【摘要】：天然產(chǎn)物由于具有選擇性強、易生物降解和環(huán)境兼容性好等優(yōu)勢,為研發(fā)高選擇性、環(huán)境友好的農(nóng)藥新品種提供了思路和基礎(chǔ)。橙酮和香豆素是兩類存在于植物中的天然產(chǎn)物,在醫(yī)藥研究領(lǐng)域受到廣泛關(guān)注,在農(nóng)藥方面的應(yīng)用研究還較少。在充分調(diào)研文獻和我們課題組的研究基礎(chǔ)上,為了提高橙酮和香豆素類化合物的除草活性,本論文基于活性片段拼接原理,將芳氧羧酸類除草劑的活性結(jié)構(gòu)(芳氧乙酰氧基)引入到橙酮、香豆素結(jié)構(gòu)中,設(shè)計、合成了兩類共46個目標(biāo)化合物,在表征結(jié)構(gòu)的基礎(chǔ)上,研究它們的除草活性和構(gòu)效關(guān)系。具體內(nèi)容如下:一、6-芳氧乙酰氧基橙酮衍生物的合成與除草活性研究以間苯二酚和氯乙腈為原料制備得到2,4-二羥基-a-氯代苯乙酮,然后其與取代苯甲醛在堿性條件下縮合得到18個關(guān)鍵中間體——6-羥基橙酮衍生物(I-1~I-18),通過不同芳氧乙酰氯(D1~D3)和I-1~I-18的親核取代反應(yīng),合成了27個新的6-芳氧乙酰氧基橙酮衍生物(TM-1~TM-27)。所合成化合物的結(jié)構(gòu)均采用1H NMR、13CNMR、IR和元素分析進行確認(rèn)。油菜平皿法和稗草小杯法的初步除草活性測試結(jié)果表明:在10μg/mL時,部分目標(biāo)化合物對雙子葉植物油菜根長的抑制效果與商品化除草劑2,4-D相當(dāng),且選擇性優(yōu)于2,4-D。盆栽實驗(100、50和10 g/畝)進一步表明,莖葉處理的效果遠高于土壤處理的效果,并對雙子葉植物表現(xiàn)非常高的選擇性,作用機制與2,4-D可能不同,具有較高的應(yīng)用潛力和深入研究的價值。如在10 g/畝時,TM-2莖葉處理時對雙子葉植物油菜和莧菜的抑制率分別為100%和92.5%,優(yōu)于2,4-D的莖葉處理效果。此外,該類化合物還表現(xiàn)出一定的構(gòu)效關(guān)系,苯環(huán)上取代基(R1和R2)的位置和電性對除草活性有重要的影響。二、7-芳氧乙酰氧基香豆素衍生物的合成與除草活性研究不同的間苯二酚與相應(yīng)的乙酰乙酸酯類化合物在酸催化下合成了9個中間體——7-羥基香豆素衍生物(I-19~I-27),通過不同芳氧乙酰氯(D1~D4)對I-19~I-27進行酰化,合成了19個新的7-苯氧乙酰氧基香豆素衍生物(TM-28~TM-46)。所有合成化合物的結(jié)構(gòu)均經(jīng)1H NMR、13C NMR、IR和元素分析的確認(rèn)。油菜平皿法和稗草小杯法初步的除草活性測試結(jié)果表明,大部分7-芳氧乙�；〈南愣顾匮苌飳﹄p子葉植物油菜根長的的抑制率優(yōu)于對照藥2,4-D,且對單子葉植物稗草株高也有較高的抑制活性。盆栽實驗(50 g/畝)也表明,目標(biāo)化合物與2,4-D具有相當(dāng)?shù)囊种菩Ч瓦x擇性;并表現(xiàn)出一定的構(gòu)效關(guān)系,為我們進一步設(shè)計高除草活性的化合物提供了基礎(chǔ)。
[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.
【學(xué)位授予單位】：江蘇大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ450.1

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