【作者】 刘辉；

【导师】 冯俊涛；

【作者基本信息】 西北农林科技大学 ， 农药学， 2009， 硕士

【摘要】 前期研究表明芳香二脒类化合物具有不同于其它类杀菌剂的特征,并已筛选研制出高效、低毒新型杀菌剂丙烷脒;同时研究表明对芳香二脒类化合物进行进一步的结构修饰和衍生合成有望发现更高抑菌活性的化合物。鉴于此,在前期基础上,本文对芳香二脒类化合物进行进一步的合成,并系统测定合成化合物的抑菌活性。得到了如下结果:1.以芳香二脒类化合物骨架为基础,合成芳香二脒类似物9个,并采用波谱学方法确定了各化合物的化学结构。分别为:A3(4,4’-二(N-苯基)脒基1,3-二苯氧基丙烷)、A4(4,4’-二(N-苯甲酰基)脒基1,3-二苯氧基丙烷)、A5(4,4’-二(N-甲酰基)脒基1,3-二苯氧基丙烷)、A7(4,4’-二(N-叔丁基)脒基1,3-二苯氧基丙烷)、A8 (4,4’-二(N-环丙基)脒基1,3-二苯氧基丙烷)、A10(4,4’-二(N-甲基)脒基1,3-二苯氧基丙烷)、B4(4,4’-二(N-苯甲酰基)脒基1,3-二苯氧基丁烷)、B9(4,4’-二(N-乙胺基)脒基1,3-二苯氧基丁烷)、C9(4,4’-二(N-乙胺基)脒基1,3-二苯氧基戊烷)。2.生长速率法测试表明,在10 mg/L浓度下,各合成化合物对番茄灰霉病菌、白菜黑斑病菌、烟草赤星病菌菌丝生长均有一定的抑制作用,其中化合物A8对番茄灰霉病菌菌丝生长抑制毒力最高,EC50为1.46 mg/L,与丙烷脒相当;A3、A4、A5、A7、A10、B4、B9、C9等对番茄灰霉病菌菌丝生长抑制毒力较低,EC50在12.99 mg/L～153.77 mg/L之间。3.黄瓜子叶法试验表明,各合成化合物对番茄灰霉病均有一定的保护和治疗效果。10mg/L下,A8 3d的保护、治疗效果分别为49.01%、63.09%,与丙烷脒相当;A10 3d的保护效果为52.15%,相当于丙烷脒,而治疗效果为30.69%,低于丙烷脒;20mg/L下,A8、A10 3d的保护和治疗效果均相当于丙烷脒处理;其他化合物的药效均显著低于丙烷脒。4.番茄幼果穿刺法试验表明,化合物A8、A10和丙烷脒对番茄幼果有较高的药效。50mg/L剂量下,二者的分别为69.85%和59.80,59.92%和49.97%,均相当于丙烷脒处理;100 mg/L剂量下,二者的保护和治疗效果与相应剂量下丙烷脒处理相当。5.初步定性构效关系分析表明,芳香二脒类化合物对番茄灰霉病菌的抑制活性与化合物结构存在明显相关性:醚基碳链为3时,其抑菌活性高于醚基碳链为4和5的化合物;脒基取代的不同其抑菌活性差异明显,当醚基碳链为3时,环丙基取代的芳香二脒类化合物的抑菌活性明显较高;而脒基上引入苯酰基、苯基等芳香性基团时,化合物活性则明显降低。对此尚有待于进一步研究。更多还原

【Abstract】 Previous study of the Aromatic Diamidino showed that the fungicidal mechanism of the kind of compounds were different from other types of fungicides, and had developed a new fungicides Propamidine with high fungicidal activity, low toxicity; at the same time, the research showed that further structural modified or synthesis of Aromatic Diamidino would expected to find compounds with higher antibacterial activity. In view of this, based on the previous study, this article investigated the further synthesis of the Aromatic Diamidino, and systematically measured the antibacterial activity of the synthetic compounds. The results of the research have found as follows:(1)Nine Aromatic Diamidino analogues have been synthesized and identified with MS,1HNMR and 13CNMR.As follows:A3(1,4-di(N-Phenyl,4-bis(4-amidinop- -henoxy),A4(1,4-di(N-Benzoyl,4-bis(4-amidinophenoxy)propane),A5(1,4-di(N-Formyl,4-bis(4-amidinophenoxy)propane),A7(1,4-di(N-Tert-butyl,4-bis(4-amidinophenoxy)propane),A8(1,3-di(N-Cyclopropyl,4-bis(4-amidinophenoxy)propane,),A10(1,4-di(N-Methyl,4-bis(4-amidinophenoxy)propane),B4(1,4-di(N-Benzoyl,4-bis(4-amidinophenoxy)butane),B9(1,4-di(N-ethylamino,4-bis(4-amidinophenoxy)butane),C9(1,4-di(N-ethylamino,4-bis(4-amidinophenoxy)pentane).(2) As 10mg / L concentration, all compounds showed inhibitory activity against Botrytis cinerea、Alternaria brassicae Sacc. and Alter aria alternatn Keissler in vitro. With mycelial growth rate method, the EC50 value of A8 is 1.4635 mg/L, higher than propamidine. The EC50 value of A3, A4, A5, A7, A10, B4, B9, C9 is between 12.9914 mg/L and 153.7742 mg/L, all of which is lower than propamidine.(3) The protective and therapy effectiveness were experimented on cucumber Cotyledon. At 10mg/L, the protective and therapy effectiveness of A8 were 49.01% , 63.09% respectively, equaling to the effectiveness of propamidine; At 20mg/L, the protective and therapy effectiveness of A8 (58.91%, 67.92% respectively) are equaling to the effectiveness of propamidine. The protective and therapy effectiveness of other compounds are all lower than the effectiveness of propamidine.(4) The protective and therapy effectiveness had also been experimented on young tomato fruit. At 50mg/L, the protective and therapy effectiveness of A8 equal to the effectiveness of propamidine. The protective and therapy effectiveness of A10(59.92%,49.97% respectively) are lower than the effectiveness of propamidine; At 100mg/L, the protective effectiveness of A8 , A10 are equaling to the same effectiveness of propamidine; the protective and therapy effectiveness of other compounds are all lower than effectiveness of propamidine.(5) Studies of indoor leaf in vitro experiment and young fruit experiment showed pentamidine and its analogues had potently to phytopathogen, and the effciency varied with structures: when the number of ether carbon chain is 3, its antibacterial activity is higher than 4 or 5 ether-based carbon-chain compounds; the fungicidal activity of Amidine different substituted compounds are obviously difenrent. As the number of ether carbon chain is 3, the fungicidal activity of the compound replaced with cyclopropyl is most active; and the introduction of the amidine acyl benzene, aromaticity, such as phenyl group, these compounds exhibit lower activity. the structure-activity analysis of Aromatic diamidino compounds and Formamidine antibacterial activity, is worthy of further study.更多还原