作 者：
岑波;吴光燧;范钟天;段文贵;林桂汕;张文静
关键词：
樟脑;樟脑磺酸;双磺酰胺;抑菌活性;合成
摘 要：
天然樟脑是我国的天然优势资源,合成樟脑可由松节油的主要成分α-蒎烯经多步反应合成得到。樟脑及其衍生物具有多种生物活性,通过对樟脑分子的结构修饰可以合成许多具有生物活性的衍生物。以D-(+)-樟脑磺酸为原料,经多步反应合成了11个新型的N′-取代苯磺酰基-N-樟脑磺酰乙二胺化合物(4a～4k),其结构经傅里叶红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)、核磁共振碳谱(~(13)C NMR)和电喷雾电离质谱(ESI-MS)表征。采用离体法测定了目标化合物的抗真菌活性。实验结果表明:在50μg/mL质量浓度下,目标化合物对黄瓜枯萎病菌、苹果轮纹病菌、番茄早疫病菌、花生褐斑病菌和小麦赤霉病菌等5种植物病原菌有一定的抗菌活性,其中化合物4b(R=p-OCH_3)、4a(R=H)、4c(R=m-OCH_3)和4d(R=m-CH_3)对番茄早疫病菌的抑制率分别为91.3%,83.9%,83.9%和83.9%(均达B级以上活性水平),均优于阳性对照百菌清(73.9%);化合物4b和4c对花生褐斑病菌的抑制率均为82.2%(B级活性水平),优于阳性对照百菌清(73.3%);此外,化合物4b对黄瓜枯萎病菌的抑制率达到90.8%(A级活性水平)。由此可知,化合物4b显示出了广谱的抑菌活性,值得进一步研究。
译 名：
Synthesis and antifungal activity of N'-substituted benzenesulfonyl-N-camphorsulfonyl-ethylenediamine compounds
作 者：
CEN Bo;WU Guangsui;FAN Zhongtian;DUAN Wengui;LIN Guishan;ZHANG Wenjing;College of Chemistry and Chemical Engineering, Guangxi University;
关键词：
camphor;;camphorsulfonic acid;;bisulfonamide;;antifungal activity;;synthesis
摘 要：
Camphor, including the natural camphor and the synthetic camphor, is a preponderant resource of China. Synthetic camphor is prepared by isomerization, esterification, saponification and dehydrogenation reactions of α-pinene, which can be used for the main component of turpentine. Camphor itself has a variety of biological activities such as excitatory, heart-strengthening, analgesic, anti-inflammatory, antibacterial, insecticidal, and herbicidal activities. The derivatives of camphor also show a variety of biological activities such as anti-tumor, antibacterial, and herbicidal activities. Many bioactive derivatives can be synthesized by the structural modification of camphor. On the other hand, plant disease is one of the natural disasters seriously endangering agricultural production. Chemical fungicides are still an important means for disease control. However, since drug resistance can reduce the effect of chemical fungicides and lead to high residual due to the long-term use of fungicides, it is necessary to develop new efficient and broad-spectrum fungicides. In this work, D-(+)-camphorsulfonic acid chloride 2 was prepared by the acyl chlorination of D-(+)-camphorsulfonic acid, followed by the N-acylation reaction of compound 2 and ethylenediamine to obtain N-camphor sulfonyl ethylenediamine 3. Finally, 11 types of novel N′-substituted benzenesulfonyl-N-camphorsulfonyl-ethylenediamine 4 a-4 k were synthesized by the N-acylation reaction of the intermediate 3 with various substituted benzenesulfonyl chlorides. The structures of the target compounds were characterized by the Fourier infrared spectrum(FT-IR), proton nuclear magnetic resonance(~1H NMR), carbon-13 nuclear magnetic resonance(~(13)C NMR), and electrospray ionization-mass spectrum(ESI-MS), and their antifungal activities were also evaluated by the in vitro method. The result showed that the target compounds exhibited a certain inhibition activity against the five tested plant pathogens, including Fusarium oxysporum f. sp. Cucumerinum, Physalospora piricola, Alternaria solani, Cercospora arachidicola and Fusarium graminearum at the mass concentration of 50 μg/mL, in which the inhibition rates of compounds 4 b(R=p-OCH_3), 4 a(R=H), 4 c(R=m-OCH_3) and 4 d(R=m-CH_3) were 91.3%, 83.9%, 83.9% and 83.9%, respectively, against A. solani(all above B-class activity level), which were all better than that of the positive control chlorothanil with inhibition rate of 73.9%. Compounds 4 b and 4 c had the same inhibition rate of 82.2% against C. arachidicola(B-class activity level), better than that of the positive control chlorothanil with inhibition rate of 73.3%. The inhibition rate of compound 4 b was 90.8% against F. oxysporum f. sp. cucumerinum(A-class activity level). Owing to its broad-spectrum antifungal activity, compound 4 b is worthy of further investigation. This work aims to provide a new way for the further development and utilization of camphor, and provides a reference for the development of new agricultural fungicides.
