新型橙酮类和香豆素类化合物的设计、合成与除草活性研究
发布时间：2018-12-20 06:58
【摘要】：天然产物由于具有选择性强、易生物降解和环境兼容性好等优势,为研发高选择性、环境友好的农药新品种提供了思路和基础。橙酮和香豆素是两类存在于植物中的天然产物,在医药研究领域受到广泛关注,在农药方面的应用研究还较少。在充分调研文献和我们课题组的研究基础上,为了提高橙酮和香豆素类化合物的除草活性,本论文基于活性片段拼接原理,将芳氧羧酸类除草剂的活性结构(芳氧乙酰氧基)引入到橙酮、香豆素结构中,设计、合成了两类共46个目标化合物,在表征结构的基础上,研究它们的除草活性和构效关系。具体内容如下:一、6-芳氧乙酰氧基橙酮衍生物的合成与除草活性研究以间苯二酚和氯乙腈为原料制备得到2,4-二羟基-a-氯代苯乙酮,然后其与取代苯甲醛在碱性条件下缩合得到18个关键中间体——6-羟基橙酮衍生物(I-1~I-18),通过不同芳氧乙酰氯(D1~D3)和I-1~I-18的亲核取代反应,合成了27个新的6-芳氧乙酰氧基橙酮衍生物(TM-1~TM-27)。所合成化合物的结构均采用1H NMR、13CNMR、IR和元素分析进行确认。油菜平皿法和稗草小杯法的初步除草活性测试结果表明:在10μg/mL时,部分目标化合物对双子叶植物油菜根长的抑制效果与商品化除草剂2,4-D相当,且选择性优于2,4-D。盆栽实验(100、50和10 g/亩)进一步表明,茎叶处理的效果远高于土壤处理的效果,并对双子叶植物表现非常高的选择性,作用机制与2,4-D可能不同,具有较高的应用潜力和深入研究的价值。如在10 g/亩时,TM-2茎叶处理时对双子叶植物油菜和苋菜的抑制率分别为100%和92.5%,优于2,4-D的茎叶处理效果。此外,该类化合物还表现出一定的构效关系,苯环上取代基(R1和R2)的位置和电性对除草活性有重要的影响。二、7-芳氧乙酰氧基香豆素衍生物的合成与除草活性研究不同的间苯二酚与相应的乙酰乙酸酯类化合物在酸催化下合成了9个中间体——7-羟基香豆素衍生物(I-19~I-27),通过不同芳氧乙酰氯(D1~D4)对I-19~I-27进行酰化,合成了19个新的7-苯氧乙酰氧基香豆素衍生物(TM-28~TM-46)。所有合成化合物的结构均经1H NMR、13C NMR、IR和元素分析的确认。油菜平皿法和稗草小杯法初步的除草活性测试结果表明,大部分7-芳氧乙酰基取代的香豆素衍生物对双子叶植物油菜根长的的抑制率优于对照药2,4-D,且对单子叶植物稗草株高也有较高的抑制活性。盆栽实验(50 g/亩)也表明,目标化合物与2,4-D具有相当的抑制效果和选择性;并表现出一定的构效关系,为我们进一步设计高除草活性的化合物提供了基础。
[Abstract]:Due to the advantages of high selectivity, easy biodegradation and good environmental compatibility, natural products provide the idea and foundation for the development of new pesticide varieties with high selectivity and environmental friendliness. Orange ketone and coumarin are two kinds of natural products which exist in plants. In order to improve the herbicidal activity of Orange ketone and coumarin compounds, this paper is based on the principle of active fragment splicing. The active structure of aromatic carboxylic acid herbicides (aryl oxyethyl) was introduced into the structure of orange ketone and coumarin. Two kinds of 46 target compounds were designed and synthesized. Based on the characterization of the structure, the herbicide activity and structure-activity relationship were studied. The main contents are as follows: (1) Synthesis and herbicidal activity of 6-aryl acetyl orange ketone derivatives; the synthesis and herbicidal activity of 6-aryloxyacetoxy Orange derivatives from resorcinol and chloracetonitrile were used as raw materials to obtain 2o 4-dihydroxy-achloro-acetophenone. Then 18 key intermediates, 6-hydroxyorange derivatives (I-1~I-18), were synthesized by condensation of substituted benzaldehyde with substituted benzaldehyde under alkaline conditions. The nucleophilic substitution reactions of different aryl acetyl chloride (D1~D3) and I-1~I-18 were carried out. Twenty-seven new derivatives of 6-aroxyacetyl Orange ketone (TM-1~TM-27) were synthesized. The structures of the synthesized compounds were confirmed by 1H NMR,13CNMR,IR and elemental analysis. The results of preliminary herbicidal activity test of rape plate method and barnyardgrass cup method showed that at 10 渭 g/mL, the inhibition effect of some target compounds on root length of dicotyledonous plant rapeseed was equal to that of commercial herbicide 2n4-D, and the selectivity was better than that of 2nc-4-D. Pot experiment (100g / mu and 10g / mu) further showed that the effect of stem and leaf treatment was much higher than that of soil treatment, and showed a very high selectivity to dicotyledonous plants, and the mechanism might be different from that of 24-D. It has high application potential and deep research value. For example, at 10 g / mu, the inhibitory rates of TM-2 on dicotyledonous rapeseed and amaranth were 100% and 92.5%, respectively, which were better than that of 24-D treatment. In addition, some structure-activity relationships were observed, and the positions and electrical properties of substituents (R1 and R2) on benzene rings had important effects on herbicidal activity. II. Synthesis and herbicide activity of 7-Aryloxyacetylcoumarin Derivatives; nine intermediates, 7-hydroxycoumarin derivatives (I-19~I-27), were synthesized from resorcinol and corresponding acetoacetate esters under acid catalysis. Nineteen new 7-phenoxyacetyl coumarin derivatives (TM-28~TM-46) were synthesized by acylation of I-19~I-27 with different aromatic acetyl chloride (D1~D4). The structures of all the synthesized compounds were confirmed by 1H NMR,13C NMR,IR and elemental analysis. The results of herbicidal activity test of rape plate method and barnyard grass cup method showed that most of the coumarin derivatives substituted by 7-aryloxyacetyl group could inhibit the root length of the dicotyledonous plant rapeseed more effectively than that of the control drug 24-D. It also had high inhibitory activity on the plant height of Monocotyledonous barnyard grass. Pot experiment (50 g / mu) also showed that the target compound had considerable inhibitory effect and selectivity with 2n4-D, and showed a certain structure-activity relationship, which provided the basis for further design of high herbicidal activity compounds.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ450.1
