含硫化合物在有机合成、药物化学以及材料化学等领域具有重要的作用.到目前为止,科学家已经在C-S键的构建领域进行了很多工作.在构建C-S键的众多方法中,金属催化的C-S键合成反应是一类很重要的反应,但是此方法存在着催化剂对空气敏感、环境不友好等问题.因此,发展无金属催化的C-S键构建反应受到了人们越来越多的重视.基于我们在碘催化相关反应方面的研究,本文报道了一种碘催化的硫化吡唑啉酮类化合物的合成方法.我们选用3-甲基-1-苯基-2-吡唑啉-5-酮与二苯二硫醚为底物进行条件筛选实验,发现I_2(10%)为催化剂,二氧六环为溶剂,H_2O_2为氧化剂为最优化的实验条件,目标产物硫化吡唑啉酮最高产率为88%.在最优化的反应条件下,我们尝试了带有不同官能团(NO_2,Cl,OH等)的吡唑啉酮与二硫醚的反应,均能以较高产率得到目标产物.当含有杂环的二硫醚(2,2’-二硫二吡啶)作为反应底物时,也能以中等以上的产率得到相应的目标产物.另外还进行了对比试验,例如在反应体系中加入自由基捕获剂TEMPO,反应产率会大大降低,说明反应中应该有自由基中间体生成;如果反应体系中不加碘,则反应产率为零;如果反应体系中不加H_2O_2,则反应产率由88%降低至48%,说明碘和H_2O_2在反应中都起到了重要作用.通过以上对比试验,提出了可能的反应机理:首先,二硫醚发生均裂反应生成苯硫基自由基,然后苯硫基自由基与碘反应生成亲电的PhSI活性中间体,PhSI与异构化的吡唑啉酮发生亲电取代反应,生成目标产物硫化吡唑啉酮和HI,HI可以被H_2O_2氧化生成I_2继续参与下一轮催化反应.以3-甲基-1-苯基-2-吡唑啉-5-酮与二苯二硫醚为底物,我们对此反应进行了放大试验,结果显示反应产率几乎没有降低,这为此反应的大规模应用奠定了基础.在此,我们发展了一种简单高效的合成硫化吡唑啉酮的反应,此方法无需金属催化剂,利用常见的碘为催化剂就可以以较高的产率得到目标产物.为合成含硫化合物提供了一种新的方法 Sulfur-containing compounds play an important role in the fields of organic synthesis, medicinal chemistry and material chemistry, etc. So far, scientists have done a lot of work in the field of CS bond formation.In many ways to construct CS bonds, metal-catalyzed CS bonds Synthetic reaction is a very important reaction, but this method has the problems that the catalyst is air-sensitive and environment-friendly, therefore, more and more attention has been paid to the development of metal-free catalytic CS bond building reaction. Iodine-catalyzed reactions, an iodine-catalyzed method for the synthesis of sulfurized pyrazolones has been reported. We selected 3-methyl-1-phenyl-2-pyrazolin- Benzene disulfide as the substrate for the conditions of screening experiments found I_2 (10%) as a catalyst, dioxane as a solvent, H_2O_2 as an oxidizing agent for the optimization of the experimental conditions, the target product sulfated pyrazolone maximum yield of 88 %. Under the optimized reaction conditions, we tried pyrazolones with different functional groups (NO 2, Cl, OH, etc.) to react with disulfides to obtain the target product with higher yield. Ring of disulfide (2,2’-disulfide Dipyridine) as the reaction substrate, the corresponding target product can also be obtained with a moderate or higher yield.In addition, comparative experiments such as TEMPO with a radical scavenger in the reaction system have been performed, the yield of the reaction will be greatly reduced, indicating that If the reaction system without iodine, the reaction yield was zero; if the reaction system without H_2O_2, the reaction yield decreased from 88% to 48%, indicating that iodine and H_2O_2 in The reaction has played an important role.Through the above comparison test, the possible reaction mechanism is proposed: First, the disulfide cleavage reaction generated phenylthio free radicals, and then phenylthio free radicals react with iodine to generate electrophilic PhSI The active intermediates, PhSI and isomerization of pyrazolone electrophilic substitution reaction to generate the target pyrazolone and sulfur vulcanization, HI H_2O_2 can be oxidized to I_2 continue to participate in the next round of catalytic reactions to 3- Phenyl-2-pyrazoline-5-one and diphenyl disulfide as substrates, we conducted a magnification test on this reaction and the results showed that the reaction yield hardly decreased, which led to a large reaction The scale of application laid the foundation. Here, we developed Species simple and efficient synthesis of pyrazolone vulcanization reaction, this method does not require a metal catalyst, can be obtained in a high yield the title compound as a catalyst using a common iodine Providing a new method for the synthesis of sulfur-containing compound