樟脑基咪唑盐类化合物的合成及其抑菌活性

Synthesis and antifungal activity of camphor derived imidazolium salts

摘要:

以天然可再生资源樟脑磺酸为原料制备了10-碘代樟脑，10-碘代樟脑再经过季铵化反应、离子交换后得到16个樟脑基咪唑盐。通过HRMS、1HNMR、13CNMR和19FNMR对目标化合物结构进行了表征，采用菌丝生长速率法测定了它们对立枯丝核菌（Rhizoctonia solani）、层出镰刀菌（Fusarium proliferatum）和灰葡萄球菌（Botrytis cinerea）的抑制率。结果表明，目标化合物对3种真菌均具有一定的抑制作用，部分目标化合物对于灰葡萄球菌的抑制效果显著，3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-1-(2,4,6-三甲基)苯基-1H-咪唑-3-鎓双三氟甲磺酰亚胺盐（Ⅲd）、1-(4-氯苯基)-3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-1H-咪唑-3-鎓碘盐（Ⅴa）抑制率可达100%，效果优于阳性药百菌清；化合物Ⅲd、Ⅳa〔1-(2,6-二异丙基)苯基-3-(7,7-二甲基-2-氧代双环[2.2.1]庚-1-基)甲基-1H-咪唑-3-鎓碘盐〕对层出镰刀菌有较好的抑制活性，抑制率分别可达为66.2%、70.4%，效果与阳性药百菌清相近；目标化合物对立枯丝核菌的抑制效果整体不及百菌清。

Abstract:

1-Iodomethyl-7,7-dimethyl-bicyclo[2.2.1]heptan-2-one was synthesized with recyclable camphorsulfonic acid as raw material and used to design and synthesize sixteen camphor derived imidazolium salts by quaternization and metathesis reaction. These target compounds were characterized by HRMS, 1HNMR, 13CNMR and 19FNMR. Their inhibition rates against Rhizoctonia solani, Fusarium proliferatum and Botrytis cinerea were tested by mycelial growth method. The results indicated that these compounds had certain inhibitory effects on three fungi. Some of the target compounds showed significant inhibitory effects on Botrytis cinerea, among them, 3-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl-1-(2,4,6-trimethyl)phenyl-1H-imidazol-3-ium bis(trifluoromethylsulfonyl) imide (Ⅲd) and 1-(4-bromophenyl)-3-(7,7-dimethyl-2-oxobicyclo [2.2.1]heptan-1-yl)methyl)-1H-imidazol-3-ium iodide (Ⅴa) had inhibition rates of 100%, better than chlorothalonil. Compounds Ⅲd and Ⅳa 1-(2,6-diiso-propylphenyl)-3-(7,7-dimethyl-2-oxobicyclo [2.2.1]heptan-1-yl)methyl)-1H-imidazol-3-ium iodide had good inhibitory activities against Fusarium proformi, with inhibition rates of 66.2% and 70.4%, respectively, which were samilar to that of chlorothalonil. The inhibition effects of the target compounds against Rhizoctonia solani were not as good as that of chlorothalonil.