本文選題：cyclen + 對稱四氮雜化合物��； 參考：《華東師范大學(xué)》2017年碩士論文

【摘要】：氮雜大環(huán)化合物及其N-取代衍生物,因具有易與金屬陽離子絡(luò)合的性質(zhì)而備受關(guān)注。四氮雜環(huán)的選擇性N-官能化,可通過調(diào)節(jié)配位亞基的性質(zhì)來允許微調(diào)其絡(luò)合物性質(zhì)。此前多是研究各種不對稱氮雜大環(huán)化合物的合成(受氮雜環(huán)和烷基化試劑影響較大),但對稱四氮雜化合物的合成研究較少。另吡啶基三氮雜化合物 PCTA(Pyridine Containing Tri Aza-macrocyclic)因增加了熱力學(xué)穩(wěn)定性和具有7個(gè)可能的供體位點(diǎn),通過N-烷基化,來獲得大量的配合物。然而合成四氮雜化合物才是以上研究最關(guān)鍵的步驟�；诖吮菊撐膶m合工業(yè)化生產(chǎn)的cyclen的合成、對稱四氮雜化合物的合成以及PCTA的合成進(jìn)行研究。cyclen的兩種合成方法:(1)以二乙烯三胺(DIEN)、二乙醇胺為原料,分別經(jīng)過磺�；�、合環(huán)反應(yīng),最后在98%H2SO4作用下脫保護(hù)得到cyclen;(2)以三乙烯四胺(TETA)為原料,先與乙二醛縮合成雙咪唑環(huán)化合物,在堿催化下與雙親核試劑1,2-二溴乙烷合環(huán)成四環(huán)化合物,最后用溴素或鹽酸羥胺開環(huán)得到cyclen。兩類cyclen衍生物的合成:(1)cyclen經(jīng)草酸二乙酯保護(hù)兩個(gè)相鄰N原子,然后與烷基化試劑:芐氯、BrCH2COOC(CH3)3發(fā)生SN2反應(yīng),脫保護(hù)得到對稱的1N,4N-二烷基化cyclen;(2)2,6-二氯甲基吡啶與3Ts-保護(hù)的二乙烯三胺通過SN2反應(yīng)合環(huán),98%H2S04脫保護(hù)得到PCTA。本論文在文獻(xiàn)方法的基礎(chǔ)上,結(jié)合每一步反應(yīng)機(jī)理,經(jīng)原料選擇、反應(yīng)條件篩選(包括催化劑、溶劑、反應(yīng)時(shí)間和溫度、破壞性探索等)、后處理優(yōu)化等方面的探索得到了高收率、高純度且操作簡單的合成路線。
[Abstract]:Nitrogen heterocyclic compounds and their N-substituted derivatives have attracted much attention for their easy complexation with metal cations. The selective N-functionalization of tetraazo rings allows fine tuning of their complex properties by adjusting the properties of the coordination subunits. Most of the previous studies were on the synthesis of asymmetric heterocyclic compounds (mainly influenced by heterocyclic nitrogen and alkylation reagents), but less on the synthesis of symmetric tetraazides. In addition, the pyridyl triazo compound PCTA(Pyridine Containing Tri Aza-macrocyclichas increased thermodynamic stability and has seven possible donor sites to obtain a large number of complexes by N-alkylation. However, the synthesis of tetraazides is the most important step in the above research. In this paper, the synthesis of cyclen suitable for industrial production, the synthesis of symmetric tetraazides and the synthesis of PCTA were studied. The two synthetic methods of PCTA were as follows: diethyltriamine, diethanolamine and diethanolamine, respectively, were sulfonated, respectively, using diethylenetriamine, diethanolamine, diethanolamine and diethanolamine as raw materials. Cyclization reaction, finally deprotection under the action of 98%H2SO4, gave cyclenyl 2) from triethylenetetramine (TETAA) as raw material, condensation with Glyoxal to form diimidazole ring compound, and then formed a tetracyclic compound with amphiphilic reagents 1h2- dibromoethane under alkali catalysis. Finally, cyclenes were obtained by ring opening with bromine or hydroxylamine hydrochloride. Synthesis of two kinds of cyclen Derivatives: two adjacent N atoms were protected by diethyl oxalate, and then SN2 reaction took place with alkylation reagent: benzyl chloride BrCH2COOCU CH3H3. The symmetrical 1N- 4N- dichloromethyl pyridine and the 3Ts- protected diethylenetriamine were obtained by deprotection of 1Nb4N- dialkylated cyclenyl pyridine and 3Ts- protected diethylenetriamine through SN2 reaction and cyclization 98% H2S04. In this paper, based on the methods of literature, combined with the reaction mechanism of each step, the reaction conditions (including catalyst, solvent, reaction time and temperature) were selected by the selection of raw materials and reaction conditions. High yield, high purity and simple operation were obtained from the exploration of destructive exploration and post-treatment optimization.
【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O626

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