邻位异腈基和腈基的芳基叔膦化合物的反应性能研究

发布时间：2018-05-24 05:38

本文选题：苯并氮磷杂环戊二烯 + λ5-磷杂萘　；参考：《郑州大学》2017年博士论文

【摘要】：P-C键选择性切断的研究主要集中在磷杂环戊二烯衍生物上,对于开环的芳基叔膦化合物的研究较少。本论文以此为出发点,设计并合成了邻位异腈基和腈基的芳基叔膦化合物。通过研究其反应性能,我们发现了多个基于邻位异腈基和腈基的芳基叔膦化合物分子内的新环化反应,其中主要是发展了1,2-和1,3-氮磷杂环戊二烯和λ5-磷杂苯衍生物的新合成方法,具体分为以下四个章节进行阐述。第一章主要概述1,2-和1,3-氮磷杂环戊二烯及其衍生物的电子属性、结构特征、合成方法、反应性能及其应用。第二章主要研究一类易于制备的邻-(二芳基膦)芳香异腈的丰富多彩的反应性能。异腈官能团具有特殊的化学键结构和特有的反应性能,在合成化学和配位化学有着巨大的应用价值。将其引入三苯基膦类化合物骨架中,合成邻-(二芳基膦)芳香异腈类化合物还从未被报道过。从合成的角度考虑,邻-(二芳基膦)芳香异腈被金属锂选择性切断P-C键发生分子内关环反应,形成1,3-苯并氮杂磷环戊二烯负离子被发现。为研究这类负离子化合物的反应活性,分别加入不同的亲电试剂RX(苄溴和碘甲烷)可以合成3H-1,3-苯并氮磷杂环戊二烯。当苯并氮磷杂环戊二烯负离子质子化时,重要的λ3σ2-P 1H-1,3-苯并氮磷杂环戊二烯被制备。据此,我们发现了一类P-C键被碱金属选择性切断的新化合物,同时也发展了一种新颖简单的合成1H和3H-1,3-苯并氮磷杂环戊二烯的新方法(Scheme1)。另外,为深入研究邻位异腈基的芳基叔膦化合物的化学反应性能,我们又考察分子内磷叶立德进攻异腈基发生的环化反应,同时合成了一类λ5-1,4-苯并氮磷杂六元环新化合物(Scheme 2)。从配位化学角度考虑,邻-(二芳基膦)芳香异腈是一类新型的双齿配体。为研究其配位性能,我们利用邻-(二芳基膦)芳香异腈与四氢噻吩氯化金反应得到了双配位的金配合物,但与氯化钯反应却合成了稀少的钯-卡宾配合物。更令人意外的是,邻-(二芳基膦)芳香异腈在氯化镍的作用下自身关环形成一类稠环的苯并氮磷杂六元环新化合物(Scheme 3)。可见,邻-(二芳基膦)芳香异腈的配位性能也表现出丰富多彩性。第三章主要介绍一类由简单易得的邻-(二苯基膦)芳香腈合成1,2-苯并氮磷杂环戊二烯的新方法。在金属锂的作用下,邻-(二苯基膦)芳香腈中P-C键被选择性切断后,发生分子内关环反应,从而合成了1,2-苯并氮磷杂环戊二烯负离子。这类负离子化合物磷化学位移在165 ppm左右,根据文献报道这种处于如此低场磷化学位移的负离子是很少见的。由于其化学活性较高,我们不能分离纯化这类1,2-苯并氮磷杂环戊二烯负离子,但是通过亲电试剂(苄溴、溴丙烷和1,2-二溴乙烷)进行捕捉,从而合成了极少报道的1,2-氮磷杂吲哚类化合物,即2H-1,2-苯并氮磷杂环戊二烯。另外,根据理论计算预测,1,2-苯并氮磷杂环戊二烯负离子质子化反应会发生在氮原子上,且得到的1H-1,2-苯并氮磷杂环戊二烯既是一类平面结构,也是一类10π的芳香体系。实验中通过1,2-苯并氮磷杂环戊二烯负离子与水的反应,我们检测到1H-1,2-苯并氮磷杂环戊二烯的生成(31P NMR 157 ppm)。由于其反应活性较高,通过与N-苯基马来酰胺发生[4+2]环加成反应进行捕捉再硫化,从而合成了氮磷杂降冰片烯硫化物,且通过单晶结构得以表征。至此,通过P-C键选择性切断的策略,我们探索并开发了一类新颖简单的由邻位腈基的芳基叔膦化合物合成1H和2H-1,2-苯并氮磷杂环戊二烯的新方法(Scheme 4)。第四章主要研究一类新颖简单的合成稠环λ5-磷杂萘的新方法。λ3σ2-磷杂苯之所以被称为“化学奇物”,主要是因为磷杂苯及其衍生物作为膦配体在金属催化的烯烃的氢甲酰化反应中表现出良好的性能以及其在功能分子材料方面潜在的应用价值。目前,λ3-磷杂苯的研究日趋完善和成熟。相对而言,λ5-磷杂苯及其衍生物的研究才刚刚起步,目前的合成方法较少,且存在很大的局限性。利用磷原子与缺电子炔烃的亲核反应,成功设计了分子内两性离子中间体进攻腈基发生关环的反应,从而合成了λ5-磷杂苯衍生物(即稠环的λ5-磷杂萘)(Scheme 5)。该合成方法具有新颖简单、反应条件温和、底物适用性好以及原子高效性等特点,代表性产物达17个之多。从这些制备的产物中,我们发现磷原子上带有烷基的λ5-磷杂萘在紫外灯照射下具有黄-绿色荧光现象,而磷原子上带有芳基的λ5-磷杂萘却没有这种现象。于是,初步研究了部分代表性产物的紫外吸收和荧光光谱性质。除此之外,磷原子上带有两个叔丁基的λ5-磷杂萘在高温下能够裂解转化为芳香性的λ3-磷杂萘。这类含有λ3σ2P=C键的磷杂环具有较高的反应活性,限制了其分离纯化。但是,通过与2,3-二甲基-1,3-丁二烯[4+2]环加成反应进行捕捉后再硫化,分离纯化的产物通过单晶结构表征证实了λ3-磷杂萘的生成。
[Abstract]:The selective cutting of P-C bonds is mainly focused on the derivatives of phosphorus heteropentadiene, and there are few studies on the open TERT phosphine compounds. In this paper, we designed and synthesized the aryl TERT phosphine compounds of the adjacent ISO nitrile and nitrile based compounds. By studying their reaction properties, we found a number of adjacent ISO nitriles and nitriles. New cyclization reactions within the base of aryl TERT phosphine compounds, including the development of new synthesis methods for 1,2- and 1,3- nitrogenous cyclopentadiene and lambda 5- phosphonium derivatives, are described in the following four chapters. The first chapter mainly outlines the electronic properties, structural characteristics, and properties of 1,2- and 1,3- nitrogen and phosphorus heterocyclic dioprene and its derivatives. The second chapter mainly studies the rich and colorful reaction properties of a class of easy prepared ortho (two aryl phosphine) aromatic nitriles. ISO functional groups have special chemical bond