【摘要】：近年來,過酸酯以及烯丙基酯類化合物由于它們?cè)诨瘜W(xué)領(lǐng)域的諸多應(yīng)用而受到了人們廣泛的關(guān)注。目前,雖然已有多種方法可以用來合成該類物質(zhì),但其中大部分存在諸如反應(yīng)條件比較苛刻,底物適應(yīng)性較差等缺點(diǎn)。隨著綠色化學(xué)這一觀念的逐漸深入人心,探究操作簡單、條件溫和且環(huán)境友好的碳碳、碳雜鍵構(gòu)筑方法已經(jīng)成為如今有機(jī)合成領(lǐng)域的研究熱點(diǎn)。與此同時(shí),C-H活化在有機(jī)合成化學(xué)領(lǐng)域受到了廣泛關(guān)注。它具有原子經(jīng)濟(jì)性高、污染小等優(yōu)點(diǎn)。正因?yàn)槿绱?通過醛的C-H活化來合成過酸酯以及由此衍生的烯丙基酯無疑具有重要的研究價(jià)值,為這類化合物的合成提供了一種新的合成方法。本文通過對(duì)配體、催化劑、溫度、溶劑等條件的探索優(yōu)化,發(fā)展了一種以醛為底物,高效的銅催化的合成過酸叔丁酯的方法,然后在此基礎(chǔ)上與烯烴反應(yīng)成功實(shí)現(xiàn)了烯丙基酯的一鍋法串聯(lián)合成反應(yīng)。具體研究內(nèi)容如下:(1)Cu(I)配合物催化的以醛為底物合成過酸叔丁酯的方法研究該方法以10 mol%Cu I為催化劑、10 mol%bpy為配體,醛為原料,無需溶劑,在近于室溫條件下與TBHP(過氧叔丁醇)反應(yīng)2~6 h,以良好的收率合成得到過酸酯化合物。實(shí)驗(yàn)證明:多齒氮配體的加入對(duì)該銅催化的反應(yīng)起到了關(guān)鍵的調(diào)控作用。與以往文獻(xiàn)中所報(bào)道的方法相比,該反應(yīng)體系顯著縮短了反應(yīng)時(shí)間,無需溶劑,具有更好的官能團(tuán)容忍性和底物適應(yīng)性,并以較高收率得到目標(biāo)產(chǎn)物。(2)Cu(I)配合物催化的一鍋法合成烯丙基酯的方法研究在不需要添加額外催化劑的情況下,Cu I催化醛與TBHP反應(yīng)2~6 h后,向體系中添加適量的環(huán)己烯,升溫反應(yīng)6~18 h便可成功地以醛為底物一鍋法制備烯丙基酯。與以往文獻(xiàn)報(bào)道不同的是,該反應(yīng)體系使用了廉價(jià)易得的銅催化劑,無需溶劑,反應(yīng)可以在較短時(shí)間內(nèi)以良好的收率得到一系列烯丙基酯類化合物,該反應(yīng)體系同時(shí)也具有很好的底物適應(yīng)性。此外,據(jù)我們所知,這是首次報(bào)道的銅催化一鍋法串聯(lián)合成烯丙基酯類化合物。通過以上兩種合成方法,成功地得到了十三種過酸叔丁酯及十一種烯丙基酯,并對(duì)它們進(jìn)行了結(jié)構(gòu)表征。
[Abstract]:In recent years, peracid esters and allyl esters have attracted wide attention due to their many applications in the chemical field. At present, although there are many methods to synthesize this kind of substances, most of them have disadvantages such as harsh reaction conditions, poor substrate adaptability and so on. With the development of green chemistry, the carbon and carbon bond construction methods, which are simple in operation, mild in conditions and friendly in environment, have become the research focus in the field of organic synthesis. At the same time, the activation of C-H has attracted extensive attention in the field of organic synthesis chemistry. It has the advantages of high atomic economy and low pollution. Because of this, the synthesis of peracid esters by C-H activation of aldehydes and the allyl esters derived from them are undoubtedly of great research value, which provides a new synthetic method for the synthesis of these compounds. In this paper, by optimizing the conditions of ligand, catalyst, temperature, solvent and so on, a method of synthesis of tert-butyl peracid catalyzed by copper with aldehydes as substrate was developed. On this basis, the one-pot series synthesis of allyl esters was successfully realized with olefin reaction. The main contents of the study are as follows: (1) the synthesis of tert-butyl peracid using aldehyde as substrate catalyzed by) Cu (I) complex was studied. The method used 10 mol%Cu I as catalyst, 10 mol%bpy as ligand, aldehyde as raw material, no solvent, Peracid ester compound was synthesized by reaction with TBHP (peroxy tert-butanol) at room temperature for 2 h for 6 h. Experimental results show that the addition of polydentate nitrogen ligands plays a key role in the copper-catalyzed reaction. Compared with the methods reported in previous literatures, the reaction system can significantly shorten the reaction time, do not need solvent, and has better functional group tolerance and substrate adaptability. The method of one-pot synthesis of allyl ester catalyzed by 2) Cu (I) complex was used to study the reaction of aldehydes with TBHP in the presence of CuI catalyst for 2h, and then the cyclohexene was added to the system for 6 h. Allyl esters were prepared by one pot method using aldehydes as substrate in 6 鈩，

本文編號(hào)：2202797