摘要
21世纪,人口增长与粮食供给之间的矛盾日渐突出,由于城市扩张和环境恶化等因素导致的耕地减少更加剧了这种矛盾的激化。为了提高劳动生产率和增加粮食产量,大范围地使用农药就成为现代农业生产中一种有效的手段和必然的发展趋势。而除草剂在农药中所占比重很大,全世界每年农药总销售额中除草剂约占50%。因此,优秀除草剂品种的开发受到了各国农药公司及研究机构的高度重视。
二甲戊乐灵(pendimethalin)由美国氰胺公司(现归属巴斯夫公司)开发,属于苯胺类除草剂,化学名称N-(1-乙基丙基)-2,6-二硝基-3,4-二甲基苯胺,其他名称二甲戊灵、施田补、除芽通、除草通、胺硝草、杀草通、菜草通等。二甲戊乐灵作为世界上最大的选择性除草剂之一,持效期长达45～60天,施药后可解决作物整个生育期的杂草危害,使用方式灵活,可播前混土、播后芽前或作物移栽前施用等方法使用;也可以和多种除草剂混用,扩大杀草谱,提高杀草效果。该品低毒,对人畜、多数作物、环境安全性高,大白鼠急性经口LD_(50)1050～1250TC/kg。作为芽前水、旱田除草剂,它对大多数作物具有很高的安全性。又因为土壤对其吸附性强,不易淋溶,在土壤中移动性小,环境友好,深受使用者的欢迎。
In the 21'st century the conflicts between population increase and foodsupplies are becoming serious. Moreover, plowland decreasing caused by cityexpanding and circumstance worsen made the situation being more serious. Toincrease the working efficiency and quantity of food supplies, large scaleemploying of pesticide in modern agriculture produce are necessarily. Sinceherbicide play a key role in pesticide, development and research of good herbicidearising attentions of pesticide company and research institutes.
Pendimethalin, which was firstly developed by American CyanamiolCompany(now belonging to BASF), was a kind of aniline herbicide. Being themost widely used herbicide, Pendimethalin owns many good properties such ashigh efficiency, long period of validity, versatile appling methods, low toxicity tohuman and livestock, friendly to circumstance, etc. Consequently it was used formany crops and vegetables include cotton, potato and corns.
Traditional synthesis route of Pendimethalin which used 3,4-dimethylanilineas starting material has many shortages includes low purity of product, high acidcontent of wasted water, large consumption of hydrochloric acid, high failurepercent for equipment and severe operating conditions. In this thesis, a greensynthesis route was determined.
The green route is described as below: 4-nitrodimethylbenzene was used asstarting materials, which was converted to N-(1-ethylpropyl)-3,4-dimethylaniline
via hydrogen adding reaction, after another nitrating reaction pendimethalin wasobtained. This synthesis route has several advantage compared to the route using3,4-dimethylaniline: Firstly, the steps of reaction was compressed from three stepreactions to one step reaction ,the cost of raw materials was reduced. Nitrogencompounds are low toxic to catalyst then its service time was extended;Secondly,the feed resolving is easily because to 4-nitro-1,2-dimethylbenzene is diffluent in3-pentanone compared to 3,4-dimethylaniline which need an additional solvingstill;The solvent for nitrating was changed from trichloromethane todichloromthane then removal of solvent could be completed at normal pressure.The consumption of hydrochloric acid was reduced to 1/10 of those in the oldroute. The failure percent of equipment was depressed while the operatingconditions were improved. Post-treat was easily since all wash was performed inone still, however the old route need another two wash still one solvent-removalstill. The content of waste acid in waste water was decreased form 50% to 1%.Lastly, the purity of product could reach above 96% at same conversion rate.Additionally, the product could be washed after dissolving in xylol to obtainedlatex, consequently the cost was reduced compared to the old route sincepetroleum ether was saved.Generally, the route discovered in this thesis could made resources beingutilized enough and made waste product being decreased, while contribute toagriculture production and environment production.
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