三酮類和吲哚-3-乙酸類化合物的合成與除草活性研究
發(fā)布時間：2018-12-27 10:17
【摘要】：除草劑是農(nóng)藥的重要品種,是農(nóng)田雜草防治、糧食作物穩(wěn)定生產(chǎn)的重要保障。隨著化學除草在農(nóng)業(yè)中占據(jù)主導地位,除草劑選擇性差、環(huán)境污染嚴重和抗性增強等問題日漸突出。因此發(fā)展高效、低毒和環(huán)境友好的新型除草劑對保障糧食生產(chǎn)有重要意義。據(jù)有關報道,前除草劑相比活性成分有諸多的優(yōu)點,例如高選擇性和高穩(wěn)定性等;另外生長素除草劑具有高選擇性以及產(chǎn)生抗性慢等優(yōu)點。本文設計合成了一系列新型的三酮類和吲哚-3-乙酸類化合物,并對其進行生物活性研究,以及通過除草活性的結果初步判斷合成的三酮類化合物是否具有前除草劑的特性。主要內(nèi)容包括以下四個部分:1.簡要概述了三酮類化合物和生長素除草劑的研究進展,并對前除草劑做了簡單的綜述。以此為基礎,提出了本論文的兩個研究思路。2.基于磺草酮和硝磺草酮為活性成分,選用合適的可裂解的官能團,設計了一系列新型的的三酮類化合物。以取代苯甲酸為原料,通過多步合成得到3-(N-取代胺)-2-(2-取代基-4-甲砜基苯甲�；�)環(huán)己-2-烯酮和3-苯硫醚-2-(2-取代基-4-甲砜基苯甲�；�)-環(huán)己-2-烯酮兩類化合物。并通過1HNMR、13CNMR、FTIR和HRMS等分子結構鑒定手段對目標化合物進行結構確認。3.基于結構的藥物設計方法,設計合成了一系列新型α取代的吲哚-3-乙酸衍生物以及3,3-二吲哚丙酸類化合物,并通過1HNMR、13CNMR、FTIR、MS和元素分析等分子結構鑒定手段進行結構確認。文獻報道吲哚-3-乙酸類化合物可以和生長素受體蛋白TIR1結合,阻礙TIR1-IAA-Aux/IAA復合物的形成,抑制了生長素響應基因的表達。選用吲哚-3-乙酸和TIR1受體結合的活性口袋進行分子對接,發(fā)現(xiàn)α取代的吲哚-3-乙酸α鏈上的苯環(huán)和TIIR1受體中的Phe82和Phe380形成強烈的作用,羧基部分能與TIR1受體中的Arg403和Ser438形成氫鍵相互作用。4.采用室內(nèi)平皿法,對合成的兩類目標化合物進行室內(nèi)除草活性初篩�；钚詼y試結果表明三酮類化合物8a-g在100 ppm和10 ppm的濃度下均能使稗草和油菜產(chǎn)生嚴重的白化癥狀,從而較好的控制稗草和油菜的生長,可初步判斷化合物8a-g具有前除草劑的特性。另外α取代吲哚-3-乙酸類化合物的抑制規(guī)律符合生長素型除草劑的選擇性規(guī)律,能較好的控制雙子葉植物。其中化合物15d和15h在100 ppm濃度下對油菜根的抑制率分別達到96%和95%;在10 ppm濃度下,其抑制率也能分別達到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 偽 -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 偽 substituted indole 3-acetic acid 偽 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 偽 -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.
【學位授予單位】：華中師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O626;TQ457.2
本文編號：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 偽 -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 偽 substituted indole 3-acetic acid 偽 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 偽 -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.
【學位授予單位】：華中師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O626;TQ457.2
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