HIV protease inhibitor derivative, preparation thereof and use in antineoplastic medicament preparation
A protease inhibitor and anti-tumor drug technology, which is applied in chemical synthesis and pharmaceutical fields, can solve the problem of low anti-tumor activity of HIV protease inhibitors, achieve the effect of inhibiting tumor cell activity, and have broad application prospects
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Embodiment 1
[0042] Embodiment 1: the synthesis of compound CH05-05
[0043] Synthesis of compound CH05-01 (C 9 h 10 o 2 )
[0044] In a 500ml three-necked round bottom flask, add 180ml88% formic acid solution, under stirring, the H 2 o 2 (30%) 42ml was added dropwise, after dropping, stirred at 35°C for 15min. Then, 34.8g of indene (CH05-SM1) was added slowly, the rate of addition was controlled, and the temperature was kept at 35-40°C. After dropping, the mixture was stirred at 40° C. for 1 h and reacted overnight. Concentrate under reduced pressure, remove formic acid and water, add 50ml NaOH aqueous solution (10mol / L), stir for 10min, extract 6 times with ethyl acetate while hot, combine organic phases, and dry over anhydrous sodium sulfate. The solvent was removed and recrystallized to obtain 22.6 g of a white powdery solid with a yield of 50%. CH05-01:
[0045] ESI-MS: 151 (M+H) + ;
[0046] 1 H NMR (400MHz, CDCl 3 )d: 2.26 (brs, 2H), 2.93-2.99 (m, 1H), 3.10-3.16 (m, 1H)...
Embodiment 2
[0063] Embodiment 2: the synthesis of compound CH05-08
[0064] Synthesis of compound CH05-07 (C 27 h 38 N 4 o 4 )
[0065] Add 2.4g indinavir (CH05-06), 30ml ethanol, 2g KOH into a 100ml round bottom flask, heat to reflux for 3h, TLC (dichloromethane:methanol=10:1, v / v) shows that the raw material disappears. Concentrate, add water and ethyl acetate, separate layers, extract the aqueous layer with ethyl acetate 3 times, the combined solution is concentrated after drying over anhydrous sodium sulfate, and then go through silica gel column chromatography (dichloromethane:methanol=10:1, v / v) Separate and purify to obtain 1.2 g of white solid (compound CH05-07), with a yield of 75%. CH05-07:
[0066] ESI-MS: 505(M+H) + ;
[0067] 1 H NMR (400MHz, MeOD)d: 1.09(s, 9H), 1.63(m, 1H,), 2.01-2.30(m, 5H), 2.31-2.51(m, 3H), 2.52-2.62(m, 2H) , 2.63-2.74(m, 1H), 2.75-2.88(m, 3H), 2.89-2.94(m, 2H), 3.29(s, 2H), 3.65(d, 1H, J=8.0Hz), 6.83-6.92 (m, 1H), 6.95-7.10(m, 4H), 7.15-7.23...
Embodiment 3
[0072] Embodiment 3: the synthesis of compound CH05-10
[0073] Synthesis of compound CH05-09 (C 45 h 65 N 5 o 5 Si)
[0074] In a 25ml round bottom flask, add 200mg compound CH05-08, 77mg compound CH05-05, 84mg EDCI, 59mg HOBT, 101mg Et 3 N, 2 mL of anhydrous DMF, stirred at room temperature for 3 hours, TLC (petroleum ether:THF=1.5:1, v / v) tracking showed that the starting material disappeared. The solvent was removed by rotary evaporation, 40 mL of dichloromethane was added, 20 mL of saturated NaHCO 3 Washing, washing with saturated brine, drying over anhydrous sodium sulfate, and rotary evaporation to remove the solvent, the resulting solid was purified by silica gel column chromatography (petroleum ether: ethyl acetate=1:1, v / v) to obtain a foamy off-white solid (compound CH05- 09) 160 mg, yield 61%.
[0075] CH05-09:
[0076] ESI-MS: 784(M+H) +
[0077] 1 H NMR (400MHz, CDCl 3 )d: 0.07(s, 3H), 0.09(s, 3H), 0.88(s, 9H), 1.01(s, 3H), 1.26(s, 3H), 1.32(s, 9H), 2...
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