本文選題：含氮化合物 + C-N鍵　； 參考：《湘潭大學(xué)》2017年博士論文

【摘要】：含氮化合物廣泛存在于天然產(chǎn)物、醫(yī)藥、農(nóng)藥以及功能材料等領(lǐng)域,因此,C-N鍵的選擇性構(gòu)建一直是有機(jī)合成化學(xué)研究的重點和熱點。環(huán)己酮作為一種廉價易得的大宗化工原料,在合成化學(xué)中也被廣泛應(yīng)用。近年來的研究結(jié)果表明,環(huán)己酮可以“脫氫”作為潛在的芳基來源用于進(jìn)一步轉(zhuǎn)化反應(yīng)。隨著環(huán)境友好綠色化學(xué)的概念逐步推廣,發(fā)展簡單、高效、綠色以及條件溫和的有機(jī)合成方法已經(jīng)成為當(dāng)今有機(jī)合成化學(xué)的研究重點。本論文圍繞“環(huán)己酮參與的選擇性C-N鍵生成反應(yīng)”這一核心主題,以環(huán)己酮為主要原料,開展了一系列構(gòu)建C-N鍵的研究工作,主要內(nèi)容如下:1、發(fā)展了一種鈀催化芳香硝基化合物和環(huán)己酮“一鍋”合成二芳胺的新方法。該反應(yīng)首次利用芳香硝基化合物和環(huán)己酮衍生物為原料在鈀催化下采用“借氫戰(zhàn)略”合成二芳基胺。利用該方法我們高選擇性、高產(chǎn)率地合成了一系列的二芳胺。硝基被環(huán)己酮脫下來的氫直接還原并用于進(jìn)一步轉(zhuǎn)化反應(yīng),在無需添加額外還原劑和氧化劑的條件下實現(xiàn)了硝基的還原、環(huán)己酮脫氫、亞胺的形成及還原,為二芳胺的合成提供了一條高效的新途徑。2、發(fā)展了一種無過渡金屬條件下脒和酮“一鍋”高效合成4,5-二氫-1H-咪唑-5-酮衍生物的新方法。各種帶取代基的脒與酮都能發(fā)生反應(yīng)并以較好的產(chǎn)率得到相應(yīng)的產(chǎn)物。當(dāng)使用環(huán)狀酮作為反應(yīng)底物時,能高選擇性、高產(chǎn)率的得到的含螺環(huán)的4,5-二氫-1H-咪唑-5-酮衍生物,反應(yīng)中發(fā)生了基團(tuán)的遷移重排。該方法條件簡單,不需要使用過渡金屬催化劑,為合成咪唑啉酮類化合物特別是含有螺環(huán)的4,5-二氫-1H-咪唑-5-酮衍生物提供了一條有效途徑。3、發(fā)展了一種無金屬條件下2-氨基吡啶類化合物和環(huán)己酮衍生物高效合成苯并[4,5]咪唑并[1,2-a]吡啶衍生物的新方法。非芳香性的環(huán)己酮類化合物在綠色的氧化劑氧氣的作用下實現(xiàn)脫氫芳構(gòu)化作為芳基來源。該方法為具有生物活性的含氮雜環(huán)化合物苯并[4,5]咪唑并[1,2-a]吡啶類化合物的合成提供了一條高效的途徑。4、發(fā)展了一種無金屬條件下以環(huán)狀酮和2-氨基苯并噻唑為原料“一鍋”合成咪唑并[2,1-b]苯并噻唑衍生物的新方法。單質(zhì)硫在無金屬參與的條件下能有效的促進(jìn)反應(yīng)的進(jìn)行。環(huán)己酮衍生物以及一些大環(huán)環(huán)狀酮在該反應(yīng)體系下能順利的與2-氨基苯并噻唑發(fā)生反應(yīng)構(gòu)建兩個新的C-N鍵得到相應(yīng)的產(chǎn)物。
[Abstract]:Nitrogen-containing compounds are widely used in natural products, medicine, pesticides and functional materials, so the selective construction of C-N bonds has been the focus and hotspot of organic synthesis chemistry. Cyclohexanone, as a cheap and easily available chemical raw material, is also widely used in synthetic chemistry. Recent studies have shown that cyclohexanone can be used as a potential aryl source for further conversion. With the gradual promotion of the concept of environmentally friendly green chemistry, the development of simple, efficient, green and mild organic synthesis methods has become the focus of organic synthesis chemistry. In this paper, a series of studies on the construction of C-N bond were carried out with cyclohexanone as the main raw material, focusing on the core theme of "selective C-N bond formation reaction involving cyclohexanone". The main contents are as follows: 1. A new palladium catalyzed "one pot" synthesis method of aromatic nitro compounds and cyclohexanone was developed. In this reaction, aromatic nitro compounds and cyclohexanone derivatives were used as raw materials to synthesize diaryl amines under the catalysis of palladium for the first time. A series of diarylamines were synthesized with high selectivity and high yield by this method. Nitro was directly reduced by hydrogen removed from cyclohexanone and used for further conversion reaction. The reduction of nitro, the dehydrogenation of cyclohexanone, the formation and reduction of imine were realized without adding additional reductant and oxidant. This paper provides a new efficient way for the synthesis of diarylamine, and develops a new method for the synthesis of 4o 5-dihydro-1H-imidazole-5-one derivatives under the condition of transition metal free from amidine and ketone "one pot". All kinds of substituted amidines can react with ketones and obtain the corresponding products in a better yield. When cycloketone was used as the substrate of the reaction, the group migration rearrangement occurred in the reaction, which was characterized by high selectivity and high yield of 4H _ 5H _ 1H _ (imidazole-5-one) derivatives containing snails. The method is simple and does not require the use of transition metal catalysts. This paper provides an effective way for the synthesis of Imidazolinone compounds, especially 4H- dihydro-1H-imidazole-5-one derivatives containing snails, and develops a highly efficient combination of 2-aminopyridine compounds and cyclohexanone derivatives under metal-free conditions. A New method for the formation of Benzo [4H _ 5] imidazo [1o _ 2-a] pyridine Derivatives. Non-aromatic cyclohexanone compounds were dehydroaromorphic to aryl source under the action of green oxidant oxygen. This method provides a high efficient way for the synthesis of benzo [4o 5] imidazo [1o 2-a] pyridine compounds with biological activity, and develops a metal-free method based on cyclic ketone and 2-aminobenzothiazole. A new method for the synthesis of imidazo [2o 1 b] benzothiazole derivatives from one pot. Elemental sulfur can effectively facilitate the reaction without metal participation. Cyclohexanone derivatives and some macrocyclic ketones can successfully react with 2-aminobenzothiazole to form two new C-N bonds.
【學(xué)位授予單位】：湘潭大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O621.25

