双氨基酸氢膦烷与烯丙式卤代烃的反应及其机理探究

发布时间：2018-06-10 16:14

本文选题：膦烷负离子 + 反应机理　；参考：《郑州大学》2016年硕士论文

【摘要】：在磷化学的研究中,五配位有机磷化合物扮演着重要的角色。氢膦烷是一类含有P-H键的有机五配位磷化合物,由于其具有良好的生物活性、活泼的化学性质以及反应的多样性而得到不断深入地研究。双氨基酸氢膦烷是具有手性中心的氢膦烷,具有较好的稳定性。我们小组在合成双氨基酸氢膦烷的基础上,系统地研究了双氨基酸氢膦烷与酚、胺等试剂的类Atherton-Todd反应。为进一步探究双氨基酸氢膦烷的化学性质,本论文以双氨基酸氢膦烷为原料,研究了其与烯丙式卤代烃的反应,合成了系列含五配位P-C键的新型螺磷烷化合物。首先,我们对反应溶剂、碱、温度以及相转移催化剂用量等条件筛选,得到最佳反应条件:DMF为溶剂、碳酸铯作为碱(3 eq)、室温、四丁基碘化铵(1 eq)、烯丙式卤代烃(2 eq)。在最佳反应条件下,探究了不同结构的双氨基酸氢膦烷与苄氯反应,研究发现双氨基酸氢膦烷侧链结构位阻增大时,反应速率降低。随后探究了双缬氨酸氢膦烷与不同类型卤代烃的反应,发现卤代烃的种类及其位阻是影响反应速率的主要因素,同时利用熔点、红外、核磁以及高分辨等手段对合成的含五配位P-C键的螺磷烷产物进行了结构表征。其次,对双氨基酸氢膦烷与烯丙式卤代烃的反应机理进行了探究,提出了双氨基酸氢膦烷与烯丙式卤代烃反应的机理。认为双氨基酸氢膦烷在碳酸铯和相转移催化剂的共同作用下首先生成双氨基酸膦烷负离子的铯盐,然后烯丙式卤代烃进攻双氨基酸膦烷负离子发生亲电取代反应,从而生成含五配位P-C键的螺磷烷产物。最后,对新型磷烷化合物波谱学性质进行分析。利用一维NMR和简单的二维NMR确定了化合物的平面结构;由于氨基酸单元中两个手性碳原子的构型在反应过程中保持不变,利用二维谱图NOESY技术对中心磷原子的相对构型进行了推断。通过分析非对映异构体中磷原子构型与偶合常数JCCNP的关系,得出含五配位P-C键新型新型螺磷烷化合物非对映异构体之间的偶合常数存在JCCNP(ΔP)JCCNP(ΛP)的规律,该波谱学规律对于推断含五配位P-C键的磷化合物的构型和研究其立体化学性质具有重要的意义。
[Abstract]:Five-coordinated organophosphorus compounds play an important role in the study of phosphorus chemistry. Hydrophosphonane is a kind of organic five-coordinated phosphate compounds with P-H bond. It has been studied deeply because of its good biological activity, active chemical properties and diversity of reactions. Diamino acid hydrophosphonane is a hydrophosphine with chiral center and has good stability. Based on the synthesis of diamino acid hydrophosphonane, the Atherton-Todd reaction of diamino acid hydrophosphonane with phenols and amines was studied systematically. In order to further study the chemical properties of diamino acid hydrophosphonane, a series of novel spirophosphorane compounds containing five coordination P-C bonds were synthesized by using diamino acid hydrophosphonane as raw material to study its reaction with allyl halogenated hydrocarbons. First of all, the reaction solvent, alkali, temperature and the amount of phase transfer catalyst were selected. The optimum reaction conditions were obtained, such as: DMF as solvent, cesium carbonate as alkaloid 3 eqn, room temperature, 4 Ding Ji ammonium iodide 1 eqn, allyl halogenated hydrocarbon 2 eqn. Under the optimum reaction conditions, the reaction rate of bis-amino acid hydrophosphonane with benzyl chloride was studied. It was found that the reaction rate decreased with the increase of side chain structure hindrance of bis-amino acid hydrophosphonane. The reaction of divaline hydrophosphine with different types of halogenated hydrocarbons was studied. It was found that the species and steric hindrance of halogenated hydrocarbons were the main factors affecting the reaction rate. At the same time, the melting point, IR, IR and FTIR were used to determine the reaction rate. The synthesized spirophosphorane products with five coordination P-C bonds were characterized by NMR and high resolution. Secondly, the reaction mechanism between diamino acid hydrophosphonane and allyl halogenated hydrocarbon was studied, and the reaction mechanism of diamino acid hydrophosphine with allyl halogenated hydrocarbon was put forward. It is considered that the diamino acid hydrophosphonane first forms the cesium salt of the anion of diamino acid phosphane under the combined action of cesium carbonate and phase transfer catalyst, and then the allyl halogenated hydrocarbon attacks the anion of diamino acid phosphonane to take place electrophilic substitution reaction. Thus, a spirophosphate product containing a five-coordinated P-C bond was formed. Finally, the spectroscopic properties of the new phosphorane compounds were analyzed. The planar structure of the compounds was determined by one-dimensional NMR and simple two-dimensional NMR, because the configuration of two chiral carbon atoms in amino acid units remained unchanged during the reaction. The relative configuration of central phosphorus atom was inferred by NOESY technique. By analyzing the relationship between the configuration of phosphorus atom and the coupling constant JCCNP in the enantiomer, it is concluded that the coupling constant between the diaenomeric isomers of a new type of spirophosphate compound containing five coordination P-C bonds is JCCNP (螖 P0 JCCNP (A P). The spectral law is of great significance to infer the configuration and study the stereochemical properties of phosphorus compounds with five coordination P-C bonds.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O643.12

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