【作者】 赵娜；

【导师】 涂海洋； 张爱东；

【作者基本信息】 华中师范大学 ， 有机化学， 2009， 硕士

【摘要】 乙酰辅酶A羧化酶(ACCase)是植物中脂肪酸生物合成的关键酶,可以催化乙酰辅酶A生成丙二酰单酰辅酶A,是除草剂的重要作用靶标之一。芳氧苯氧丙酸酯类(APP类)化合物为ACCase抑制剂的一种,被广泛应用于阔叶作物中苗后防除一年或多年生禾本科杂草。本论文根据文献报道,利用生物电子等排原理,将嘧啶环与嘧啶并三唑环引入APP类化合物的分子结构中,并通过改变嘧啶环与嘧啶并三唑环上的取代基希望获得良好生物活性的化合物。具体研究内容如下:(1)以丙二酸二乙酯与脒为原料,合成了含有嘧啶环的新型APP类化合物48个,其分子结构经过NMR,MS,IR进行了确认,结构通式如下:(2)对含有取代氨基的嘧啶类化合物亚硝化的位置,及将含有取代氨基的嘧啶类化合物引入APP类化合物的合成方法进行了探讨。(3)以4,6-二氯-5-氨基嘧啶为原料,合成了含有嘧啶并三唑环的APP类化合物16个,其分子结构经过NMR,MS,IR等进行了确认,结构通式如下:(4)将所合成的化合物进行了除草活性测试,测试结果表明:所合成的含有嘧啶环及嘧啶并三唑环的芳氧苯氧丙酸酯类衍生物对油菜、稗草的根茎均有一定的抑制作用,对根的抑制作用好于对茎的抑制作用;总体来看,嘧啶并三唑环的引入比嘧啶环的引入更能提高除草活性,有继续研究的价值。更多还原

【Abstract】 Acetyl-coenzyme A carboxylase (ACCase) is a key enzyme in fatty acid biosynthesis in both eukaryotes and prokaryotes. ACCase is a biotinylated enzyme that catalyzes the carboxylation of acetyl-CoA to produce malonyl-CoA. Inhibitors of the ACCase have been widely used as herbicides. Aryloxyphenoxypropionate (APP) derivatives have been found to be strong inhibitor of acetyl-coacarboxylase (ACCase) and used as a very important class of postemergence herbicides for the control of annual and perennial grasses in broadleaf crops.In seeking to develop novel herbicides that inhibit both sensitive and resistant forms of ACCase in grass weeds, we introduced the pyramidines and 1,2,3-triazolo[4,5-d] pyrimidines to the APP based on the bioisosterism theory, and synthesized a series ofaryloxyphenoxypropionates as potential inhibitors against ACCase.(1) 48 novel Aryloxyphenoxypropionates containing pyrimidines were synthesized by using the diethyl malonate and amidine as starting materials, their molecular structures were confirmed by NMR, MS, IR. The skeleton structure of the target molecules is shown as follows:(2) Nitrosation location of amino-containing compounds of the pyrimidines were discussed, we also attempted the method for the synthesis of aryloxyphenoxypropionates containing amino-pyrimidines.(3) 16 novel aryloxyphenoxypropionates containing 1,2,3-triazolo[4,5-d]pyrimidines by using the 4,6-dichloropyrimidin-5-amine as the starting material, and their molecular structures were confirmed by NMR, MS, IR. The skeleton structure of the target molecules is shown as follows:(4) The herbicidal activities of the synthesized compounds have been preliminarily investigated. The results indicated that many of them exhibit good herbicidal activity against rape and barnyard grass.The inhibitory rates to root were higher than that to stem, in general, the inhibitory rates of aryloxyphenoxypropionates containing 1,2,3-triazolo [4,5-d]pyrimidines were higher than aryloxyphenoxypropionates containing pyrimidines, and the formers are wealthy of further investigation.更多还原