5-亚环己基-2-取代氨基咪唑啉酮类化合物的合成及其杀菌活性研究
收稿日期: 2012-04-25
修回日期: 2012-05-30
网络出版日期: 2012-06-06
基金资助
国家“12×5”科技支撑计划(No. 2011BAE06B04)、国家自然科学基金(No. 21172254)和南开大学元素有机化学国家重点实验室开放基金(Nos. 0902, 201003)资助项目.
Synthesis and Fungicidal Activity of 5-Cyclohexylidene-2- aminoimidazolin-4-one Derivatives
Received date: 2012-04-25
Revised date: 2012-05-30
Online published: 2012-06-06
Supported by
Project supported by the National Key Technologies R&D Program (No. 2011BAE06B04), the National Natural Science Foundation of China (No. 201172254) and the National Key Laboratory of Elemento-Organic Chemistry in Nankai University (Nos. 0902, 201003).
以环己酮和2-硫代乙内酰脲为起始原料, 经Knoevenagel缩合反应制得5-亚环己基-2-硫代咪唑啉-4-酮(1), 化合物1在乙醇钠/乙醇体系中与碘甲烷反应得到5-亚环己基-2-甲硫基咪唑啉-4-酮(2), 化合物2再与相应的取代苯胺或苄胺在冰醋酸体系中回流制得目标化合物5-亚环己基-2-取代氨基咪唑啉酮3a～3r, 它们的化学结构经1H NMR, IR, MS和X-ray单晶衍射确证. 5-亚环己基-2-对氯苄氨基咪唑啉酮(3q): Mr＝335.83, C16H18ClN3O·CH4O, Monoclinic, P2(1)/n, ρ＝1.264 g/cm3, F(000)＝712, Z＝4, a＝0.59895(12) nm, b＝1.2161(2) nm, c＝2.4289(5) nm, β＝94.03(3)°. 初步生物活性测定结果表明: 在50 μg/mL浓度下, 部分目标化合物均对供试菌种显现出一定的抑制活性, 其中5-亚环己基-2-对氟苄氨基咪唑啉酮(3p)对油菜菌核的EC50为24.37 μg/mL, 3q对辣椒疫霉的EC50为28.68 μg/mL.
关键词： 5-亚环己基-2-氨基取代咪唑啉酮; 2-硫代乙内酰脲; Knoevenagel缩合反应; 杀菌活性
雷建平 , 韩金涛 , 徐志红 , 董宏波 , 王明安 . 5-亚环己基-2-取代氨基咪唑啉酮类化合物的合成及其杀菌活性研究[J]. 有机化学, 2012 , 32(10) : 1993 -1998 . DOI: 10.6023/cjoc201204026
A series of new 5-cyclohexylidene-2-aminoimidazolin-4-one derivatives 3a～3r were synthesized via Knoevenagel condensation, methylation and substitution reaction using cyclohexanone and 2-thiohydantoin as starting material. Their structures of compounds 3a～3r were confirmed by 1 H NMR, IR, MS techniques and X-ray diffraction. 5-Cyclohexylidene- 2-p-chlorobenzylaminoimidazolin-4-one (3q): Mr＝335.83, C16H18ClN3O·CH4O, Monoclinic, P2(1)/n, ρ＝1.264 g/cm3, F(000)＝712, Z＝4, a＝0.59895(12) nm, b＝1.2161(2) nm, c＝2.4289(5) nm, β＝94.03(3)°. The preliminary bioassay shows that some of the compounds have certain fungicidal activities at the concentration of 50 μg/mL. The EC50 value of 5-cyclohexylidene-2-p-fluorobenzylaminoimidazolin-4-one (3p) against Sclerotinia scleotiorum is 24.37 μg/mL, and that of 3q against Phytophthora capsici is 28.68 μg/mL, respectively.
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