【作者】 方利；

【导师】 江洪；

【作者基本信息】 华中农业大学 ， 农药学， 2007， 硕士

【摘要】 N-硝基化合物是一类具有生物调节作用的多功能化合物，而二硝基苯胺类除草剂具有高效低毒、除草谱广的特点。本文对芳胺的氨基N-硝化和以取代的2，6-二硝基苯胺为基体的N-硝基脲类化合物的合成进行研究与探讨。并对所合成的目标产物进行了生物活性实验。主要研究内容如下：一、芳胺的氨基N-硝化（1） N-硝基-4-硝基苯胺、N-硝基-2-硝基苯胺的合成在合成N-硝基-4-硝基苯胺（a）、N-硝基-2-硝基苯胺（b）时，分别以对硝基苯胺、邻硝基苯胺为原料，以冰乙酸为溶剂，乙酰硝酸酯为硝化剂，硝化剂与取代苯胺的物料比为2∶1～3∶1，反应时间在1～2h，反应温度控制在18～20℃为宜。（2） N-硝基-2，4，6-三硝基苯胺的合成在N-硝基-2，4，6-三硝基苯胺（c）的合成中，以2，4-二硝基苯胺为原料，以浓硫酸为溶剂，乙酰硝酸酯为硝化剂，硝化剂与取代苯胺的物料比为2∶1～3∶1，反应时间在1～2h，反应温度控制在18～25℃为宜。（3）对N-烷基-N-硝基-2，6-二硝基-4-三氟甲基苯胺的合成1R=H；2R=CH₃；3R=CH₂CH₂CH₃；4R=CH（CH₃）₂；5R=CH₂CH₂CH₂CH₃：N-烷基-N-硝基-2，6-二硝基-4-三氟甲基苯胺的结构如图2，该类化合物的合成以浓硫酸为溶剂，乙酰硝酸酯做硝化剂，均可得到较高产率的目标产物。实验结果表明：在取代苯胺的N-硝化时，采用乙酰硝酸酯做硝化剂，溶剂的选择至关重要，用冰醋酸作溶剂只发生胺基的N-硝化，而采用浓硫酸做溶剂，则会同时发生胺基的N-硝化以及苯环上邻、对位硝化的产物。二、N-硝基脲的合成（1）目标化合物N-硝基-2，4，6-三硝基苯基脲的合成6R=2Cl、4Cl、6Cl；7R=2Br、4Br、6Br；8R=2Cl、4Cl；9R=2Cl、5Cl；10R=3Cl、4Cl；11R=2Br、5Br；12R=2Br、4Br；目标化合物N-硝基-2，4，6-三硝基苯基脲的结构如图3。该类N-硝基脲目标化合物的合成采用酰氯法，即以N-硝基化合物为起始原料，三乙胺做引发剂和缚酸剂，二氯甲烷为溶剂，和固体光气反应得到酰氯，然后将溶剂二氯甲烷更换为甲苯，与另一个取代苯胺反应得到目标产物N-硝基-2，4，6-三硝基苯基脲。（2）目标化合物N-硝基-2，6-二硝基-4-三氟甲基苯基脲的合成13R=2Cl；14R=3Cl；15R=4Cl；16R=2CH₃；17R=4CH₃；18R=2F；19R=3F；目标化合物N-硝基-2，6-二硝基-4-三氟甲基苯基脲如图4所示，合成方法同N-硝基-2，4，6-三硝基苯基脲类似。但一直以二氯甲烷做溶剂。本文共计合成19种未见文献报道的N-硝基化合物，并通过元素分析、IR、¹H NMR、MS对其结构进行了表征。三、生物活性测试对19种目标产物进行生物活性测试，目标产物的实验浓度梯度为1000mg·kg^-1、500 mg·kg^-1、100 mg·kg^-1、50 mg·kg^-1、20 mg·kg^-1，供试作物为水稻、油菜，供试杂草为稗草、苋菜。采用Gaussian03程序中的PM3方法，计算该脲类化合物的结构参数，对化合物的结构参数与稗草生物活性进行相关性分析。实验结果表明：N-硝基-2，4，6-三硝基苯基取代芳基脲对水稻的校正死亡率较小，但对水稻的根生长表现为抑制作用，在高浓度时，对水稻的茎表现为抑制作用，而低浓度时表现为促进作用。N-硝基-2，4，6-三硝基苯基取代芳基脲对油菜、稗草、苋菜有较高的校正死亡率，表现为明显的抑制作用。如化合物2、3、4、5、6、7对油菜的校正死亡率在500mg·kg^-1时均达到C级；化合物4对稗草在100mg·kg^-1时校正死亡率达到B级，在500mg·kg^-1时达到A级，化合物2、4、5、6、7在1000mg·kg^-1时，达到A级；化合物4、6、7对苋菜在500mg·kg^-1及以上浓度时，达到A级，化合物5在1000mg·kg^-1时达到A级。而N-硝基-2，6-二硝基-4-三氟甲基苯基取代芳基脲整体上对四种作物表现为促进增长作用，但调节作用相对较弱。N-烷基-N-硝基取代苯胺整体上对四种作物表现为高浓度时为抑制作用，低浓度时为促进作用，但调节作用相对较弱。从生物活性数据与结构参数进行相关分析的数据来看，活性与结构参数之间的相关性不明显。更多还原

