發(fā)布時間：2018-03-18 20:12

  本文選題：單質(zhì)硫　切入點：芳基二硫醚　出處：《遼寧大學》2017年碩士論文　論文類型：學位論文

【摘要】：隨著社會的迅速發(fā)展,有機二硫醚類化合物作為一種廣泛使用的精細化工原料及有機合成中間體,越來越被重視。例如在醫(yī)藥、農(nóng)藥、染料、橡膠硫化劑、潤滑劑、食品添加劑、電池儲能材料及抗癌藥物方面得到廣泛應用。也因此,人們對于如何能大量、高效、快速的合成二硫醚的需求也在持續(xù)不斷的上升。尤其是芳基二硫醚,制作條件更加苛刻,對于儀器設備的要求更加精密,給芳基二硫醚的批量生產(chǎn)帶來了更大的挑戰(zhàn)。目前工業(yè)上用來制備二硫醚的方法有硫醇氧化法、納米催化合成法等,這些方法都存在或多或少的缺點,如成本高、生產(chǎn)條件苛刻、環(huán)境污染等。本文旨在探索一種生產(chǎn)成本低、產(chǎn)量高、工藝簡單、綠色無污染且易于大量生產(chǎn)的合成方法。本文以單質(zhì)硫為反應試劑,水作為氫源,一氧化碳作為羰基來源,DMSO作為反應溶劑,常壓條件下,將底物制備為芳基二硫醚化合物。此方法實現(xiàn)了一鍋法制備芳基二硫醚的反應,且產(chǎn)率高,操作簡單,工藝時間短,成本低、后處理容易且綠色無污染,符合綠色化學的發(fā)展要求。我們以單質(zhì)硫制備二硫醚而不用硒催化制備二硫醚,不僅大大降低了成本,而且使反應的后處理更加簡單,且不會產(chǎn)生二硒醚等雜質(zhì),產(chǎn)率高。本實驗以2,4-二硝基氯苯制備雙(2,4-二硝基苯基)二硫醚為例,初步探究了其反應機理,并通過大量實驗對反應溫度、反應時間、溶劑、助催化劑等做了研究,最后得出了最佳的反應條件。最佳反應條件如下:2,4-二硝基氯苯5mmol,單質(zhì)硫5mmol,水0.5mL,碳酸鈉5mmol,溫度95℃,在一氧化碳持續(xù)鼓泡條件下反應1h,可得雙(2,4-二硝基苯基)二硫醚的產(chǎn)率為96.85%,適當?shù)母淖儣l件,可將此反應應用于其他鹵素取代的芳基化合物制備二硫醚的反應。
[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，

本文編號：1631120