【參考文獻(xiàn)】

相關(guān)期刊論文 前9條

1 王希;劉水平;;Olmutinib(Olita)[J];中國藥物化學(xué)雜志;2016年06期

2 陳本川;;治療慢性淋巴細(xì)胞白血病新藥——維奈托克(venetoclax)[J];醫(yī)藥導(dǎo)報;2016年11期

3 王巍;劉晶晶;張龍;;苯酚催化氫轉(zhuǎn)移制環(huán)己酮的新工藝[J];化工進(jìn)展;2013年09期

4 房承宣;于泳;王亞濤;屈一新;;環(huán)己烯水合催化劑及工藝研究進(jìn)展[J];現(xiàn)代化工;2012年12期

5 白翔;王世榮;李祥高;徐國輝;;三芳胺類空穴傳輸材料結(jié)構(gòu)與性能的關(guān)系[J];化學(xué)工業(yè)與工程;2007年06期

6 薛金強(qiáng),王世榮,李祥高;二芳胺類化合物的合成及其在光電功能材料中的應(yīng)用[J];化學(xué)工業(yè)與工程;2005年02期

7 張麗芳,陳赤陽,項志軍;環(huán)己烷氧化制備環(huán)己酮和環(huán)己醇工藝研究進(jìn)展[J];北京石油化工學(xué)院學(xué)報;2004年02期

8 于良民,姜曉輝,董磊,徐煥志,劉登良;異噻唑啉酮類化合物及其在海洋防污涂料中的應(yīng)用[J];涂料工業(yè);2004年05期

9 梁皇英;何祖鈿;;氨基甲酸酯類殺蟲劑[J];山西農(nóng)業(yè)科學(xué);1990年08期

，

本文編號：1976354