【摘要】：氮氧化物是一類“奇異的”氧化物。低濃度下時,充當著生物體內的信號傳遞分子;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(氮價態(tài)在+1到+4)以及轉變的可逆性相關,常能呈現(xiàn)出一些奇異的性質。本文主要研究氮氧化物在金屬離子誘導下與酚酸酯反應,發(fā)生直接高選擇性重氮化反應的條件與機理。研究結果證明:在沒有金屬離子作用下,過量氮氧化物只與水楊酸甲酯發(fā)生少量的硝基化反應。但當存在金屬離子(RE3+,Zn2+,Cu2+,Ni2+,Ca2+等)的高氯酸鹽時,過量氮氧化物與水楊酸酯能夠發(fā)生直接的重氮化反應,得到高選擇性的5-重氮基水楊酸甲酯高氯酸鹽,并以結晶的形式從反應體系析出。對反應過程中反應物的配比(稀土離子與水楊酸甲酯的摩爾比)、氮氧化物的通入速度、反應時間、反應溫度以及反應溶劑等因素對這一重氮化反應的影響研究結果證明:該反應的發(fā)生主要經歷了金屬離子對水楊酸甲酯的配位活化、三氧化二氮對酚羥基對位氫的直接取代、后續(xù)氮氧化物對取代中間體的連續(xù)還原和重氮化合物的結晶析出等階段。結合反應過程的紅外光譜、紫外可見光譜以及質譜分析數據,認為具有鄰羥基苯甲酰結構的化合物(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,使對位和鄰位的氫得到活化,而取代反應是由氮氧化物整個分子(N2O3或N2O3H+)直接進攻的,由于空間位阻效應,使取代反應只發(fā)生在對位,得到高選擇性的羥基對位重氮化產物。該重氮化反應沒有經歷亞硝基水楊酸甲酯這一中間態(tài)物質,而是通過N2O3(或N2O3H+)直接接入苯環(huán),離去H+,得到-NONO2結構;隨后在溶液中的還原性物質(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量氮氧化物接觸能夠發(fā)生重氮化反應,得到重氮鹽結晶的現(xiàn)象,研究了多級吸收瓶對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.
【學位授予單位】：南昌大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O621.25

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本文編號：2334112