【Abstract】 N-nitro compounds are kinds of compounds with diverse biological activities, 2, 6-dinitroaniline compounds are kinds of pesticide with high efficiency and low toxicity. They have been used widely as herbicide. This paper aims to synthesize the nitramides and the N-nitro ureas which are derived from the 2, 6-dinitroanilines. We explored the optimum conditions for the synthesis of the nitramides and the N-nitro ureas. The preliminary biological tests of the target compounds were also carried out in libratory.ⅠThe N-nitration of the arylamines（1） The synthesis of the N-nitro-4-nitroaniline and the N-nitro-2-nitroanilineWhen the para or ortho nitroaniline were treated with acetyl nitrate in glacial acetic acid, the ratio of the reactants is 2∶1, stirred for 2h at 20℃, N-nitro-4-nitroaniline （a） and the N-nitro-2-nitroaniline （b） were the main products respectively.（2） The synthesis of the N-nitro-2, 4, 6-trinitroanilinesThe process for the synthesis of N-nitro-2, 4, 6-trinitroanilines（c） was as follows: the 2, 4-dinitroaniline was treated with acetyl nitrate in sulfuric acid, the ratio of the reactants is 3∶1, stirred for 2h under 25℃.（3） The synthesis of N-alkyl-N-nitro-2, 6-dinitro-4-trifluoromethylaniline 1 R=H; 2 R=CH₃; 3 R=CH₂CH₂CH₃; 4 R=CH（CH₃）₂; 5 R=CH₂CH₂CH₂CH₃The structure of the N-alkyl-N-nitro-2, 6-dinitro-4-trifluoromethylaniline is described as Figure 2. The synthetic method of these compounds was as follows: N-alkyl- 2, 6-dinitro-4-trifluoromethylanilines were treated with acetyl nitrate in sulfuric acid. By this procedure, the products were produced in high yields.All in all, the solvent is vital to the synthesis of the N-nitro substituted aniline, when the glacial acetic acid was used as the solvent, the amino group of the phenylamines were nitrated by acetyl nitrate, while the sulfuric acid was used as the solvent, both the aromatic ring and the amine were nitrated.ⅡThe synthesis of N-nitro urea（1） The synthesis of target product N-nitro-2, 4, 6-trinitrophenyl urea 6 R=2Cl、4Cl、6Cl; 7 R=2Br、4Br、6Br; 8 R=2Cl、4Cl; 9 R=2Cl、5Cl; 10 R=3Cl、4Cl; 11 R=2Br、5Br; 12 R=2Br、4Br;The structure of the N-nitro-2, 4, 6-trinitrophenyl urea is described as Figure 3. When triethylamine used as the reaction initiator and HCl scavenger, treaing N-nitro-2, 4, 6-trinitroaniline with bis（trichloromethyl） carbonate in dichloromethane lead to acyl chloride. Then making acyl chloride reacted with substituted anilines in toluene gave the target products.（2） The synthesis of target product N-nitro-2, 6-dinitro-4-trifluoromethylphenyl urea 13 R=2Cl; 14 R=3Cl; 15 R=4Cl; 16 R=2CH₃; 17 R= 4CH₃; 18 R=2F; 19 R=3F;The structure of the N-nitro-2, 6-dinitro-4-trifluoromethylphenyl urea is described as Figure 4. This type of compounds was prepared almost in the same way as that of N-nitro-2, 4, 6-trinitrophenyl urea except that the dichloromethane was used as the solvent during the whole process.19 novel N-nitro compounds of the three types were synthesized. Their structures were confirmed by elemental analysis, IR, MS and ¹HNMR.ⅢThe preliminary biological testThe biological activities of the target molecules on rape, rice, echinochloa crusgalli L, amaranthus albus L were tested at the concentration of 1000 mg·kg^-1, 500 mg·kg^-1, 100 mg·kg^-1, 50 mg·kg^-1, 20 mg·kg^-1 respectively. The herbicidal and the biological regulating effects were investigated. The structure parameters of urea derivatives were caculated using PM3 approach in Gaussian03 program. The correlation analysis between their structures and their biological activities was analyzed. The result of the preliminary biological tests showed that: the death rate of rice is low by the N-nitro-2, 4, 6-trinitrophenyl ureas, but it showed certain inhibitory activity against the root of rice, and it demonstrated inhibitory activity against the stem at high concentration and promotion activity at low concentration. The death rates of rape, echinochloa crusgalli L, amaranthus albus L induced by N-nitro-2, 4, 6-trinitrophenyl ureas were high. The inhibitory activity of N-nitro-2, 4, 6-trinitrophenyl ureas on thethree kinds of plants proved obvious, for example the death rate of rape induced by such compounds as 2, 4, 5, 6, 7 reached C level at the concentration of 500 mg·kg^-1, and the death rate by compound 4 on echinochloa crusgalli L reached B level at 100 mg·kg^-1, A level at 500 mg·kg^-1 respectively. The compounds 2, 4, 5, 6 on echinochloa crusgalli L reached A level at 1000 mg·kg^-1. The death rate of amaranthus albus L: compounds 4, 6, 7 reached A level when the concentration above 500 mg·kg^-1; compound 5 reach A level at the concentration of 1000 mg·kg^-1. The N-nitro-2, 6-dinitro-4-trifluoromethylphenyl urea mainly showed promoting activities on the plants, but the regulating effect was below D level. The N-alkyl-N-nitroanilines showed inhibitory activities on plants at high concentration, and promoting activities at low concentration. but the regulating effects were not strong.According to the date of the correlation analysis between structures of the target urea compounds and their biological activities, there are no significant correlation between them.更多还原