三酮类和吲哚-3-乙酸类化合物的合成与除草活性研究
发布时间：2018-12-27 10:17
【摘要】：除草剂是农药的重要品种,是农田杂草防治、粮食作物稳定生产的重要保障。随着化学除草在农业中占据主导地位,除草剂选择性差、环境污染严重和抗性增强等问题日渐突出。因此发展高效、低毒和环境友好的新型除草剂对保障粮食生产有重要意义。据有关报道,前除草剂相比活性成分有诸多的优点,例如高选择性和高稳定性等;另外生长素除草剂具有高选择性以及产生抗性慢等优点。本文设计合成了一系列新型的三酮类和吲哚-3-乙酸类化合物,并对其进行生物活性研究,以及通过除草活性的结果初步判断合成的三酮类化合物是否具有前除草剂的特性。主要内容包括以下四个部分:1.简要概述了三酮类化合物和生长素除草剂的研究进展,并对前除草剂做了简单的综述。以此为基础,提出了本论文的两个研究思路。2.基于磺草酮和硝磺草酮为活性成分,选用合适的可裂解的官能团,设计了一系列新型的的三酮类化合物。以取代苯甲酸为原料,通过多步合成得到3-(N-取代胺)-2-(2-取代基-4-甲砜基苯甲酰基)环己-2-烯酮和3-苯硫醚-2-(2-取代基-4-甲砜基苯甲酰基)-环己-2-烯酮两类化合物。并通过1HNMR、13CNMR、FTIR和HRMS等分子结构鉴定手段对目标化合物进行结构确认。3.基于结构的药物设计方法,设计合成了一系列新型α取代的吲哚-3-乙酸衍生物以及3,3-二吲哚丙酸类化合物,并通过1HNMR、13CNMR、FTIR、MS和元素分析等分子结构鉴定手段进行结构确认。文献报道吲哚-3-乙酸类化合物可以和生长素受体蛋白TIR1结合,阻碍TIR1-IAA-Aux/IAA复合物的形成,抑制了生长素响应基因的表达。选用吲哚-3-乙酸和TIR1受体结合的活性口袋进行分子对接,发现α取代的吲哚-3-乙酸α链上的苯环和TIIR1受体中的Phe82和Phe380形成强烈的作用,羧基部分能与TIR1受体中的Arg403和Ser438形成氢键相互作用。4.采用室内平皿法,对合成的两类目标化合物进行室内除草活性初筛。活性测试结果表明三酮类化合物8a-g在100 ppm和10 ppm的浓度下均能使稗草和油菜产生严重的白化症状,从而较好的控制稗草和油菜的生长,可初步判断化合物8a-g具有前除草剂的特性。另外α取代吲哚-3-乙酸类化合物的抑制规律符合生长素型除草剂的选择性规律,能较好的控制双子叶植物。其中化合物15d和15h在100 ppm浓度下对油菜根的抑制率分别达到96%和95%;在10 ppm浓度下,其抑制率也能分别达到92%和93%。
[Abstract]:Herbicide is an important variety of pesticides, is an important guarantee for the control of weeds in farmland and the stable production of grain crops. With the dominant position of chemical herbicide in agriculture, the problems of poor herbicide selectivity, serious environmental pollution and increased resistance have become increasingly prominent. Therefore, it is important to develop new herbicides with high efficiency, low toxicity and environmental friendliness to ensure grain production. According to relevant reports, proherbicides have many advantages over active components, such as high selectivity and high stability, and auxin herbicides have the advantages of high selectivity and low resistance. In this paper, a series of new triketones and indole-3-acetic acid compounds were designed and synthesized, and their biological activities were studied. The main contents include the following four parts: 1. The research progress of triketones and auxin herbicides is briefly reviewed, and the preherbicides are briefly reviewed. On this basis, this paper puts forward two research ideas. 2. A series of new triketones were designed based on sulfoxone and nitratoxanone as active components and suitable pyrolytic functional groups were selected. Using substituted benzoic acid as raw material, Synthesis of 3- (N-substituted amines) -2- (2-substituted -4-methylsulfone benzoyl) cyclohexenone and 3- (2-substituted -4-methylsulfone benzoyl) by multi-step synthesis -Cyclohexane-2-ketene compounds. The structure of the target compound was confirmed by 1HN MR-13CNMR-FTIR and HRMS. A series of novel 伪 -substituted indole-3-acetic acid derivatives and 3H-3-diindopylic acid compounds were designed and synthesized based on structure-based drug design method, and were synthesized by 1HNMR-13CNMR-FTIRs. MS and elemental analysis were used to identify the molecular structure. It is reported that indole 3-acetic acid compounds can bind to auxin receptor protein (TIR1), block the formation of TIR1-IAA-Aux/IAA complex, and inhibit the expression of auxin responsive gene. The active pocket of indole 3-acetic acid and TIR1 receptor was used for molecular docking. It was found that the benzene ring in 伪 substituted indole 3-acetic acid 伪 chain and the Phe82 and Phe380 in TIIR1 receptor formed a strong effect. The carboxyl group can form hydrogen bond interaction with Arg403 and Ser438 in TIR1 receptor. 4. Two kinds of synthetic target compounds were screened for herbicidal activity in laboratory by plate method. The results of activity test showed that 8a-g could cause serious albinism symptoms of barnyardgrass and rape at the concentration of 100 ppm and 10 ppm, thus controlling the growth of barnyardgrass and rape. It can be preliminarily judged that compound 8a-g has the property of proherbicide. In addition, the inhibition of 伪 -substituted indole-3-acetic acid compounds was consistent with the selective rule of auxin herbicides and could control dicotyledonous plants well. The inhibition rates of the compounds on rape roots were 96% and 95% at 100 ppm concentration and 92% and 93% at 10 ppm concentration, respectively.
