二硝基苯胺类除草剂二甲戊乐灵研究

【作者】 张国富；

【导师】 许丹倩； 徐振元；

【作者基本信息】 浙江工业大学 ， 精细化工， 2001， 硕士

【摘要】 本文在查阅了大量文献的基础上，对二硝基苯胺类除草剂的典型化合物二甲戊乐灵的合成路线和方法、生物活性和作用机制、毒性和三致作用及环境行为和生物代谢等方面作了较为详细的综述。 在此基础上对二甲戊乐灵的合成和开发进行了重点研究。合成过程中，选用了3，4-二甲基苯胺路线，并对该路线进行了改进，以3，4-二甲基硝基苯为起始原料，在高效缩合催化剂和加氢还原催化剂的存在下，使硝基还原、胺同3-戊酮亲核加成、脱水成亚胺、不饱和双键加氢还原四步反应合并在一起进行，减少了反应操作步骤，提高了收率。在硝化过程中采用未见文献报道的混酸分步硝化法代替硝酸硝化法和常见的混酸一步硝化法，反应产生的废酸经回收浓缩后套用，方法先进，无“三废”污染。在消除亚硝胺阶段，以硫酸和氯化钠代替易挥发的盐酸，反应彻底，脱亚硝基效果好，产品质量可以达到美国环保局对亚硝胺含量的限制要求。在合成过程中通过研究二甲戊乐灵的最佳反应条件，使反应总收率比文献值高5％左右。此外还对得到的最佳反应条件分别进行了放大试验，结果表明，合成方法先进可行，收率稳定，条件可靠。通过工业化试验方案设计，拟建成年产600吨33％乳油的生产车间，投入工业化生产。 通过红外光谱（IR）、氢核磁共振谱（~1HNMR）和气质联用（GC-MS）对合成的二甲戊乐灵及其关键中间体进行了结构表征，其分析结果与合成的化合物结构相符合；研究并确定了二甲戊乐灵及其中间体的定量分析方法。 二甲戊乐灵的急性毒性试验表明，二甲戊乐灵是一种对人、畜和大多数哺乳动物低毒的化合物。它的应用不会对自然界和动物造成危害。更多还原

【Abstract】 This thesis summarized the Pendimethalin, a kind of dinitroaniline-type herbicide, about its synthetic routes and methods, herbicide activities and biomechanism, animal toxicity arid three pathological effects, metabolism and environmental effects with 131 references. The research trials were paid with a particular attention on the synthesis and development of Pendimethalin. In the process of synthesis, the method through 3,4-dimethylbenzenamine was used. The progress was improved with 3,4-dimethylnitrobenzene as starting material. Reduction of 3,4-dimethylnitrobenzene, nucleophilic addition of 3 ,4-dimethylbenzenamine and diethyl ketone, dehydration and reduction of unsaturated double bond were carried out in continuous reactions in one-pot with less waste and more excellent product. During the nitration progress, the progress of using nitric acid and one-stage mixed acid were rephced with two-stage progress of using mixed acid which was never reported on 1iterat~re. Waste acid could be applied repeatedly with no waste in the progress of nitration. Through adopting never reported process of reducing nitroso-pendimethalin, that was replacing hydrochloric acid by sulfuric acid and sodium chloride, the product produced in this progress is accord with the demands of EPA (the Environmental Protection Ageney) of the U.S.A. Moreover, the amplifing trials were run on selected methods of Pendimethalin and its intermediates. Results showed the selected methods were practicably and their yields were stable while the total yield was further increased by 5% over the method reported on literatures, with more excellent product ~nd less wastes. The chemical structure of Pendimethalin and its key intermediate were characterized by means of IR, 1HMR and GC-MS. Otherwise this thesis also described the quantitative analysis methods of Pendiniethalin and its intermediate. The acute toxicity of Pendimethalin was examined. It belonged to a kind of low-to,dcity compound to humankind. domestic animals and most other mammals.更多还原