芳胺连续流动硝化及光催化脱羧硝化研究

发布时间：2018-04-08 08:41

  本文选题：硝化　切入点：硝酸铋催化　出处：《大连理工大学》2016年硕士论文

【摘要】：含硝基化合物广泛应用于医药、农药、炸药等领域,同时也是一种重要的精细化工中间体。本文主要包括芳胺的连续流动硝化制备硝基芳胺和光催化脱羧硝化制备p-硝基苯乙烯衍生物两部分内容。第一部分研究了在连续流动微反应器中,以硝酸铋为催化剂,硝酸为硝化试剂,选择性硝化芳胺。相比于传统的混酸硝化方法,具有反应条件较为温和,反应易于精确控制,邻位选择性高等优点。以芳基伯胺为原料,考察了反应温度、反应停留时间(泵流速)、乙酸酐用量、硝酸用量、硝酸铋用量等对硝化收率以及邻对位选择新的影响。最终确定10 m01%五水硝酸铋,2.0倍量浓硝酸(65wt.%),9.0倍量乙酸酐,二氯甲烷为溶剂,在30℃条件下反应50分钟。通过连续流动微反应器,扩展了14个邻硝基芳胺类底物。同时以苯胺为原料,将反应规模放大了五倍,仍然得到了93%的分离收率。第二部分主要对α,β-不饱和羧酸在光催化条件下脱羧硝化生成β硝基苯乙烯进行了初步的探索。通过对光催化剂种类,添加物,氧化剂和溶剂的初步筛选,最终确定反应条件为：肉桂酸,0.2 mmol;亚硝酸叔丁酯,0.6 mmol;BI-OH,0.1 mmol;光催化剂Ru(bpy)3(PF6)2,0.004 mmol;乙腈,2 mL,氧气氛围反应,在室温下,用蓝光照射17 h。在此基础上,我们对底物适应性进行了初步扩展,发现以3,4,5-三甲氧基苯丙烯酸为底物时气相收率能达到50%。
[Abstract]:Nitro-containing compounds are widely used in medicine, pesticides, explosives and other fields, but also an important fine chemical intermediates.This paper mainly includes two parts: continuous flow nitration of aromatic amines and preparation of p-nitrostyrene derivatives by photocatalytic decarboxylation and nitration.In the first part, selective nitration of aromatic amines with bismuth nitrate as catalyst and nitric acid as nitration reagent in continuous flow microreactor was studied.Compared with the traditional mixed acid nitration method, the reaction conditions are mild, the reaction is easy to control accurately, and the site selectivity is high.The effects of reaction temperature, reaction residence time (pump flow rate, acetic anhydride, nitric acid, bismuth nitrate) on the nitrification yield and the selection of o-para-position were investigated with aryl primary amine as raw material.It was determined that 10m01% bismuth nitrate pentahydrate 2.0 times concentrated nitric acid 65 wt.and 9.0 times acetic anhydride, dichloromethane as solvent, reacting at 30 鈩，

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