含苯并咪(噻)唑环的β-咔啉衍生物的合成与杀菌活性（英文）

Synthesis and Fungicidal Evaluation of Novel β-CarbolineBenzimidazole and β-Carboline-Benzothiazole Hybrids

为了寻找结构新颖的活性分子,采用活性结构拼接方法,合成了14个具有β-咔啉和苯并咪唑或者同它的生物电子等排体苯并噻唑连接的新分子,其结构经~1HNMR、^(13)CNMR和HRMS确证.进一步测试了这些化合物对棉花立枯丝核菌、棉花枯萎病原菌、葡萄灰霉病原菌、向日葵菌核和油菜菌核的杀菌活性.离体杀菌活性测定结果表明,在50μg·m L^(-1)时,多数目标化合物对供试5种病原菌表现出一定的抑制活性,但活性均不高.其中β-咔啉环9位为乙基、苄基、3-氯苄基的苯并咪唑衍生物(4a、4c和4e)对向日葵菌核有较高抑制率,而1-苯并咪唑-9-乙基-β-咔啉(4a)、1-苯并咪唑-9-丁基-β-咔啉(4b)、1-苯并咪唑-9-苄基-β-咔啉(4c)、1-苯并咪唑-9-(2,3,4,5,6-五氟苄基)-β-咔啉(4f)、1-苯并噻唑-9-(3-氯苄基)-β-咔啉(5e)和1-苯并噻唑-9-(2,3,4,5,6-五氟苄基)-β-咔啉(5f)则对油菜菌核表现出令人满意的抗菌活性.其中化合物4c对大多数的测试菌株表现出广谱活性.

In order to discover novel compounds with biological activities, new molecular hybrids combining benzimidazole or its bioisostere benzothiazole with β-carboline were synthesized. The benzimidazole or benzothiazole scaffold was linked at position-1 with β-carboline which was further characterized by 1H NMR, 13 C NMR and HRMS. All of the target compounds were evaluated in vitro for their antifungal activity against Rhizoctorzia solani, Fusarium oxysporum, Botrytis cinerea Pers., sunflower sclerotinia rot and rape sclerotinia rot by mycelia growth inhibition assay at 50 μg·m L-1. The preliminary results showed that most compounds exhibit mild inhibiting effect against all the tested strains. Among them, 1-(1H-benzo[d]-imidazol-2-yl)-9-ethyl-β-carboline(4a), 1-(1H-benzo[d]imidazol-2-yl)-9-benzyl-β-carboline(4c) and 1-(1H-benzo[d]imidazol-2-yl)-9-(3-chlorobenzyl)-β-carboline(4e) showed satisfactory antifungal activity against sunflower sclerotinia rot, 1-(1H-benzo[d]-imidazol-2-yl)-9-ethyl-β-carboline(4a), 1-(1H-benzo[d]imidazol-2-yl)-9-n-butyl-β-carboline(4b), 1-(1H-benzo[d]imidazol-2-yl)-9-benzyl-β-carboline(4c), 1-(1H-benzo[d]imidazol-2-yl)-9-((perfluorophenyl)methyl)-β-carboline(4f), 1-(benzo[d]-thiazol-2-yl)-9-(3-chlorobenzyl)-β-carboline(5e) and 1-(benzo[d]thiazol-2-yl)-9-((perfluorophenyl)methyl)-β-carboline(5f)displayed excellent fungicidal activity against rape sclerotinia rot. Specifically, compound 4c exhibited broad-spectrum fungicidal activity against most of the tested fungi.