本文選題：2-芳基惡唑啉衍生物 + 氮雜雙環(huán)衍生物　； 參考：《濟南大學(xué)》2016年碩士論文

【摘要】：本文歸納總結(jié)了2-芳基惡唑啉衍生物和氮雜雙環(huán)衍生物的合成意義和國內(nèi)外研究現(xiàn)狀,選取了腈類化合物與氨基醇合成2-芳基惡唑啉衍生物和二烯醛化合物與乙氮烯合成氮雜雙環(huán)化合物兩類合成反應(yīng)為研究對象,我對它們各自的四個合成反應(yīng)體系的反應(yīng)機理分別進行了理論研究,目的在于探討2-芳基惡唑啉和氮雜雙環(huán)類化合物的合成反應(yīng)規(guī)律。本文采用的研究方法是密度泛函理論B3LYP法,采用基組6-311++G**進行計算,利用高斯程序Gaussian 09,全面優(yōu)化了反應(yīng)勢能面上各個能量最低點(即我們通常所說的“駐點”)的構(gòu)型,我們?nèi)客ㄟ^振動分析進一步確認各平衡結(jié)構(gòu)構(gòu)型、過渡態(tài)構(gòu)型的真假性(虛頻有且只有一個)和各物種的熱力學(xué)函數(shù),并考慮了甲醇的溶劑化效應(yīng)。為了確認過渡態(tài)的屬性,我們進一步計算了內(nèi)稟反應(yīng)坐標(IRC)。我們通過對腈類化合物與氨基醇合成2-芳基惡唑啉衍生物的四個反應(yīng)體系合成機理的理論探究,證實它們的反應(yīng)原理是大致相同的,反應(yīng)的歷程包含了三個化學(xué)反應(yīng),三個化學(xué)反應(yīng)由五個基元反應(yīng)而構(gòu)成。腈類化合物首先與溶劑甲醇發(fā)生了一加成反應(yīng),生成了一中間產(chǎn)物。然后,它依次通過一置換反應(yīng),異構(gòu)化反應(yīng),環(huán)化反應(yīng),脫NH3反應(yīng)生成了最終產(chǎn)物2-芳基惡唑啉衍生物。三個化學(xué)反應(yīng)的摩爾吉布斯自由能變(?rGm)均小于零,并且三個化學(xué)反應(yīng)都是放熱反應(yīng)。我們通過對二烯醛化合物與乙氮烯合成氮雜雙環(huán)衍生物的四個反應(yīng)體系合成反應(yīng)理的理論探究,證實它們的反應(yīng)原理是大致相同的,反應(yīng)過程包括三個步驟。二烯醛化合物與乙氮烯首先通過一氫遷移反應(yīng)生成了一中間體。然后,它依次通過一異構(gòu)化反應(yīng),環(huán)化反應(yīng)生成了最終產(chǎn)物氮雜雙環(huán)化合物。所研究反應(yīng)的摩爾吉布斯自由能變(?rGm)均小于零,都是放熱反應(yīng)。
[Abstract]:In this paper, the significance of synthesis of 2-aryl oxazoline derivatives and aza-heterocyclic derivatives and the current research situation at home and abroad are summarized and summarized. The synthesis of 2-aryl oxazoline derivatives from nitriles and amino alcohols and the synthesis of azobicyclic compounds from dienal compounds and ethylenes were studied. In this paper, we have studied the reaction mechanism of their four synthetic reaction systems respectively. The aim of this study is to study the synthesis of 2-aryl oxazoline and azobicyclic compounds. The research method used in this paper is the density functional theory (DFT) B3LYP method, the basis set 6-311 GW * is used to calculate, and the Gao Si program Gaussian 09 is used to optimize the configuration of the lowest point of energy on the surface of the reaction potential (that is, the "stationary point"). Through vibration analysis, we further confirm the true and false (virtual frequency and only one) and thermodynamic functions of each equilibrium structure, transition state configuration, and consider the solvation effect of methanol. In order to confirm the properties of the transition state, we further calculate the intrinsic reaction coordinates (IRC). The mechanism of synthesis of 2-aryl oxazoline derivatives from nitrile compounds and amino alcohols has been investigated theoretically. It has been proved that the reaction mechanism is approximately the same, and the reaction process includes three chemical reactions. Three chemical reactions consist of five elementary reactions. Nitriles first reacted with solvent methanol to form an intermediate product. Then, the final product 2-aryl oxazoline derivative was obtained by a displacement reaction, an isomerization reaction, a cyclization reaction and a deNH3 reaction. The molar Gibbs free energy variation (RGm) of the three chemical reactions is less than zero, and the three chemical reactions are exothermic reactions. Through the theoretical study on the synthesis of azobicyclic derivatives from dienal compounds and ethylenes, it is proved that their reaction mechanism is approximately the same, and the reaction process consists of three steps. Dienal compounds first reacted with ethylenes to form an intermediate through a hydrogen migration reaction. Then, the final product nitrogen heterobicyclic compounds were obtained by one isomerization reaction and the cyclization reaction. The molar Gibbs free energy variations (RGm) of the reactions studied are all less than zero and they are all exothermic reactions.
【學(xué)位授予單位】：濟南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O626

【參考文獻】

相關(guān)期刊論文 前3條

1 柳開文;徐德然;濮社班;;乙內(nèi)酰脲類化合物的研究進展[J];中國野生植物資源;2010年03期

2 白雪媛;楊椏楠;王永生;;海因類化合物的藥理作用進展[J];中成藥;2006年10期

3 張勝利,許祖勛,黃錦霞,陳祖興;N,N-二鹵代二甲基乙內(nèi)酰脲的合成及殺菌性能研究[J];湖北大學(xué)學(xué)報(自然科學(xué)版);2002年01期

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本文編號：2085665