本文選題：芳基碘化物 + CuAAC反應(yīng)�。� 參考：《河南師范大學(xué)》2017年碩士論文

【摘要】：自2001年由諾貝爾化學(xué)獎獲得者Sharpless首次提出點擊化學(xué)(click chemistry)的概念以來,以疊氮化合物與末端炔的環(huán)加成(CuAAC)反應(yīng)成為“點擊化學(xué)”中的經(jīng)典。點擊化學(xué)可廣泛應(yīng)用于醫(yī)藥、農(nóng)藥、電極表面修飾、染料、生化試劑、高分子及功能聚合材料等各個領(lǐng)域。由于端基炔的局限性及其昂貴性,探求一種更有效、區(qū)域選擇性更好的有機催化的疊氮化物-醛[3+2]環(huán)加成反應(yīng)也成為繼CuAAC反應(yīng)之后的又一熱點。本論文的主要工作簡要介紹如下:本文第一部分對芳基疊氮化合物的研究進(jìn)展、兩組分合成1,2,3-三氮唑和多組分合成1,2,3-三氮唑的合成方法進(jìn)展及三氮唑化合物在醫(yī)藥、農(nóng)藥及工業(yè)生產(chǎn)等各個領(lǐng)域的應(yīng)用進(jìn)展方面進(jìn)行了綜述。本文第二部分研究了CuI/DBU(1,8-二氮雜二環(huán)[5.4.0]十一碳-7-烯)和Cu(OAc)2·H2O/DBU(1,8-二氮雜二環(huán)[5.4.0]十一碳-7-烯)兩個催化體系分別作用于芳基碘與疊氮化鈉的親核取代反應(yīng),建立了一種合成芳基疊氮化合物的新方法。通過對反應(yīng)條件的優(yōu)化,主要包括催化劑的篩選、堿的篩選、溶劑的選擇、催化體系用量的比例控制以及溫度的考察,得到最優(yōu)的反應(yīng)條件:CuI(20 mol%),DBU(30 mol%),1.2當(dāng)量疊氮化鈉,DMSO,95℃;或者Cu(OAc)2·H2O(10 mol%),DBU(15 mol%),1.2當(dāng)量疊氮化鈉,DMSO,95℃。該方法具有反應(yīng)時間短、普適性好、收率高等優(yōu)點,并探索可能的催化機理。本文第三部分建立了芳基碘、疊氮化鈉和端基炔的三組分兩步一鍋法合成1,2,3-三氮唑的研究方法。通過對反應(yīng)條件的優(yōu)化,得到最佳的反應(yīng)條件:第一步,1.0 mmol芳基碘,1.2 mmol疊氮化鈉,3.0 mL DMSO,10 mol%的Cu(OAc)2·H2O和20 mol%的DBU,95℃;第二步,室溫,0.5 mmol端基炔。該方法將原位生成的芳基疊氮化合物不經(jīng)分離直接引入到端基炔上,避免了從反應(yīng)混合物中分離所產(chǎn)生的危險性疊氮化合物。該方法操作簡便、普適性好。本文第四部分建立了芳基碘、疊氮化鈉和醛的三組分兩步一鍋法合成1,2,3-三氮唑的研究方法。通過對反應(yīng)條件的優(yōu)化,得到最佳的反應(yīng)條件:第一步,1.0 mmol芳基碘,1.2 mmol疊氮化鈉,3.0 mL DMSO,10 mol%的Cu(OAc)2·H2O和20 mol%的DBU,95℃;第二步,室溫,0.5 mmol醛。該方法將原位生成的芳基疊氮化合物不經(jīng)分離直接引入到醛上,避免了從反應(yīng)混合物中分離所產(chǎn)生的危險性疊氮化合物。該方法操作簡便,對底物適用范圍廣。
[Abstract]:Since Sharpless, Nobel laureate in chemistry, first introduced the concept of click-chemistry (click chemistry) in 2001, the cycloaddition of azide compounds with terminal acetylene has become a classic in click-chemistry. Click chemistry can be widely used in medicine, pesticide, electrode surface modification, dyes, biochemical reagents, polymer and functional polymeric materials and other fields. Because of the limitation of terminal acetylene and its high cost, the search for a more effective and better regioselectivity of azide aldehyde [32] cycloaddition reaction has become another hot spot after CuAAC reaction. The main work of this thesis is as follows: in the first part of this paper, the progress of the research on aryl azide compounds, the synthesis methods of 1ttriazole and multicomponent synthesis, and the application of triazoles in medicine, The progress in application of pesticide and industrial production is reviewed. In the second part of this paper, we studied the nucleophilic substitution of aryl iodine with sodium azide by Cui / DBU (1) -diaza-dicyclo [5.4.0] undecyl -7-ene and Cu (OAC) _ 2H _ 2O / DBU (1) -diaza-dicyclo [5.4.0] undecyl -7-ene, respectively. A new method for the synthesis of aryl azide compounds was established. Through the optimization of reaction conditions, including the screening of catalyst, the selection of alkali, the selection of solvent, the proportion control of catalyst system and the investigation of temperature, the optimum reaction conditions were obtained as follows: 1: CuI (20 mol%) DBU (30 mol%) 1. 2 equivalent sodium azide at 95 鈩，

本文編號：2078067