisopropylethylamine and acid chloride dissolved in dichloromethane to it at 0°C (in 10min Added in 3 times), reacted for 1h and then transferred to room temperature and stirred for 1h. After the reaction was completed, quenched by adding 1M hydrochloric acid, extracted with dichloromethane, washed the organic phase with saturated sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and separated by a column to obtain a white solid, namely 2- Bromo-4,5-dimeth...
Embodiment 28
[0052] Example 2.8, Preparation of 9-dimethoxy-1,2,3,4-tetrahydrobenzo[c]phenanthridine-6(5H)-one (4)
[0053] Take compound (3) (0.640g, 1.49mmol), add 2mL of trifluoroacetic acid, and heat to reflux at 75°C for 10h. Cool to room temperature after reaction finishes, add ethyl acetate, water to quench, ethyl acetate extracts, organic phase washes with water, saturated sodium bicarbonate washes, after anhydrous sodium sulfate is dried, with dichloromethane and ethyl acetate volume ratio 10: The eluent of 1 was subjected to column separation to obtain a white solid, which was 8,9-dimethoxy-1,2,3,4-tetrahydrobenzo[c]phenanthridin-6(5H)-one (4 ), yield: 75.6%. m.p.253.0~255.0℃; IR(KBr,cm -1 ):3439,3132,1651,1610,1496,1398,1234,1129,1079,836; 1 H-NMR (500MHz, CDCl 3 )δ8.56(s,1H),7.87(d,J=7.4Hz,2H),7.59(s,1H),7.03(d,J=8.3Hz,1H),4.10(s,3H),4.04( s,3H),2.88(t,J=6.1Hz,2H),2.77(t,J=6.4Hz,2H),2.51-2.47(m,1H),2.01-1.94(m,2H),1.88-1.81 (m,2H); 13 C-NMR (126MHz, CDCl 3 )δ153.79, 149...
Embodiment 3
[0054] Example 3. Preparation of 6-chloro-8,9-dimethoxy-1,2,3,4-tetrahydrobenzo[c]phenanthridine (5)
[0055] Put compound (4) (0.02mmol) into a reaction flask, add 40mL of phosphorus oxychloride, and heat to reflux at 105°C for 2h. Cool to room temperature after the reaction is over, carefully pour into a beaker with ice water, add concentrated ammonia dropwise until the pH is alkaline, filter the precipitate, wash the filter cake with water several times, and use petroleum ether and dichloromethane at a volume ratio of 1: 1 eluent for column separation to obtain a white solid, which is 6-chloro-8,9-dimethoxy-1,2,3,4-tetrahydrobenzo[c]phenanthridine (5), producing Rate: 84.8%. m.p.201.3~202.3℃; IR(KBr,cm -1 ):3434,3133,2928,1613,1578,1523,1501,1465,1402,1299,1249,1206,1160,1081,1043,953,840; 1 H-NMR (500MHz, CDCl 3 )δ8.13(d, J=8.4Hz, 1H), 7.83(s, 1H), 7.72(s, 1H), 7.35(d, J=8.5Hz, 1H), 4.14(s, 3H), 4.09( s,3H),3.35(t,J=6.1Hz,2H),2.96(t,J=6.0Hz,2H),1.93(ddd,J=17.9,10.9,5....
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