【作者】 王飞艳；

【导师】 岳霞丽；

【作者基本信息】 华中农业大学 ， 农药学， 2011， 硕士

【摘要】 取代脲类化合物大多具有生物活性,广泛用作杀虫剂、杀菌剂、除草剂及植物生长调节剂,其发展应符合农药发展趋势即高效、低毒、无残留及环境相容性好。因氟原子具有模拟效应、渗透效应、电子效应和阻碍效应,而嘧啶环结构简单、作用方式独特,本文根据活性亚结构拼接法,在保留脲桥的基础上,在脲桥一端的氮原子上引入含氟原子或三氟甲基的苯环,在脲桥另一端的氮原子上引入取代嘧啶环,设计合成了32个含氟苯基嘧啶脲类化合物,其中16个化合物未见文献报道,通过测定熔点及红外光谱、核磁共振氢谱对其进行结构表征,对目标化合物进行了初步植物生长调节活性及除草活性实验。主要研究内容如下：1含氟苯基嘧啶脲类化合物的合成及结构表征采用基于光气的异氰酸酯法,中间产物异氰酸酯不经分离纯化,直接与取代嘧啶胺进行亲核加成反应生成目标产物,反应操作简单,安全易定量;采用红外和核磁对其进行结构表征。目标化合物结构通式如下：1 R1=2-CF3,R2,R3=OCH3;2 R1=3-CF3,R3=-OCH3;3 R1=2-F,R2,R3=OCH3:4 R1=3-F,R2,R3=OCH3;5 R2,R3-OCF3;6 R1=CHaR*=Q8 Rp2-F,Rf<H3Rr-Cl;9 R,=3-F, ll Ri=2-€F3> Rr-CH3RfOH;12 R4=K373, Rr-CH3,R3-OH;13 R,=2-F, Rr<H3R3=OH;16 R,=2-CF3, RaR.3<Hs 17 R,=3-CF3,R2,Rf-CH3;18 R,=2-F, RaJlr-CHs; 19 Ri=3-F, RaJlf^CHs^O RaRH^H^l Ri=2-CF3, R2,Rr^22 R,=3-CF3, RiRf-H; 23 R,=2-F, RaRr^H; 24 R,=3-F, R2Jlf-H; 25 Ra^r-H^ R2=-OCH3, R3=X^27 R,=2-F, Rr-Offl3R3<^Rr2^3,Rj<X3i3R3<^9R,=3^3,RfMDCH3Rr<^0R^^ 31 R,=2-CF3; 32 R,=3-CF32初步生物活性测试采用“幼苗生根法”和“除草平皿法”分别初步测试了目标化合物在10、25、50、100、200 mg/L五个浓度梯度下的室内植物生长调节活性和除草活性。初步活性结果表明：目标化合物的植物生长调节活性最佳促进剂量为10 mg/L,在在此浓度时,化合物3、4、8、11、23、27和28对水稻的茎长和根长促长率均在80%以上,而化合物4、12、13、22和31对油菜的茎长和根长促长率均在74%以上,且茎比根对药液更加敏感,促进效果更好；对白苋的根比茎抑制效果好,有的化合物校正根长抑制率高达100%以上,在100 mg/L时,化合物4、10、13和27对白苋的茎长和根长抑制率均在30%以上；但对狼尾草的茎比根抑制作用好,大部分化合物的校正茎长抑制率在90%以上,但校正根长抑制率在50%左右,化合物16和20对狼尾草生长的抑制效果最好。更多还原

【Abstract】 Most of unsymmetrical substituted ureas are kinds of compounds with diverse biological activity. Because their structure contains a peptide bond, they are widely used for insecticide, fungicide, herbicide and plant growth regulator. The development trend of future pesticide is super high effectivity, low toxicity, no residue and good environmental compatibility. Fluorine atom has simulative, osmotic, electronic and obstructive function, and the structure of pyrimidine ring is simple and particular mode of action. In this paper, the benzene ring containing fluorine atom or trifluoromethyl was introduced to the N atom of urea bridge, and the substituted pyrimidine ring was leaded into the other N atom of urea bridge.32 urea compounds were synthesized. Thereinto, sixteen of which were novel compounds. Their structures were confirmed by melting point, IR and’HNMR. At the same time, the primary biological activity of target compounds were also studied. The main contents of study as following:I Synthesis and characterization of fluorophenyl-pyrimidinyl urea derivativesThe synthetic method of ureas generally phosgene-based isocyanates, intermediate isocyanate was directly used to react with pyrilamine to product target compounds without further purification. This synthesis method was simple, safe and easy to fix on quantity. IR and’HNMR were adopted to define the compounds’structure. The structures of urea derivatives were shown as following: 1 R,=2-CF3. RzJlfOCH^ Rp3-Oyi2,Rf<)CH33 Ri=2-F, RaRj=OCHs4 Rr^JRaJ^OCH^ R,=3-CF3, Rf^RK^ R,=2-F,R-KH3Rf-a9 Ri=3-F, R|=2-CF3. Rf^RfOH;^ RpJCFi Rp€H3R3=OH;13 R=2-F, Rj-}3R3=-OH;14 R, 3-F,Rf--CH3R-0R;15 R_r--CHAR,, -OR16 R, 2-CF3,3, 17 R,=2-CF3, R^r-CHi 17 R1=3-CF3, RaflHt 23 R,=2-F, R^Rf-H; 24 R,=3-F, R^H; 25 R^H^ R:OCH3. R^-027 R,=2-F, RfMXH3.R3M33Rr2<T3,Rf<X^3RH^9Ri=3<T3,Rf<)CH3R3<130Ri^-F; 31 Rf=2-CF3; 32 Ri=3-CF3II The preliminary biological activity test"The seeding root law" and "Petri dish testing for herbicidal bioactivity" were respectively adopted to test the plant growth regulating, herbicidal activities of target compounds with the concentration of 10、25、50、100 and 200 mg/L.The preliminary bioassay results showed that:The optimal concentration of most compounds was 10 mg/L. on this concentration, compounds 3、4、8、11、23、27 and 28 in promoting growth rate were 80% for rice, as well as compounds、12、13、22 and 31 in promoting growth rate were 75% for rape, Simultaneously, the promoting effect on the stem was better than the root; For amaranthus albus L, the inhibitory effect on the root was better than the stem, the inhibition rate of root length of some compounds reached up to 100%. on the concentration 100 mg/L, the inhibition rate of compounds 4、10、13 and 27 were more than 30%. The weeding effect was better. However, the inhibitory effect on the stem was better than the root of pennisetum, the inhibition rate of stem length reached up to 90%, the inhibition rate of root length was only 50%, compound 16 and 20 stronge herbicidal activity of amaranthus.更多还原