芳基二硫醚化合物常压制备研究

发布时间：2018-03-18 20:12

  本文选题：单质硫　切入点：芳基二硫醚　出处：《辽宁大学》2017年硕士论文　论文类型：学位论文

【摘要】：随着社会的迅速发展,有机二硫醚类化合物作为一种广泛使用的精细化工原料及有机合成中间体,越来越被重视。例如在医药、农药、染料、橡胶硫化剂、润滑剂、食品添加剂、电池储能材料及抗癌药物方面得到广泛应用。也因此,人们对于如何能大量、高效、快速的合成二硫醚的需求也在持续不断的上升。尤其是芳基二硫醚,制作条件更加苛刻,对于仪器设备的要求更加精密,给芳基二硫醚的批量生产带来了更大的挑战。目前工业上用来制备二硫醚的方法有硫醇氧化法、纳米催化合成法等,这些方法都存在或多或少的缺点,如成本高、生产条件苛刻、环境污染等。本文旨在探索一种生产成本低、产量高、工艺简单、绿色无污染且易于大量生产的合成方法。本文以单质硫为反应试剂,水作为氢源,一氧化碳作为羰基来源,DMSO作为反应溶剂,常压条件下,将底物制备为芳基二硫醚化合物。此方法实现了一锅法制备芳基二硫醚的反应,且产率高,操作简单,工艺时间短,成本低、后处理容易且绿色无污染,符合绿色化学的发展要求。我们以单质硫制备二硫醚而不用硒催化制备二硫醚,不仅大大降低了成本,而且使反应的后处理更加简单,且不会产生二硒醚等杂质,产率高。本实验以2,4-二硝基氯苯制备双(2,4-二硝基苯基)二硫醚为例,初步探究了其反应机理,并通过大量实验对反应温度、反应时间、溶剂、助催化剂等做了研究,最后得出了最佳的反应条件。最佳反应条件如下:2,4-二硝基氯苯5mmol,单质硫5mmol,水0.5mL,碳酸钠5mmol,温度95℃,在一氧化碳持续鼓泡条件下反应1h,可得双(2,4-二硝基苯基)二硫醚的产率为96.85%,适当的改变条件,可将此反应应用于其他卤素取代的芳基化合物制备二硫醚的反应。
[Abstract]:With the rapid development of society, organic disulfide compounds, as a kind of widely used fine chemical raw materials and organic synthetic intermediates, have been paid more and more attention to, for example, in medicine, pesticides, dyes, rubber vulcanizers, lubricants, etc. Food additives, battery energy storage materials and anticancer drugs are widely used. Therefore, the demand for how to synthesize disulfide in large quantities, efficiently and quickly is also increasing, especially aryl disulfide. The production conditions are more stringent and the requirements for instruments and equipments are more precise, which poses a greater challenge to the mass production of aryl disulfide. At present, the industrial methods used to prepare disulfide are mercaptan oxidation method, nanometer catalytic synthesis method, etc. These methods have more or less disadvantages, such as high cost, harsh production conditions, environmental pollution, etc. The purpose of this paper is to explore a kind of low production cost, high output, simple process, etc. In this paper, simple sulfur is used as reaction reagent, water as hydrogen source, carbon monoxide as carbonyl source and DMSO as reaction solvent. In this method, aryl disulfide was prepared by one-pot method with high yield, simple operation, short processing time, low cost, easy post-treatment and no pollution. In accordance with the requirements of green chemistry, we prepared disulfide from elemental sulfur instead of using selenium as catalyst, which not only greatly reduced the cost, but also made the post-treatment of the reaction simpler, and the impurities such as disulfide were not produced. The yield is high. In this experiment, the reaction mechanism of Bis 2N 4- dinitrophenylyl) disulfide was preliminarily investigated, and the reaction temperature, reaction time, solvent, cocatalyst and so on were studied by a large number of experiments. Finally, the optimum reaction conditions were obtained as follows: 1: 2N 4- dinitrochlorobenzene 5 mmol, sulfur 5 mmol, water 0.5 mmol, sodium carbonate 5 mmol, temperature 95 鈩，

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