本文選題：芳香烴 + 對甲苯磺酸鐵��； 參考：《合肥工業(yè)大學(xué)》2017年碩士論文

【摘要】：芳烴以及雜環(huán)芳烴是一類很重要的有機化學(xué)成分中間體,它們被廣泛地應(yīng)用于醫(yī)藥、農(nóng)藥、紡織和精細化學(xué)品等中。對芳香化合物的研究一直受到化學(xué)工作者的重視,新的研究領(lǐng)域不斷地被開拓,傳統(tǒng)的合成方法也不斷地被改進、創(chuàng)新,從而發(fā)展為更加簡單高效的合成方法來合成更加復(fù)雜的化合物,C-H鍵直接官能團化是近年來研究比較熱的研究領(lǐng)域并取得了很好的成果。通過對芳環(huán)上的C-H鍵活化直接官能團化來在芳環(huán)上引入其他官能團的研究將具有非常重要的研究意義。本文以過渡金屬為催化劑,對芳香烴的sp2 C-H鍵進行活化烷基化以及胺化反應(yīng)進行了研究。經(jīng)過條件優(yōu)化,篩選確定了最佳的反應(yīng)條件,在最優(yōu)條件下對底物進行了拓展,并對實驗結(jié)果進行了相關(guān)討論。本文第一部分是以對甲苯磺酸鐵為催化劑,以過氧酰作為烷基化試劑,催化芳香烴以及雜環(huán)芳烴的C-H鍵進行活化烷基化反應(yīng),合成了一系列的芳烴烷基化產(chǎn)物。通過反應(yīng)條件的優(yōu)化,篩選出了最佳優(yōu)化條件是:在氮氣保護條件下,反應(yīng)溫度為100℃,0.5 mmol過氧酰,5 mL芳香烴,2.5 mol%對甲苯磺酸鐵,反應(yīng)時間為5小時。實驗結(jié)果表明此反應(yīng)條件更適宜于吸電子基的芳香烴的烷基化反應(yīng),與傳統(tǒng)的傅克烷基化反應(yīng)形成互補,反應(yīng)更傾向于生成鄰位取代產(chǎn)物。本文第二部分是以溴化銅作為催化劑,醋酸碘苯作為氧化劑,N-氯代酞酰亞胺作為氮源,進行芳烴的C-H鍵活化官能團化反應(yīng),實現(xiàn)了芳烴的C-H鍵的胺化,合成了一系列的氨基芳烴。通過反應(yīng)條件的優(yōu)化,篩選出了最佳優(yōu)化條件是:0.5 mmol N-氯代酞酰亞胺、2mL芳烴(既作為反應(yīng)底物,又作為溶劑),10mol%溴化銅、2 mmol醋酸碘苯,溫度為130℃,反應(yīng)時間為8小時。實驗結(jié)果表明此反應(yīng)中芳香烴取代基的電子效應(yīng)對反應(yīng)有很重要的影響,反應(yīng)條件更適合于富電子基的芳香烴的胺化反應(yīng)。
[Abstract]:Aromatic hydrocarbons and heterocyclic aromatic hydrocarbons are important organic chemical intermediates, which are widely used in medicine, pesticides, textiles and fine chemicals. The study of aromatic compounds has been paid attention to by chemists, new research fields have been continuously developed, and traditional synthetic methods have been continuously improved and innovated. It is a hot research field in recent years to develop a more simple and efficient synthesis method to synthesize more complex compounds such as C-H bond direct functionalization and has achieved good results. The introduction of other functional groups to aromatic rings by activation of C-H bonds on aromatic rings will be of great significance. The activation alkylation and amination of sp2 C-H bonds of aromatic hydrocarbons were studied using transition metal as catalyst. The optimum reaction conditions were determined by optimizing the conditions, the substrate was expanded under the optimal conditions, and the experimental results were discussed. In the first part of this paper, a series of aromatics alkylation products were synthesized by using ferric p-toluenesulfonate as catalyst and peroxy as alkylation reagent to catalyze the C-H bond of aromatic hydrocarbons and heterocyclic aromatics. By optimizing the reaction conditions, the optimum conditions were as follows: under the condition of nitrogen protection, the reaction temperature was 100 鈩，

本文編號：1912813