含喹啉环的螺磷烷化合物的合成及其质谱裂解规律的研究

发布时间：2018-03-14 11:30

  本文选题：双氨基酸螺环氢膦烷　切入点：类Atherton-Todd反应　出处：《郑州大学》2016年硕士论文　论文类型：学位论文

【摘要】：在生命体内,磷元素被誉为“生命活动的调控中心”。生命体中生物分子DNA、RNA等水解过程中,五配位磷化合物中间体被认为起到了关键的作用。五配位氢膦烷是一种重要的五配位磷化合物,其特殊性在于分子中活泼的P-H键,因此能发生多种化学反应,并且氢膦烷化合物含有磷手性中心,存在反应前后磷构型变化的现象。双氨基酸氢膦烷有很好的稳定性,而且分子中有三个手性中心,利于研究五配位磷化合物的立体化学特性,因此五配位氢膦烷是研究五配位磷化合物性质很好的模板分子。我们课题组在研究双氨基酸氢膦烷的基础上,对其类Atherton-Todd反应进行了深入的研究。本文中以双氨基酸氢膦烷为原料,研究了其与8-羟基喹啉类化合物的类Atherton-Todd反应,经过柱色谱分离提纯,得到了一系列新型螺磷烷化合物。产物结构均经过了核磁、高分辨质谱、红外以及部分单晶衍射的确定。对该类反应进行核磁磷谱信号跟踪,发现反应经过氯磷烷中间体,确认了其类Atherton-Todd反应机理。结合我们课题组对氢膦烷与酚类反应的研究,提出了双氨基酸氢膦烷与8-羟基喹啉类化合物的类Atherton-Todd反应机理。另外,我们对含喹啉结构单元的新型螺磷烷产物进行了电喷雾质谱裂解规律的研究,提出了该类化合物正离子模式下[M+Na]+离子的质谱裂解规律和路径,通过高分辨质谱进一步证明了路径的准确性。结合对酚氧螺磷烷类化合物质谱裂解数据的分析,总结了可能影响这两类化合物质谱裂解路径的因素,并通过密度泛函理论进行计算,发现了电荷分布对裂解路径有很大程度的影响。该类化合物电喷雾质谱裂解规律的研究对利用电喷雾质谱研究相似五配位磷化合物的裂解规律和其结构鉴定提供了帮助,具有较大的参考价值。同时,我们对由氢膦烷合成的新型氨基甲酸螺磷烷酯类化合物分子内N-C(=O)键的旋转现象进行了进一步研究。对化合物变温核磁的氢谱和磷谱信号的变化做了细致的研究,并根据磷谱信号,利用Gutowsky-Holm方程和Eyring公式对氨基甲酸螺磷烷酯类化合物分子内N-C(=O)键的旋转自由能(?G≠)进行了计算,结果显示大约为16-18 kcal/mol。实验发现当分子内氮原子上连有苄基时,会提高分子内N-C(=O)键的旋转自由能。另外运用密度泛函理论进行能量计算,推断出了该类分子的优势构型,并得到了单晶结构数据的支持。
[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，

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