本文選題：過硫酸鹽　切入點(diǎn)：硝基化　出處：《湖南大學(xué)》2016年碩士論文

【摘要】：烯烴和炔烴作為含有不飽和碳碳鍵的烴類化合物,其轉(zhuǎn)化是有機(jī)合成中重要的化學(xué)反應(yīng)。硝基烯烴作為烯烴和炔烴的轉(zhuǎn)化產(chǎn)物之一,在有機(jī)合成和藥物研究中是非常重要的中間體。因此,硝基烯烴類化合物的合成方法研究一直是科學(xué)家關(guān)注的一個(gè)研究領(lǐng)域。雖然科技工作者在此領(lǐng)域取得了很大的進(jìn)展,但是仍然存在一些缺點(diǎn),比如反應(yīng)條件比較苛刻,得到的產(chǎn)物為E/Z的混合物,方法的適用性不好以及反應(yīng)時(shí)間較長等。因此發(fā)展一種環(huán)境友好,操作簡單,經(jīng)濟(jì)性好并且實(shí)用高效的硝基烯烴合成方法依然是很有必要的。在本論文中,我們對烯烴和炔烴通過直接硝基化反應(yīng)合成硝基烯烴類化合物進(jìn)行了研究,發(fā)展了一種綠色環(huán)保,簡單高效并且適用性好的新方法。1.對烯烴和炔烴在不同硝基化試劑的作用下,合成硝基烯烴類化合物的反應(yīng)進(jìn)行了簡要的總結(jié),并對各種合成方法進(jìn)行了簡單的對比,闡述了本論文在目前研究基礎(chǔ)上的研究背景和意義。2.系統(tǒng)研究了烯烴類化合物的硝基化反應(yīng)。首先以苯乙烯為底物,對反應(yīng)的條件進(jìn)行了篩選和優(yōu)化,并得到了最優(yōu)反應(yīng)條件：苯乙烯0.5 mmol, NaNO2 0.75 mmol, K2S2O8 1.0 mmol, TEMPO 0.6 mmol,1,2-二氯乙烷2 mL,在100℃條件下,反應(yīng)24 h,分離產(chǎn)率為85%。以單取代烯烴和多取代烯烴為例,對該硝基化反應(yīng)的底物適用范圍進(jìn)行了系統(tǒng)的考察,結(jié)果表明芳香族、脂肪族以及雜環(huán)類烯烴都能在該反應(yīng)中得到硝基化產(chǎn)物,而且反應(yīng)的官能團(tuán)兼容性較好。我們同時(shí)發(fā)現(xiàn)單取代烯烴的硝基化產(chǎn)物只有E式,而多取代烯烴的產(chǎn)物則會(huì)有E式和Z式兩種構(gòu)型。隨后對反應(yīng)的立體選擇性進(jìn)行了初步的研究,并以二苯乙烯為例對烯烴硝基化反應(yīng)的過程進(jìn)行了監(jiān)測。3.對炔烴的硝基化反應(yīng)進(jìn)行了探索和研究,先后對硝基化試劑、氧化劑、碘源、反應(yīng)溶劑、溫度以及時(shí)間等影響反應(yīng)的因素進(jìn)行了考察,最終確定了苯乙炔硝基化反應(yīng)的最優(yōu)條件：苯乙炔0.5 mmol, NaNO2 2.5 mmol, K2S2O8 1.0 mmol, I2 0.25 mmol,1,2-二氯乙烷2 mL和水1 mL。在室溫20℃條件下反應(yīng)2 h,分離產(chǎn)率為76%。在此基礎(chǔ)上,對該方法的底物范圍進(jìn)行了拓展,研究了該方法的適用性。該方法對芳香族和雜環(huán)類的炔烴能夠很好的適用,但是對于脂肪族炔烴并沒有得到相應(yīng)產(chǎn)物；而且當(dāng)苯環(huán)上有較強(qiáng)電子效應(yīng)的取代基時(shí),會(huì)致使該反應(yīng)的效率降低。4.分別對烯烴和炔烴硝基化反應(yīng)的機(jī)理進(jìn)行了初步的探討。通過實(shí)驗(yàn)的設(shè)計(jì)、結(jié)果的討論與分析,并綜合相關(guān)的文獻(xiàn)報(bào)道,分別提出了烯烴與炔烴硝基化反應(yīng)的可能的機(jī)理,并根據(jù)機(jī)理對部分實(shí)驗(yàn)現(xiàn)象進(jìn)行了解釋,初步驗(yàn)證了機(jī)理的合理性。
[Abstract]:The conversion of alkenes and alkynes, as hydrocarbons containing unsaturated carbon bonds, is an important chemical reaction in organic synthesis. It is a very important intermediate in organic synthesis and drug research. Therefore, the research of synthesis method of nitroolefin compounds has been a research field that scientists pay close attention to. Although scientists have made great progress in this field, But there are still some disadvantages, such as the reaction conditions are harsh, the product is the mixture of E / Z, the method is not suitable and the reaction time is longer, so the development of a kind of environmental friendly, simple operation, etc. In this paper, we studied the synthesis of nitroolefin compounds by direct nitration reaction between alkenes and alkynes, and developed a kind of green environmental protection. The reaction of alkenes and alkynes to synthesize nitroolefin compounds under the action of different nitration reagents was summarized, and the synthesis methods were compared. In this paper, the background and significance of the present research are described. 2. The nitration reaction of olefin compounds is systematically studied. Firstly, the reaction conditions are screened and optimized with styrene as substrate. The optimum reaction conditions were obtained as follows: styrene 0.5 mmol, NaNO2 0.75 mmol, K2S2O8 1.0 mmol, TEMPO 0.6 mmol 路L ~ (-1) 2-dichloroethane 2 mL. At 100 鈩，

本文編號：1666572