本文選題：硝化　切入點：硝酸鉍催化　出處：《大連理工大學(xué)》2016年碩士論文

【摘要】：含硝基化合物廣泛應(yīng)用于醫(yī)藥、農(nóng)藥、炸藥等領(lǐng)域,同時也是一種重要的精細化工中間體。本文主要包括芳胺的連續(xù)流動硝化制備硝基芳胺和光催化脫羧硝化制備p-硝基苯乙烯衍生物兩部分內(nèi)容。第一部分研究了在連續(xù)流動微反應(yīng)器中,以硝酸鉍為催化劑,硝酸為硝化試劑,選擇性硝化芳胺。相比于傳統(tǒng)的混酸硝化方法,具有反應(yīng)條件較為溫和,反應(yīng)易于精確控制,鄰位選擇性高等優(yōu)點。以芳基伯胺為原料,考察了反應(yīng)溫度、反應(yīng)停留時間(泵流速)、乙酸酐用量、硝酸用量、硝酸鉍用量等對硝化收率以及鄰對位選擇新的影響。最終確定10 m01%五水硝酸鉍,2.0倍量濃硝酸(65wt.%),9.0倍量乙酸酐,二氯甲烷為溶劑,在30℃條件下反應(yīng)50分鐘。通過連續(xù)流動微反應(yīng)器,擴展了14個鄰硝基芳胺類底物。同時以苯胺為原料,將反應(yīng)規(guī)模放大了五倍,仍然得到了93%的分離收率。第二部分主要對α,β-不飽和羧酸在光催化條件下脫羧硝化生成β硝基苯乙烯進行了初步的探索。通過對光催化劑種類,添加物,氧化劑和溶劑的初步篩選,最終確定反應(yīng)條件為：肉桂酸,0.2 mmol;亞硝酸叔丁酯,0.6 mmol;BI-OH,0.1 mmol;光催化劑Ru(bpy)3(PF6)2,0.004 mmol;乙腈,2 mL,氧氣氛圍反應(yīng),在室溫下,用藍光照射17 h。在此基礎(chǔ)上,我們對底物適應(yīng)性進行了初步擴展,發(fā)現(xiàn)以3,4,5-三甲氧基苯丙烯酸為底物時氣相收率能達到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，

本文編號：1720879