發(fā)布時(shí)間：2018-03-14 11:30

  本文選題：雙氨基酸螺環(huán)氫膦烷　切入點(diǎn)：類(lèi)Atherton-Todd反應(yīng)　出處：《鄭州大學(xué)》2016年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：在生命體內(nèi),磷元素被譽(yù)為“生命活動(dòng)的調(diào)控中心”。生命體中生物分子DNA、RNA等水解過(guò)程中,五配位磷化合物中間體被認(rèn)為起到了關(guān)鍵的作用。五配位氫膦烷是一種重要的五配位磷化合物,其特殊性在于分子中活潑的P-H鍵,因此能發(fā)生多種化學(xué)反應(yīng),并且氫膦烷化合物含有磷手性中心,存在反應(yīng)前后磷構(gòu)型變化的現(xiàn)象。雙氨基酸氫膦烷有很好的穩(wěn)定性,而且分子中有三個(gè)手性中心,利于研究五配位磷化合物的立體化學(xué)特性,因此五配位氫膦烷是研究五配位磷化合物性質(zhì)很好的模板分子。我們課題組在研究雙氨基酸氫膦烷的基礎(chǔ)上,對(duì)其類(lèi)Atherton-Todd反應(yīng)進(jìn)行了深入的研究。本文中以雙氨基酸氫膦烷為原料,研究了其與8-羥基喹啉類(lèi)化合物的類(lèi)Atherton-Todd反應(yīng),經(jīng)過(guò)柱色譜分離提純,得到了一系列新型螺磷烷化合物。產(chǎn)物結(jié)構(gòu)均經(jīng)過(guò)了核磁、高分辨質(zhì)譜、紅外以及部分單晶衍射的確定。對(duì)該類(lèi)反應(yīng)進(jìn)行核磁磷譜信號(hào)跟蹤,發(fā)現(xiàn)反應(yīng)經(jīng)過(guò)氯磷烷中間體,確認(rèn)了其類(lèi)Atherton-Todd反應(yīng)機(jī)理。結(jié)合我們課題組對(duì)氫膦烷與酚類(lèi)反應(yīng)的研究,提出了雙氨基酸氫膦烷與8-羥基喹啉類(lèi)化合物的類(lèi)Atherton-Todd反應(yīng)機(jī)理。另外,我們對(duì)含喹啉結(jié)構(gòu)單元的新型螺磷烷產(chǎn)物進(jìn)行了電噴霧質(zhì)譜裂解規(guī)律的研究,提出了該類(lèi)化合物正離子模式下[M+Na]+離子的質(zhì)譜裂解規(guī)律和路徑,通過(guò)高分辨質(zhì)譜進(jìn)一步證明了路徑的準(zhǔn)確性。結(jié)合對(duì)酚氧螺磷烷類(lèi)化合物質(zhì)譜裂解數(shù)據(jù)的分析,總結(jié)了可能影響這兩類(lèi)化合物質(zhì)譜裂解路徑的因素,并通過(guò)密度泛函理論進(jìn)行計(jì)算,發(fā)現(xiàn)了電荷分布對(duì)裂解路徑有很大程度的影響。該類(lèi)化合物電噴霧質(zhì)譜裂解規(guī)律的研究對(duì)利用電噴霧質(zhì)譜研究相似五配位磷化合物的裂解規(guī)律和其結(jié)構(gòu)鑒定提供了幫助,具有較大的參考價(jià)值。同時(shí),我們對(duì)由氫膦烷合成的新型氨基甲酸螺磷烷酯類(lèi)化合物分子內(nèi)N-C(=O)鍵的旋轉(zhuǎn)現(xiàn)象進(jìn)行了進(jìn)一步研究。對(duì)化合物變溫核磁的氫譜和磷譜信號(hào)的變化做了細(xì)致的研究,并根據(jù)磷譜信號(hào),利用Gutowsky-Holm方程和Eyring公式對(duì)氨基甲酸螺磷烷酯類(lèi)化合物分子內(nèi)N-C(=O)鍵的旋轉(zhuǎn)自由能(?G≠)進(jìn)行了計(jì)算,結(jié)果顯示大約為16-18 kcal/mol。實(shí)驗(yàn)發(fā)現(xiàn)當(dāng)分子內(nèi)氮原子上連有芐基時(shí),會(huì)提高分子內(nèi)N-C(=O)鍵的旋轉(zhuǎn)自由能。另外運(yùn)用密度泛函理論進(jìn)行能量計(jì)算,推斷出了該類(lèi)分子的優(yōu)勢(shì)構(gòu)型,并得到了單晶結(jié)構(gòu)數(shù)據(jù)的支持。
[Abstract]:In the body of life, the phosphorus element is called "the regulating center of life activity". The intermediates of penta-coordinated phosphate compounds are considered to play a key role. Penta-coordinated hydrophosphonane is an important five-coordinated phosphate compound, whose particularity lies in the active P-H bond in the molecule, so it can take place a variety of chemical reactions. And the hydrophosphine compounds contain phosphorous chiral centers, and there are changes in the configuration of phosphorus before and after the reaction. The diamino acid hydrophosphonane has good stability, and there are three chiral centers in the molecule. It is helpful to study the stereochemical properties of pentacocoordination phosphate compounds, so pentacocoordination hydrophosphonane is a good template molecule for studying the properties of pentacocoordination phosphate compounds. Our research group is based on the study of diamino acid hydrophosphonane. In this paper, the reaction of diamino acid hydrophosphonane with 8-hydroxyquinoline compounds was studied. The reaction was separated and purified by column chromatography. A series of novel spirophosphorane compounds were obtained. The structures of the products were determined by NMR, high resolution mass spectrometry, IR and some single crystal diffraction. The mechanism of Atherton-Todd reaction between diamino acid hydrophosphonane and 8-hydroxyquinoline compounds was proposed, which was based on the study of the reaction of hydrophosphonane with phenols by our research group, and the mechanism of Atherton-Todd reaction between diamino acid hydrophosphine and 8-hydroxyquinoline compound was proposed. In this paper, we have studied the cleavage law of new spirophosphate products containing quinoline structure unit by electrospray ionization mass spectrometry (EI-MS), and put forward the decomposition law and path of [MNa] ion mass spectrometry in the positive ion mode of this kind of compounds. The accuracy of the path was further proved by high resolution mass spectrometry. Combined with the analysis of the pyrolysis data of phenoxyspirophosphate compounds, the factors that might affect the cracking paths of these two compounds were summarized. And calculated by density functional theory, It is found that the charge distribution has a great influence on the pyrolysis path. The study of the decomposition law of this kind of compounds by electrospray mass spectrometry is helpful for the study of the cleavage law and structure identification of similar five-coordination phosphorus compounds by ESI / MS. Has great reference value. At the same time, In this paper, we have further studied the rotation of the intramolecular N-Che O bond of a new type of spiroalkane carbamate synthesized from hydrophosphonane. We have made a detailed study on the changes of the hydrogen and phosphorus spectrum signals of the compounds with variable temperature NMR. According to the signal of phosphorus spectrum, Gutowsky-Holm equation and Eyring formula were used to study the rotation free energy of N-CnOO bond of spirophosphoryl carbamate compounds. G 鈮，

本文編號(hào)：1611045