7-bit substituted comptothecine kind compound and pharmaceutical use thereof
A technology of homocamptothecin and compounds, which is applied in the field of medicine and can solve the problems of high water solubility and high toxicity of drugs
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Embodiment 1
[0038] The synthesis of embodiment 1 homocamptothecin
[0039] 1.00g of 9-ethyl-9-hydroxy-2,3,8,9-tetrahydro-5H-6-oxa-3a-aza-cycloheptane-1,4,7-trione and 0.80g Anthranilic aldehyde ethylene glycol acetal in 800mL toluene, reflux to separate water, after 30 minutes, add 0.10g p-toluenesulfonic acid, continue to reflux for 1h, filter after cooling, wash with acetone and methanol to obtain 0.98g yellow solid gaocampus Alkali (70.4%).
[0040] 1 HNMR (DMSO), δ: 0.87(t, 3H), 1.86(q, 2H), 3.06(d, 1H), 3.49(d, 1H), 5.28(s, 2H), 5.39(d, 1H), 5.53 (d, 1H), 6.03(s, 1H), 7.42(s, 1H), 7.72(t, 1H), 7.87(t, 1H), 8.15(q, 2H), 8.69(s, 1H).
Embodiment 2
[0041] The synthesis of embodiment 2 7-hydroxymethyl homocamptothecin
[0042] Add 25 mL of 75% sulfuric acid dropwise to 0.98 g of homocamptothecin suspended in 30 mL of methanol and 25 mL of water, and then add 0.80 g of FeSO 4 .7H 2 O. Cool to 0°C with ice water, add dropwise 5mL 30% H 2 o 2 , Continue stirring to room temperature for 14h. After diluting with 200mL of water, a solid precipitated, filtered, washed with hot DMF, the filtrate was evaporated to remove the solvent, and purified on a silica gel chromatography column (eluent: CH 2 Cl 2 / CH 3 OH 100:4), to obtain 0.61 g of yellow solid 7-hydroxymethyl homocamptothecin (64.7%).
[0043] 1 HNMR (DMSO), δ: 0.88(t, 3H), 1.87(q, 2H), 3.06(d, 1H), 3.47(d, 1H), 5.27(d, 2H), 5.41(s, 2H), 5.40 (d, 1H), 5.53(d, 1H), 5.80(t, 1H), 6.03(s, 1H), 7.40(s, 1H), 7.71(t, 1H), 7.86(t, 1H), 8.16( d, 1H), 8.20(d, 1H).
Embodiment 3
[0044] The synthesis of embodiment 3 7-formyl homocamptothecin
[0045] Heat 0.61g 7-hydroxymethyl homocamptothecin in 200mL acetic acid to reflux for 6h, evaporate the solvent, and purify on a silica gel column (eluent: CH 2 Cl 2 / CH 3 OH 100:4), to obtain 0.32 g of yellow solid 7-formyl homocamptothecin (52.7%).
[0046] 1 HNMR (DMSO), δ: 0.87(t, 3H), 1.88(q, 2H), 3.07(d, 1H), 3.49(d, 1H), 5.42(d, 1H), 5.52(s, 2H), 5.55 (d, 1H), 6.06(s, 1H), 7.46(s, 1H), 7.92(t, 1H), 7.98(t, 1H), 8.31(d, 1H), 9.04(d, 1H), 11.10( s, 1H).
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