【作者】 黄明智；

【导师】 黄可龙；

【作者基本信息】 中南大学 ， 应用化学， 2006， 博士

【摘要】 21世纪的农药必须具有高效、安全、经济、环境友好的特点。原卟啉原氧化酶(protox)抑制剂为需光型除草剂，其独特的除草机制可保证动植物之间的良好选择性，具有十分广阔的发展前景。 本文以现有商品化protox抑制剂丙炔氟草胺等除草剂的结构为先导，针对它们物理特性或生物活性等方面的某些缺陷，采用活性亚结构拼接、生物等排体等农药分子设计技术设计具有潜在protox抑制剂活性的新化合物；运用传统有机合成方法与固载化试剂纯化目标产物技术相结合的合成手段成功制备了苯并噁嗪取代异吲哚-1，3-二酮、异吲哚-1，3-二酮取代苯并噁嗪羧酸酯、N-异吲哚-1，3-二酮取代苯基酰胺和N-异吲哚-1，3-二酮取代苯基脲四系列共九类85个新型2-取代苯基异吲哚-1，3-二酮(SPⅡDO)衍生物，利用核磁共振、质谱、红外光谱、元素分析等现代分析手段表征了新化合物的结构。首次在异吲哚-1，3-二酮取代苯并噁嗪酮衍生物中引入羧酸酯结构，首次在SPⅡDO衍生物中苯环的5-位引入N，N-不对称脲基团与苯甲酰脲基团，研究结果扩展了protox抑制剂的结构类型。 采用农药生物活性测定标准操作程序测试新化合物的除草活性，发现许多化合物表现出高的protox抑制剂的生物活性，如1个苯并噁嗪取代异吲哚-1，3-二酮衍生物的除草活性和对作物安全性与先导化合物丙炔氟草胺和B2055基本相当，3个异吲哚-1，3-二酮取代苯并嗯嗪羧酸酯化合物在75gai／ha剂量下不论芽前还是芽后施用对苘麻、藜、凹头苋等双子叶杂草和马唐、稗草、狗尾草等单子叶杂草均表现出80％以上除草活性，2个N-异吲哚-1，3-二酮取代苯基酰胺衍生物的除草谱较广，部分N-异吲哚-1，3-二酮取代苯基脲衍生物对阔叶杂草表现出芽后除草活性的新化合物。杂草中毒症状有叶片白化、卷曲、灼伤和坏死等，是protox抑制剂典型的除草特征。更多还原

【Abstract】 In the 21^th century, pesticide must have the characteristics of high effect, safety, low cost and environmentally-friend. Protoporphyriinogen oxidase （protox） inhibitors are light-dependent herbicides, which will be found a wider application because their unique herbicidal mechanism can ensure very good selectivity between human animals and plants.To overcome limitations of some lead compounds in physical property and biological activity, some novel compounds with latent protox inhibiting activity were designed by choosing commercial protox inhibitor flumioxazin and other herbicides as lead compounds based on pesticide molecular design technologies, such as activity sub-structure connecting, and bioisosteric replacement; 9 kinds, 85 novel 2-substituted phenyl isoindoline-dione （SPIIDO） derivatives were prepared by the traditional organic synthesis methods and purification technique for target products utilizing polymer-supported scavenger reagent, and these compounds could be divided into 4 series: benzoxazin-substituted isoindolinediones, isoindoline- dione-substituted benzoxazine carboxyl esters, N- isoindoline- dione-substituted phenyl acylamines and N- isoindolinedione- substituted phenyl ureas. Their structures were confirmed by ¹H NMR, IR, mass spectroscopy and elemental analysis. The first introduction of carboxyl ester group into isoindolinedione-substituted benzoxazinone derivatives and that of N, N-um-symmetrical urea group or benzylurea group into the 5-position of benzene cycle of SPIIDO derivatives expanded the chemical structural types of protox inhibitors.The bioassays of preliminary herbicidal activity were carried out according to the standard operation procedure of pesticide bioassay, and the results showed that many compounds exhibited higher inhibiting protox activity. For example, one compound of benzoxazin-substituted isoindolinedione derivatives had comparable herbicidal activity and crop safety as flumioxazin and B2055, three compounds of isoindolinedione- substituted benzoxazine carboxyl ester derivatives possed more than 80% herbicidal efficiency at 75 g ai/ha in both pre- and post-emergence treatments against both dicotyledon weeds such as Abutilon theophrasti Medic, Chenopodiun album L., Amaranthus retroflexus L. and monocotyledon weeds such as Digitaria sanguinalis L., Echinochloa crus-galli L., Setaria viridis L., two更多还原