【摘要】：氮氧化物是一類“奇異的”氧化物。低濃度下時(shí),充當(dāng)著生物體內(nèi)的信號(hào)傳遞分子;高濃度下,卻是有毒氣體,是造成大氣污染的主要污染源之一。這與氮氧化物的物種多樣性(氮價(jià)態(tài)在+1到+4)以及轉(zhuǎn)變的可逆性相關(guān),常能呈現(xiàn)出一些奇異的性質(zhì)。本文主要研究氮氧化物在金屬離子誘導(dǎo)下與酚酸酯反應(yīng),發(fā)生直接高選擇性重氮化反應(yīng)的條件與機(jī)理。研究結(jié)果證明:在沒(méi)有金屬離子作用下,過(guò)量氮氧化物只與水楊酸甲酯發(fā)生少量的硝基化反應(yīng)。但當(dāng)存在金屬離子(RE3+,Zn2+,Cu2+,Ni2+,Ca2+等)的高氯酸鹽時(shí),過(guò)量氮氧化物與水楊酸酯能夠發(fā)生直接的重氮化反應(yīng),得到高選擇性的5-重氮基水楊酸甲酯高氯酸鹽,并以結(jié)晶的形式從反應(yīng)體系析出。對(duì)反應(yīng)過(guò)程中反應(yīng)物的配比(稀土離子與水楊酸甲酯的摩爾比)、氮氧化物的通入速度、反應(yīng)時(shí)間、反應(yīng)溫度以及反應(yīng)溶劑等因素對(duì)這一重氮化反應(yīng)的影響研究結(jié)果證明:該反應(yīng)的發(fā)生主要經(jīng)歷了金屬離子對(duì)水楊酸甲酯的配位活化、三氧化二氮對(duì)酚羥基對(duì)位氫的直接取代、后續(xù)氮氧化物對(duì)取代中間體的連續(xù)還原和重氮化合物的結(jié)晶析出等階段。結(jié)合反應(yīng)過(guò)程的紅外光譜、紫外可見(jiàn)光譜以及質(zhì)譜分析數(shù)據(jù),認(rèn)為具有鄰羥基苯甲酰結(jié)構(gòu)的化合物(除水楊酸)由于苯環(huán)上酚羥基及鄰位羰基與金屬離子發(fā)生螯合配位,使對(duì)位和鄰位的氫得到活化,而取代反應(yīng)是由氮氧化物整個(gè)分子(N2O3或N2O3H+)直接進(jìn)攻的,由于空間位阻效應(yīng),使取代反應(yīng)只發(fā)生在對(duì)位,得到高選擇性的羥基對(duì)位重氮化產(chǎn)物。該重氮化反應(yīng)沒(méi)有經(jīng)歷亞硝基水楊酸甲酯這一中間態(tài)物質(zhì),而是通過(guò)N2O3(或N2O3H+)直接接入苯環(huán),離去H+,得到-NONO2結(jié)構(gòu);隨后在溶液中的還原性物質(zhì)(如NO+/HNO2)作用下,將多余的氧原子帶離,得到重氮鹽。并且證明SO2也可以作為還原劑�；诮饘汆徚u基苯甲酰類酚酸酯配合物在乙酸丁酯溶液中與過(guò)量氮氧化物接觸能夠發(fā)生重氮化反應(yīng),得到重氮鹽結(jié)晶的現(xiàn)象,研究了多級(jí)吸收瓶對(duì)氮氧化物的吸收情況,并提出了一套將有毒害性的氮氧化物轉(zhuǎn)變?yōu)橛杏弥氐}化合物的方法。
[Abstract]:Nitrogen oxides are a class of "strange" oxides. At low concentration, it acts as a signal transporter in organisms, but at high concentration, it is a toxic gas, which is one of the main sources of air pollution. This is related to the species diversity of nitrogen oxides (the valence of nitrogen is between 1 and 4) and the reversibility of the transition. In this paper, the conditions and mechanism of direct selective diazotization of nitrogen oxides with phenolic acid esters induced by metal ions are studied. The results show that the nitration of excess nitrogen oxides with methyl salicylate occurs only in the absence of metal ions. However, in the presence of perchlorates with metal ions (RE3, Zn2, Cu2, Ni2, Ca2, etc.), excessive nitrogen oxides can react directly with salicylate to obtain highly selective 5-diazo methyl salicylate perchlorates. And precipitated from the reaction system in the form of crystallization. The ratio of reactants (molar ratio of rare earth ions to methyl salicylate), the penetration rate of nitrogen oxides, the reaction time, The effects of reaction temperature and solvent on the diazotization reaction were studied. The results showed that the reaction mainly underwent the coordination activation of methyl salicylate by metal ions, and the direct substitution of p-phenolic hydroxyl hydrogen by nitrogen trioxide. Continuous reduction of substituted intermediates and crystallization of diazo compounds by subsequent nitrogen oxides. In combination with the IR, UV-Vis and MS analysis data of the reaction process, it is considered that the compounds with o-hydroxybenzoyl structure (desalicylic acid) chelate and coordinate with metal ions due to phenolic hydroxyl groups and O-carbonyl groups in benzene ring. The substitution reaction was directly attacked by the whole nitrogen oxide molecule (N2O3 or N2O3H). Due to the steric effect, the substitution reaction only occurred in the para-site, resulting in highly selective hydroxy p-diazotization products. The diazotization reaction did not go through the intermediate state of methyl nitrosalicylate, but via N2O3 (or N2O3H) directly into the benzene ring, leaving H, to obtain-NONO2 structure; Then the excess oxygen atoms were separated from the excess oxygen atoms under the action of reductive substances (such as NO / HNO2) in the solution to obtain diazo salts. It is also proved that SO2 can also be used as reducing agent. Based on the diazotization reaction of metal o-hydroxybenzoyl phenolic acid complexes in butyl acetate solution with excess nitrogen oxides, the crystallization of diazo salts was obtained. The absorption of nitrogen oxides in multistage absorption bottles was studied. A method for converting toxic nitrogen oxides into useful diazo salt compounds is proposed.
【學(xué)位授予單位】：南昌大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.25