structure and specific reaction properties, and have great application value in synthetic chemistry and coordination chemistry. They are introduced into three phenyl phosphine compounds. In the skeleton, the synthesis of O (two aryl phosphine) aromatic heteronitrile compounds has never been reported. From the synthetic point of view, the adjacent (two aryl phosphine) aromatic isonitrile is selectively cut off the P-C bond by lithium metal and takes place in the intramolecular ring reaction, forming 1,3- benzo azo phosphorus cyclopentadiene negative ions and the reaction to the study of this kind of negative ion compound. 3H-1,3- benzo - N - P heterocycladiene can be synthesized with different electrophilic reagents, RX (benzyl bromide and iodide). When the negative ion protonation of benzo - N - P heterocyclic dioprene, the important lambda 3 Sigma 2-P 1H-1,3- benzo - azopentadiene is prepared. Accordingly, we found a new class of compounds that are selectively cut off from the alkali metal by the alkali metal. A new and simple new method (Scheme1) for the synthesis of 1H and 3H-1,3- benzo - N - P heteropentadienes is also developed. In addition, in order to study the chemical reaction properties of the aryl TERT phosphine compounds of the adjacent ISO nitrile, we also examine the cyclization reaction of the intramolecular phosphorus leaf Lide attacking the isobutadiene, and syntheses a class of lambda 5-1,4- benzol N, P, six membered ring new compound (Scheme 2). From the point of coordination chemistry, O (two aryl phosphine) aromatic isonitrile is a new type of didentate ligand. In order to study its coordination properties, we have obtained a gold complex by the reaction of O (two aryl phosphine) aromatic isonitrile and four hydrogen thiophene, but the reaction with palladium chloride is rare. Less palladium - CABBEEN complexes. It is more surprising that the adjacent - (two aryl phosphine) aromatic isonitrile forms a new class of polycyclic benzo - azo phosphorous six membered ring compounds (Scheme 3) under the action of nickel chloride. The coordination properties of the adjacent - (two aryl phosphine) aromatic isonitrile are also colorful. The third chapter mainly introduces a class of simple compounds. A new method for the synthesis of 1,2- benzo - N - P heteropentadiene by easy - to - (two phenyl phosphine) aromatic nitrile. Under the action of lithium metal, the P-C bond in the adjacent - (two phenyl phosphine) aromatic nitrile is selectively cut off, and the internal ring reaction occurs, and the negative ion of 1,2- phthalazoniopentyl two ene is synthesized. The phosphorus chemical shift of this kind of negative ion compound is 165 Ppm, according to the literature, it is reported that the negative ions in such a low field phosphorus chemical shift are rare. Because of their high chemical activity, we can not separate and purify this kind of 1,2- benzoate and phosphorus heteropentadiene negative ions, but they have been captured by the electrophilic reagents (benzyl bromide, brominopropane and 1,2- two bromo ethane), resulting in a rare report of 1. 