本文编号：2387611
[Abstract]:Due to the advantages of high selectivity, easy biodegradation and good environmental compatibility, natural products provide the idea and foundation for the development of new pesticide varieties with high selectivity and environmental friendliness. Orange ketone and coumarin are two kinds of natural products which exist in plants. In order to improve the herbicidal activity of Orange ketone and coumarin compounds, this paper is based on the principle of active fragment splicing. The active structure of aromatic carboxylic acid herbicides (aryl oxyethyl) was introduced into the structure of orange ketone and coumarin. Two kinds of 46 target compounds were designed and synthesized. Based on the characterization of the structure, the herbicide activity and structure-activity relationship were studied. The main contents are as follows: (1) Synthesis and herbicidal activity of 6-aryl acetyl orange ketone derivatives; the synthesis and herbicidal activity of 6-aryloxyacetoxy Orange derivatives from resorcinol and chloracetonitrile were used as raw materials to obtain 2o 4-dihydroxy-achloro-acetophenone. Then 18 key intermediates, 6-hydroxyorange derivatives (I-1~I-18), were synthesized by condensation of substituted benzaldehyde with substituted benzaldehyde under alkaline conditions. The nucleophilic substitution reactions of different aryl acetyl chloride (D1~D3) and I-1~I-18 were carried out. Twenty-seven new derivatives of 6-aroxyacetyl Orange ketone (TM-1~TM-27) were synthesized. The structures of the synthesized compounds were confirmed by 1H NMR,13CNMR,IR and elemental analysis. The results of preliminary herbicidal activity test of rape plate method and barnyardgrass cup method showed that at 10 渭 g/mL, the inhibition effect of some target compounds on root length of dicotyledonous plant rapeseed was equal to that of commercial herbicide 2n4-D, and the selectivity was better than that of 2nc-4-D. Pot experiment (100g / mu and 10g / mu) further showed that the effect of stem and leaf treatment was much higher than that of soil treatment, and showed a very high selectivity to dicotyledonous plants, and the mechanism might be different from that of 24-D. It has high application potential and deep research value. For example, at 10 g / mu, the inhibitory rates of TM-2 on dicotyledonous rapeseed and amaranth were 100% and 92.5%, respectively, which were better than that of 24-D treatment. In addition, some structure-activity relationships were observed, and the positions and electrical properties of substituents (R1 and R2) on benzene rings had important effects on herbicidal activity. II. Synthesis and herbicide activity of 7-Aryloxyacetylcoumarin Derivatives; nine intermediates, 7-hydroxycoumarin derivatives (I-19~I-27), were synthesized from resorcinol and corresponding acetoacetate esters under acid catalysis. Nineteen new 7-phenoxyacetyl coumarin derivatives (TM-28~TM-46) were synthesized by acylation of I-19~I-27 with different aromatic acetyl chloride (D1~D4). The structures of all the synthesized compounds were confirmed by 1H NMR,13C NMR,IR and elemental analysis. The results of herbicidal activity test of rape plate method and barnyard grass cup method showed that most of the coumarin derivatives substituted by 7-aryloxyacetyl group could inhibit the root length of the dicotyledonous plant rapeseed more effectively than that of the control drug 24-D. It also had high inhibitory activity on the plant height of Monocotyledonous barnyard grass. Pot experiment (50 g / mu) also showed that the target compound had considerable inhibitory effect and selectivity with 2n4-D, and showed a certain structure-activity relationship, which provided the basis for further design of high herbicidal activity compounds.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ450.1
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