新型4-吡啶基-2-氨基嘧啶类化合物的合成及其生物活性  

Synthesis and biological activity of novel 4-pyridyl-2-aminopyrimidine derivatives

作　　者：张齐[1] 丁志彬[1] 孙楠[1] 徐徐[1,2,3] 高聪芬[4] 王石发[1,2,3] 

机构地区：[1]南京林业大学化学工程学院,南京210037 [2]江苏省生物质绿色燃料与化学品重点实验室,南京210037 [3]广西林产化学与工程重点实验室,南宁530008 [4]南京农业大学植物保护学院,南京210095

出　　处：《林业工程学报》2017年第1期51-56,共6页Journal of Forestry Engineering

基　　金：江苏省高校自然科学研究重大项目(14KJ220001);国家自然科学基金项目(31470529);广西林产化学与工程重点实验室开放基金项目(JSBEM2014010)

摘　　要：以诺蒎酮为原料,合成了新型的4-吡啶基-2-氨基嘧啶类化合物,并探索了该类化合物的抑菌和抗虫活性。诺蒎酮分别与吡啶-3-甲醛和吡啶-4-甲醛在乙醇钠催化作用下缩合制得3-(3'-吡啶)亚甲基诺蒎酮(2a)和3-(4'-吡啶)亚甲基诺蒎酮(2b),2a和2b在叔丁醇钾催化作用下与盐酸胍经环化反应,得到新型吡啶基嘧啶类化合物5,6,7,8-四氢-4-(3'-吡啶基)-7,7-二甲基-6,8-桥亚甲基喹唑啉-2-胺(3a)和5,6,7,8-四氢-4-(4'-吡啶基)-7,7-二甲基-6,8-桥亚甲基喹唑啉-2-胺(3b)。采用1H NMR、13C NMR、IR、MS和HRMS对化合物3a和3b的结构进行了表征,探讨了化合物3a和3b的抑菌活性和对萝卜蚜虫(Lipaphis erysimi)和紫薇长斑蚜虫(Tinocallis kalawaluokalani)的杀虫活性。结果表明,合成的化合物对细菌和真菌具有较好的抑制效果,其中3b对枯草芽孢杆菌(Bacillus subtilis)有较强的抑制作用,最低抑菌浓度为7.80μg/m L。化合物对蚜虫均表现出较好的杀虫活性,在50 mg/L的浓度下对蚜虫的致死率可达60%以上。通过分析化合物的抗虫活性,为开拓松节油的深加工应用提供理论依据。Novel 4-pyridyl-2-aminopyrimidine derivatives were synthesized by using nopinone as the starting material, and their antibacterial and insecticidal activities were analyzed in this paper. Nopinone were condensed with pyridine-3-carboxaldehyde and pyridine-4-carboxaldehyde to get the intermediates 3-（3＇-pyridylmethylene）nopinone（2a）and 3-（4＇-pyridylmethylene）nopinone（2b）by using sodium ethoxide as the catalyst. The 4-pyridyl-2-aminopyrimidine derivatives of 5,6,7,8-tetrahydro-4-（3＇-pyridyl）-7,7-dimethyl-6,8-methanoquinazolin-2-amine（3a）and 5,6,7,8-tetrahydro-4-（4＇-pyridyl）-7,7-dimethyl-6,8-methanoquinazolin-2-amine（3b）were obtained by condensation and cyclization from 2a and 2b under the condition of using t-BuOK as the catalyst in t-butanol. The chemical structures of 3a and 3b were determined by 1H NMR, 13C NMR, IR, MS and HRMS, and the antibacterial and insecticidal activities of the compounds 3a and 3b were also examined. The results showed that both 3a and 3b had good bacteriostatic effect against turnip aphid（Lipaphis erysimi）and Kirkaldy（Tinocallis kalawaluokalani）. The compound 3b had a strong inhibitory effect on Bacillus subtilis, minimum inhibitory concentrations（MIC）was 7.80 μg/mL, and both 3a and 3b had good insecticidal activities. The lethal rate of aphids was more than 60% under the concentration of 50 mg/L. The results of this study would provide the theoretical basis for further processing of turpentine.

关 键 词：诺蒎酮 嘧啶衍生物 抑菌活性 杀虫活性 

分 类 号：TQ453.2[化学工程—农药化工]