2- nitrogen and phosphorus heterocyclic compounds, namely 2H-1,2- benzo nitrogen and phosphorus heteropentadiene. In addition, according to theoretical calculation, the negative ion protonation of 1,2- benzo azopeniopentadiene will occur on nitrogen atoms, and the obtained 1H-1,2- benzo azopentadiene is not only a class of planar structure but also a class of 10 PI aromatic systems. The reaction of 1,2- benzo - N - P heteropentadiene anion with water, we detected the formation of 1H-1,2- benzo - azopallopentadiene (31P NMR 157 ppm). Because of its high reactive activity, it was captured and revulcanized by the [4+2] ring addition reaction with N- phenyl maleamide, thus synthesizing the nitrogen and phosphorus complex borneol sulfides and through single crystal. The structure is characterized. At this point, we have explored and developed a new and simple new method for the synthesis of 1H and 2H-1,2- benzo azopentadiene (Scheme 4) from the aromatic TERT phosphine compounds from the adjacent nitrile base (Scheme 4). In Chapter fourth, a new method of synthesis of a new simple synthesis of thick ring lambda 5- phosphonadiene was studied. [1] 3 The reason that sigma 2- phosphorous benzene is called "chemical strange" is mainly due to the good performance of phosphine and its derivatives as phosphine ligands in the hydroformylation of metal catalyzed olefin and its potential application value in functional molecular materials. At present, the study of lambda 3- phenyle is becoming more and more perfect and mature. The study of lambda 5- phosphonyl benzene and its derivatives has just started. There are few synthetic methods and great limitations. Using the nucleophilic reaction of phosphorous atoms with the electron deficient alkynes, the reaction of the intramolecular amphoteric ion intermediate attacking the nitrile ring is successfully designed, and thus the lambda 5- phosphonide derivative (the lambda 5- phosphorous compound of the thick ring) is formed. Naphthalene) (Scheme 5). The synthesis method has the characteristics of novel and simple, mild reaction conditions, good substrate applicability and atomic efficiency, and more than 17 representative products. From these products, we found that the lambda 5- phosphor naphthalene with alkyl alkyl on the phosphorous atom has yellow green fluorescence under ultraviolet light, while the phosphorus atom is on the phosphorus atom. The aryl lambda 5- phosphor naphthalene has no such phenomenon. Therefore, the UV absorption and fluorescence spectra of some representative products are preliminarily studied. In addition, the two tert butyl lambda 5- phosphor naphthalene can be cracked and converted into aromatic lambda 3- phosphine naphthalene at high temperature. This kind of heterocyclic ring containing lambda 3 Sigma 2P=C bonds has a higher inverse. The separation and purification of 2,3- two methyl -1,3- butadiene [4+2] ring was reacted and revulcanized. The product of the separation and purification confirmed the formation of lambda 3- phosphine naphthalene by the single crystal structure characterization.
【学位授予单位】：郑州大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O627.51

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