Synthesis A Fluorine-free Phosphine Ligand Modified By Carbonate

Phosphine ligand is a functional organic compound which is widely used in catalysis. Its physical and chemical properties are affected by its molecular structure (including the electronic structure and spatial structure). At the same time, many researchers carry out a lot of work about reactions in ScCO2 reaction medium, finding a lot of new problems and new phenomena. For example, in the field of homogeneous catalysis, the phosphine ligands are a commonly used catalyst ligands.The current research and work on the phosphine ligands have been common, but in ScCO2, the polar phosphine ligands and catalysts have a poor behavior in solubility.While the solubility of the catalyst in a homogeneous catalyst system is directly related to the catalytic efficiency of the catalyst and the reaction effect. Currently, to increase the solubility of the ligands in carbon dioxide mainly focus on introduction fluorine-containing groups to the molecular structures. Introducing fluorine-containing groups can increase the affinity of the ligand structure and carbon dioxide, but the introduction of fluorine-containing group does not meet the concept of green chemistry, in its use,it will be broken down into the fluorinated alkanes which are harmful to atmospheric environment; In addition, introducing fluorine-containing groups are also very uneconomical, and would increase the cost.Professor Jessop from Australia noted that:in the molecular structure, the introduction of Lewis basic atoms increases the solubility of the molecule in ScCO2. Based on this concept, the present work was designed to regard triphenylphosphine as a parent, and structurally modified, incorporated in the molecular structure containing more Lewis basic atoms-carbonic ester groups.Also we studied the synthetic method, optimized the reaction conditions, and predicted the solubility. The synthesis of this compound provides a basis for the synthesis of its derivatives.The main contents of this paper include:(1) Designed the synthesis route of the fluorine-free phosphine ligand, and explored the best synthesis method of the fluorine-free phosphine ligand. The synthesis of the phosphine ligand utilized characteristics of the symmetry, explored the impact of certain synthetic way on the reaction results. Studied the synthesis of tris (4-hydroxyphenyl) phosphine oxide.(2) Synthesis of novel intermediates tris(4-(glycidyl ether)phenyl)phosphine oxide, tris (p-(glycidyl ether carbonate)phenyl) phosphine oxide, as well as synthesis of the fluorine-free phosphine ligands:tri (p-glyceryl ether carbonate ester phenyl) phosphine and its borane complex and we characterized them by 1H-NMR,31P-NMR,13C-NMR,MS.(3) Evaluation of the current synthetic routes. The reaction scheme can successfully synthesize the free-fluorine phosphine ligand-tris (p-(glycidyl ether carbonate)phenyl) phosphine-borane complex, but it’s a longer route.