新型丙烯海松酸基双酰胺-噻二唑化合物的合成及生物活性研究  

Synthesis and biological activity of novel acrylpimaric acid-based diamide-thiadiazole compounds

作　　者：林桂汕[1] 阮战辉[1] 段文贵[1] 刘陆智[1] 杨章旗[2] 

机构地区：[1]广西大学化学化工学院,南宁530004 [2]广西林业科学研究院,南宁530002

出　　处：《林业工程学报》2017年第2期45-51,共7页Journal of Forestry Engineering

基　　金：国家自然科学基金(31060100);八桂学者专项

摘　　要：松香是来自松树的非木质林产品,是我国的再生性天然优势生物质资源,主要成分为树脂酸。为拓展松香在生物活性方面的应用途径,以松香为原料,与丙烯酸Diels-Alder加成反应制备丙烯海松酸(1),再与氨基硫脲反应获得丙烯海松酸基双噻二唑(2),最后与系列取代苯甲酰氯进行N-酰化反应,合成得到7个新型丙烯海松酸基双酰胺-噻二唑化合物(3a^3g)。采用FTIR、~1H NMR、^(13)C NMR、ESI-MS等技术手段对目标化合物进行结构表征;分别采用稗草小杯法和油菜平皿法测试目标化合物对稗草(Echinochloa crusgalli)株高生长和油菜(Brassica campestris)胚根生长的抑制活性。结果表明,在100μg/m L质量浓度下,目标化合物对油菜胚根生长的抑制活性较强,化合物3e(R=p-Br)的抑制率高达92.4%(活性级别为A级),化合物3b(R=p-CH_3)和3d(R=p-Cl)的抑制率分别为77.4%和73.2%(活性级别均为B级)。采用离体法(即琼脂稀释法)测试目标化合物对苹果轮纹病菌(Physalospora piricola)、黄瓜枯萎病菌(Fusarium oxysporum f.sp.cucumerinum)、番茄早疫病菌(Alternaria solani)、小麦赤霉病菌(Gibberella zeae)和花生褐斑病菌(Cercospora arachidicola)的抑菌活性。结果表明,目标化合物在50μg/m L质量浓度下对所测5种植物病原菌表现出一定抑制效果。目标化合物3e对油菜胚根生长具有较好的抑制活性,值得进一步研究。As a non-wood forest product obtained from pines and some other plants, rosin with its dominant component as resin acids is a renewable, natural and preponderant biomass resource of China. In an attempt to expand its utilization in biological activities, acrylpimaric acid （ 1 ） was prepared by the Diels-Alder cycloaddition reaction between rosin and acrylic acid. Then, acrylpimaric acid-based dithiadiazole （2） was prepared by the reaction of acrylpimaric acid with thiosemicarbazide. Seven novel acrylpimaric acid-based diamide-thiadiazole compounds （3a-3g） were synthetized followed by N-acylation reaction with a series of substituted benzoyl chlorides. The target compounds were characterized by means of FTIR, ^1H NMR, ^13C NMR, and ESI-MS. The herbicidal activity of the target compounds 3a- 3g was preliminarily evaluated by the barnyard grass beaker method and the rape petri dish method against the seedling-growth of barnyard grass （ Echinochloa crusgalli） and the root-growth of rape （ Brassica carnpestris）, respectively. The results showed that some target compounds had good growth inhibitory activity against the root-growth of rape at a concentration of 100 μg/mL, in which compound 3e （R =p-Br） exhibited the highest inhibitory rate of 92. 4% （ A-class level）, and compounds 3b （ R =p-CH3 ） and 3b （ R =p-Cl） displayed inhibitory rate of 77.4 % （ B-class level） and 73.2% （ B-class level）, respectively. The antifungal activity of the target compounds 3a-3g was also evaluated by in vitro method （ also known as the agar dilution method） against Physalospora piricola, Fusarium oxysporum f. sp , Alternaria solani, Gibberella zeae, and Cercospora araehidicola at a concentration of 50 μg/ mL. It was found that the title compounds 3a-3g showed a certain antifungal activity against all the tested fungi. The target compound 3e with excellent herbicidal activity is a leading compound worthy of further research.

关 键 词：松香 丙烯海松酸 双酰胺-噻二唑 除草活性 抑菌活性 

分 类 号：TQ453.2[化学工程—农药化工]