【学位授予单位】：华中师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626;TQ457.2
本文编号：2392912
[Abstract]:Herbicide is an important variety of pesticides, is an important guarantee for the control of weeds in farmland and the stable production of grain crops. With the dominant position of chemical herbicide in agriculture, the problems of poor herbicide selectivity, serious environmental pollution and increased resistance have become increasingly prominent. Therefore, it is important to develop new herbicides with high efficiency, low toxicity and environmental friendliness to ensure grain production. According to relevant reports, proherbicides have many advantages over active components, such as high selectivity and high stability, and auxin herbicides have the advantages of high selectivity and low resistance. In this paper, a series of new triketones and indole-3-acetic acid compounds were designed and synthesized, and their biological activities were studied. The main contents include the following four parts: 1. The research progress of triketones and auxin herbicides is briefly reviewed, and the preherbicides are briefly reviewed. On this basis, this paper puts forward two research ideas. 2. A series of new triketones were designed based on sulfoxone and nitratoxanone as active components and suitable pyrolytic functional groups were selected. Using substituted benzoic acid as raw material, Synthesis of 3- (N-substituted amines) -2- (2-substituted -4-methylsulfone benzoyl) cyclohexenone and 3- (2-substituted -4-methylsulfone benzoyl) by multi-step synthesis -Cyclohexane-2-ketene compounds. The structure of the target compound was confirmed by 1HN MR-13CNMR-FTIR and HRMS. A series of novel 伪 -substituted indole-3-acetic acid derivatives and 3H-3-diindopylic acid compounds were designed and synthesized based on structure-based drug design method, and were synthesized by 1HNMR-13CNMR-FTIRs. MS and elemental analysis were used to identify the molecular structure. It is reported that indole 3-acetic acid compounds can bind to auxin receptor protein (TIR1), block the formation of TIR1-IAA-Aux/IAA complex, and inhibit the expression of auxin responsive gene. The active pocket of indole 3-acetic acid and TIR1 receptor was used for molecular docking. It was found that the benzene ring in 伪 substituted indole 3-acetic acid 伪 chain and the Phe82 and Phe380 in TIIR1 receptor formed a strong effect. The carboxyl group can form hydrogen bond interaction with Arg403 and Ser438 in TIR1 receptor. 4. Two kinds of synthetic target compounds were screened for herbicidal activity in laboratory by plate method. The results of activity test showed that 8a-g could cause serious albinism symptoms of barnyardgrass and rape at the concentration of 100 ppm and 10 ppm, thus controlling the growth of barnyardgrass and rape. It can be preliminarily judged that compound 8a-g has the property of proherbicide. In addition, the inhibition of 伪 -substituted indole-3-acetic acid compounds was consistent with the selective rule of auxin herbicides and could control dicotyledonous plants well. The inhibition rates of the compounds on rape roots were 96% and 95% at 100 ppm concentration and 92% and 93% at 10 ppm concentration, respectively.
【学位授予单位】：华中师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626;TQ457.2
【参考文献】
相关期刊论文 前9条
1 陈平;刘国光;王枫亮;马京帅;黄军磊;李富华;姚琨;吕文英;;UV降解水溶液中吲哚美辛的动力学研究[J];环境科学学报;2016年06期
2 景小兰;董良利;张建华;曹昌林;郭瑞峰;史丽娟;彭之东;范娜;李光;白文斌;;中国除草剂的发展现状及其在高粱上的应用[J];中国农学通报;2015年25期
3 冯程程;马红;;除草剂应用现状及挑战[J];江苏农业科学;2014年08期
4 Yaling Song;;Insight into the mode of action of 2,4-dichlorophenoxyacetic acid(2,4-D) as an herbicide[J];Journal of Integrative Plant Biology;2014年02期
5 苏少泉;;除草剂品种开发的新靶标与前除草剂[J];农药研究与应用;2007年06期
6 谭效松;贺红武;;除草剂的作用靶标与作用模式[J];农药;2005年12期
7 付颖,叶非,王常波;生物源除草剂研究与使用进展[J];农药;2002年05期
8 吴彦超,胡方中,杨华铮;HPPD抑制剂的研究进展[J];农药学学报;2001年03期
9 魏福香;除草剂的现状及发展趋势[J];安徽农业;1999年03期
相关硕士学位论文 前1条
1 陈俊;苯并噻唑类化合物的设计合成及其生物活性研究[D];华中师范大学;2015年
，本文编号：2392912
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2392912.html
教材专著
