摘要：
Bis(indolyl)methanes are a kind of alkaloids with important biological activity, and many bis(indolyl)-methanes have been isolated from a variety of terrestrial and marine natural sources. We found that 3,3′-(phenylmeth-ylene)bis(1H-indole) can be gained in the asymmetric Friedel-Crafts Henry Reaction (F-C-H reaction) in the pres-ence of NiCl 2 . Therefore, we took the use of NiCl2 as a cheap catalyst for the synthesis of bis(indolyl)methanes based on indole and benzaldehyde. By using the catalyst NiCl 2 , the reaction was optimized in terms of the solvent, reaction temperature, reaction time, the mole ratio of indole to benzaldehyde, and the mass fraction of catalyst. The suitable conditions for the synthesis of 3,3′-(phenylmethylene)bis(1H-indole) are as follows: when indole is 2.0 mmol, n (indole):n(benzaldehyde) = 2 :1. 1;the amount of catalyst (NiCl2 ) is 5% of the amount of benzaldehyde;reaction time is 5 h and the reaction temperature is 40°C. The reaction was repeatedly performed three times under the suitable conditions and the average yield of 3,3′-( phenylmethylene) bis(1H-indole) was 82. 6% ( the yields are 82. 3%, 83. 1% and 82. 5%, respectively). The catalyst (NiCl2 ) can be easily prepared from hydrate (NiCl2·6H2 O) with low cost in the reaction system. Meanwhile, the reaction condition is mild and the post-processing is simple in this process. The structure of the 3,3′-(phenylmethylene)bis(1H-indole) purified by column chromatography (eluent:pe-troleum ether and ethyl acetate, from 8 :1 to 6 :1) was identified by infrared spectra, HRMS (high resolution mass spectrometer), 1 H NMR (proton nuclear magnetic resonance spectroscopy),and 13 C NMR (carbon-13 nuclear mag-netic resonance), and then the antifungal activity of 3,3′-(phenylmethylene)bis(1H-indole) was studied by using the cross method. Compared with the control group, the inhibition ratio of the compound is 61. 1% (Sclerotinia sclerotio-rum (Lib.) de Bary) and 60. 8%(Botrytis cinerea Pers. ex Fr.), respectively. The study on antifungal activity of 3, 3′-(phenylmethylene)bis(1H-indole) expands the application fields of bis(indolyl)methanes, and it suggests that bis (indolyl)methane would play a more important role in plant disease control.%为研究双吲哚甲烷类化合物的高效合成方法及生物活性,以吲哚和苯甲醛为原料,以NiCl2为催化剂,合成了化合物3,3′-(苯亚甲基)双吲哚,分析了溶剂种类、原料配比、反应温度、反应时间、催化剂用量等对产物收率的影响,并确定了适宜的合成条件.结果表明,3,3′-(苯亚甲基)双吲哚合成的适宜条件为以乙醇为溶剂,n(吲哚):n(苯甲醛)=2:1.1,催化剂用量是苯甲醛物质的量的5%,40°C 下反应5 h,产物收率达到82.6%.采用红外、高分辨率质谱和NMR等分析手段对产物结构进行了表征,分析了化合物对两种植物病原菌的抗真菌活性,发现3,3′-(苯亚甲基)双吲哚(10μg/mL)对油菜菌核病菌(Sclerotinia sclerotiorum(Lib.)de Bary)和黄瓜灰霉病菌(Botrytis cinerea Pers.ex Fr.)具有明显抑制作用,其抑制率分别为61.1%和60.8%.研究的双吲哚甲烷类化合物合成方法反应条件温和,后处理环保,对新型抗植物病原真菌药研究和开发具有借鉴意义.