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 孫墨杰;李治寬;鄭勝;王世杰;張?jiān)?姚杰;;Fe(Ⅱ) EDTA吸收-好氧反硝化菌處理氮氧化物的研究[J];東北電力大學(xué)學(xué)報(bào);2015年05期

2 王興;崔家友;侯紹彬;楊曉宇;賈輝;林浩;高玉峰;;高濃度氮氧化物煙氣處理技術(shù)研究及應(yīng)用[J];中國(guó)有色冶金;2015年03期

3 Andrea Predonzani;Bianca Calì;Andrielly HR Agnellini;Barbara Molon;;Spotlights on immunological effects of reactive nitrogen species: When inflammation says nitric oxide[J];World Journal of Experimental Medicine;2015年02期

4 王金民;張璐;李琦;;探討工業(yè)廢氣中氮氧化物的處理措施[J];資源節(jié)約與環(huán)保;2015年03期

5 ;Selective nitration of aromatic compounds catalyzed by Hβ zeolite using N_2O_5[J];Chinese Chemical Letters;2012年07期

6 劉艷珠;李永繡;李霞;張玲;;硝酸鐵對(duì)水楊酸甲酯的硝化及位置選擇性[J];應(yīng)用化學(xué);2010年04期

7 何志勇;羅軍;呂春緒;;綠色硝化劑N_2O_5的制備方法及其應(yīng)用進(jìn)展[J];火炸藥學(xué)報(bào);2010年01期

8 成健;姚其正;董巖;劉祖亮;;TMPSHSO_4催化N_2O_5/有機(jī)溶劑硝化2,6-二乙酰氨基吡啶-1-氧化物[J];含能材料;2009年05期

9 何小榮;周錦;;高濃度氮氧化物的測(cè)定方法[J];石油化工應(yīng)用;2009年01期

10 黨靜霜;范德勇;;配合物組成及穩(wěn)定常數(shù)的測(cè)定[J];河北工業(yè)科技;2008年02期

相關(guān)博士學(xué)位論文 前3條

1 陸金杰;基于環(huán)狀偶氮苯的新型功能性材料的高效合成及其性能研究[D];蘇州大學(xué);2016年

2 熊志波;鐵基SCR脫硝催化劑改性研究[D];山東大學(xué);2013年

3 賴俊英;偶氮類結(jié)腸靶向高分子藥物的合成、生物降解和釋藥性能的研究[D];浙江大學(xué);2006年

相關(guān)碩士學(xué)位論文 前6條

1 吳霏;不同N_2O_5硝化體系硝化反應(yīng)工藝研究[D];中北大學(xué);2016年

2 張?jiān)婈?稀土—水楊酸酯與NO_x的反應(yīng)研究及應(yīng)用[D];南昌大學(xué);2015年

3 張信莉;Mn改性γ-Fe_2O_3催化劑低溫SCR脫硝性能研究[D];山東大學(xué);2015年

4 顏農(nóng)平;新型偶氮類衍生物的合成及對(duì)陰離子識(shí)別性能的研究[D];蘭州交通大學(xué);2013年

5 鄒秀新;一氧化氮與釔—水楊酸甲酯配合物的顯色反應(yīng)及應(yīng)用[D];南昌大學(xué);2012年

6 張玲;基于水楊酸甲酯釔配合物的NO識(shí)別[D];南昌大學(xué);2010年

，

本文編號(hào)：2334112