2-吡咯类酰腙的合成、晶体结构及与小牛胸腺DNA的相互作用

doi:10.11944/j.issn.1000-0518.2016.08.150398

摘要/Abstract

摘要：

以2-吡咯甲酰肼与2,4-二羟基苯甲醛和2-羟基-3-甲氧基苯甲醛经缩合反应合成2,4-二羟基苯甲醛-2-吡咯甲酰腙C₁₂H₁₁N₃O₃(Ⅰ)和2-羟基-3-甲氧基苯甲醛-2-吡咯甲酰腙C₁₃H₁₅N₃O₄(Ⅱ),并利用红外光谱、元素分析、¹H NMR、X射线单晶衍射和热重分析进行表征,结果表明晶体Ⅰ属单斜晶系,空间群为P2₁/c,Z=4,晶胞参数为a=1.2586(4) nm,b=0.8050(3) nm,c=1.1914(4) nm;晶体Ⅱ为正交晶系,空间群为P2₁2₁2₁,Z=4,晶胞参数为a=0.4756(2) nm,b=1.2491(6) nm,c=2.2145(11) nm。热重结果显示,化合物Ⅰ和Ⅱ最大热分解峰分别出现在267.59和284.79 ℃,表观活化能分别为176.6和122.9 kJ/mol,表明化合物Ⅰ和Ⅱ具有较高的热稳定性。利用粘度实验和微量热实验研究了化合物Ⅰ和Ⅱ与CT-DNA的相互作用,均显示两种化合物均与CT-DNA发生了插入作用,且相互作用过程放热,焓变值分别为ΔH(Ⅰ)=4.67 kJ/mol和ΔH(Ⅱ)=4.40 kJ/mol。

关键词: 酰腙化合物, 晶体结构, 热稳定性, 小牛胸腺DNA

Abstract:

Two hydrazone componds(E)-N'-(2,4-dihydroxybenzylidene)-pyrrole-2-carbohydrazide C₁₂H₁₁N₃O₃(Ⅰ) and (E)-N'-(2-hydroxy-3-methoxybenzylidene)-pyrrole-2-carbohydrazide C₁₃H₁₄N₃O₄(Ⅱ) have been synthesized from 2,4-dihydroxybenzaldehyde and 2-hydroxy-3-methoxybenzaldehyde with pyrrole-2-carbohydrazide, respectively. The compounds have been characterized by IR spectroscopy, elemental analysis, ¹H NMR spectroscopy, single-crystal X-ray diffraction and thermogravimetric analysis. The crystal of compound Ⅰ belonged to monoclinic crystal lattice, space group P2₁/c, Z=4, with unit cell parameters a=1.2586(4) nm, b=0.8050(3) nm, c=1.1914(4) nm, and compound Ⅱ crystallized in the orthorhombic system, space group P2₁2₁2₁, Z=4, with unit cell parameters a=0.4756(2) nm, b=1.2491(6) nm, c=2.2145(11) nm. The TG-DTG result shows that the compounds Ⅰ and Ⅱ display good thermal stability, the maximum decomposition peaks are at the temperature of 267.59 ℃ and 284.79 ℃, and their apparent activation energy values are 176.6 kJ/mol and 122.9 kJ/mol, respectively. The thermogenic curves of the compounds Ⅰ and Ⅱ reacting with calf thymus DNA(CT-DNA) measured by viscosity and microcalorimetry, indicate that the interactions of compounds Ⅰ and Ⅱ with CT-DNA belong to the intercalation mode, and the interacting processes are all endothermic, their enthalpies are ΔH(Ⅰ)=4.67 kJ/mol and ΔH(Ⅱ)=4.40 kJ/mol, respectively.

Key words: hydrazone, crystal structures, thermal stability, calf thymus DNA

毛新洁, 刘向荣, 赵顺省, 杨再文, 闫森. 2-吡咯类酰腙的合成、晶体结构及与小牛胸腺DNA的相互作用[J]. 应用化学, 2016, 33(8): 923-931.

MAO Xinjie, LIU Xiangrong, ZHAO Shunsheng, YANG Zaiwen, YAN Sen. Synthesis, Crystal Structures and Calf Thymus DNA Binding of Acylhydrazone Bearing Pyrrole Ring[J]. Chinese Journal of Applied Chemistry, 2016, 33(8): 923-931.

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