甲酰基硫脲化合物的合成、结构、生物活性、热分解动力学及量化理论研究
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摘要
合成出4-(1,2,4,-三唑-5-酮-4-基)-3-硫代脲酸甲酯,缩写(TOTCM)、4-(1,2,4,-三唑-5-酮-4-基)-3-硫代脲酸乙酯,缩写(TOTCE)、4-(4,6-二甲基嘧啶-2-基)-3-硫代脲酸甲酯,缩写(MPTCM)、4-(4,6-二甲基嘧啶-2-基)-3-硫代脲酸乙酯,缩写(MPTCE)、4-(4,6-二甲氧基嘧啶-2-基)-3-硫代脲酸甲酯,缩写(MOPTCM)、4-(4,6-二甲氧基嘧啶-2-基)-3-硫代脲酸乙酯,缩写(MOPTCE)六种甲酰基硫脲化合物并通过元素分析、红外光谱、核磁共振等方法对它们进行结构表征。首次培养出TOTCM、TOTCE、MPTCM、MPTCE、MOPTCM五种化合物的单晶并用X-射线衍射法测定了晶体结构。通过差示扫描量热分析仪SDT Q600和热重同步差热仪TGA/SDTA851~e对TOTCM、MPTCM、MPTCE、MOPTCM这四种甲酰基硫脲化合物进行了热力学性质和非等温动力学研究:选择具有代表性的粮食类、果蔬类及经济农作物常见病菌,小麦赤霉病菌、烟草赤星病菌、苹果树干腐病对甲酰基硫脲化合物进行生物活性测试,得到TOTCM、TOTCE、MPTCM、MPTCE、MOPTCM这五种甲酰基硫脲化合物的室内毒力回归方程和EC50和EC95值。
对TOTCM、TOTCE、MPTCM、MPTCE、MOPTCM单分子结构进行量化理论研究,获得键长、键角、二面角等优化几何参数与实验值相一致。构建甲酰基硫脲化合物的混合体系和二聚体,并进行几何构型和分子间相互作用的理论计算。
进一步研究化合物结构与其生物活性之间的关系。建立根据化合物分子结构与生物活性相关的研究手段和方法,使该类化合物的合成更具有目的性和定向性,从而可以有目的地设计某些实用新品种,降低杀菌剂研制的成本。
N' -(l,2,4-triazol-5-one-4-yl)-N-substituted formyl thioureas and N' -(substituted pyrimidin-2-yl)-N-substituted formyl thioureas were synthesized and their structure were characterized by elemental analysis, IR and NMR. Five kinds Single crystal of N-substituted formyl thioureas compound were cultured. Crystal structures were determined by X-ray diffraction analysis. Theirs thermal behaviors were studied by DSC and TG/DTG on SDT Q600 and TGA/SDTA851~e Calorimetry. The kinetic parameters and mechanism function were determined by non-isothermal method.The bactericidal activity of N-substituted formyl thioureas compound were studied by microbe of Gibberella saubinetii, Gibberella nicotiancola and Apple black fruit rot fermentation test and obtained theirs EC50 and EC95 value.The experimental geometry of N' -(l,2,4-triazol-5-one-4-yl)-N-substituted formyl thioureas and N' -(substituted pyrimidin-2-yl)-N-substituted formyl thioureas were used as the initial geometry and optimized with Gaussian 03W. Their calculated bond distances, bond angles and IR frequencies were compared with the experimental values and the theoretical values were in accord with those of the experimental. The structural characters and structure-activity relationships were analyzed according to the calculation results.The quantum chemistry study on the N-substituted formyl thioureas compound shows: (1) There was close relationship between the active groups of the compounds and their
activities;(2) The calculated results were in good agreement with the experimental ones, which reflect the structure-activity relationship very well;(3) The research methods of basising the relationship of the molecular structure and bioactivity were founded, which made the synthesis of this kind of compounds have definite purpose and direction. Therefore, new applied breed can be designed on purpose and the research cost of bactericide can be reduced.
对TOTCM、TOTCE、MPTCM、MPTCE、MOPTCM单分子结构进行量化理论研究,获得键长、键角、二面角等优化几何参数与实验值相一致。构建甲酰基硫脲化合物的混合体系和二聚体,并进行几何构型和分子间相互作用的理论计算。
进一步研究化合物结构与其生物活性之间的关系。建立根据化合物分子结构与生物活性相关的研究手段和方法,使该类化合物的合成更具有目的性和定向性,从而可以有目的地设计某些实用新品种,降低杀菌剂研制的成本。
N' -(l,2,4-triazol-5-one-4-yl)-N-substituted formyl thioureas and N' -(substituted pyrimidin-2-yl)-N-substituted formyl thioureas were synthesized and their structure were characterized by elemental analysis, IR and NMR. Five kinds Single crystal of N-substituted formyl thioureas compound were cultured. Crystal structures were determined by X-ray diffraction analysis. Theirs thermal behaviors were studied by DSC and TG/DTG on SDT Q600 and TGA/SDTA851~e Calorimetry. The kinetic parameters and mechanism function were determined by non-isothermal method.The bactericidal activity of N-substituted formyl thioureas compound were studied by microbe of Gibberella saubinetii, Gibberella nicotiancola and Apple black fruit rot fermentation test and obtained theirs EC50 and EC95 value.The experimental geometry of N' -(l,2,4-triazol-5-one-4-yl)-N-substituted formyl thioureas and N' -(substituted pyrimidin-2-yl)-N-substituted formyl thioureas were used as the initial geometry and optimized with Gaussian 03W. Their calculated bond distances, bond angles and IR frequencies were compared with the experimental values and the theoretical values were in accord with those of the experimental. The structural characters and structure-activity relationships were analyzed according to the calculation results.The quantum chemistry study on the N-substituted formyl thioureas compound shows: (1) There was close relationship between the active groups of the compounds and their
activities;(2) The calculated results were in good agreement with the experimental ones, which reflect the structure-activity relationship very well;(3) The research methods of basising the relationship of the molecular structure and bioactivity were founded, which made the synthesis of this kind of compounds have definite purpose and direction. Therefore, new applied breed can be designed on purpose and the research cost of bactericide can be reduced.
引文
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