Study Of Titanocene Dichloride/zinc Restored Disulfides And Its Application

Organic and organic sulfides as old as history, Thiocarbonyl a class of compounds are very important organic compounds, can be synthesized a variety of important organic synthetic intermediates in organic synthesis plays an extremely important role. As a result of disulfide in the air more stable, odorless, and it is organic sulfur, an important intermediate in the reaction. At present, there are many methods restored disulfide, but there are a lot of shortages. Titanocene dichloride relatively was stable, while the zinc is a cheap metal and easy to get, therefore, this article designed as titanocene dichloride / zinc for a system to restore the disulfide and study the formation of free radicals and the phenylthio-anhydride,α-bromo carbonyl compounds,α,β-unsaturated compounds, as well as tetrahydrofuran reaction, the main research work are as follows:At first, we studied titanocene dichloride / zinc system for the reducing agent, the reaction was a dark green titanocene chloride, and then we joined the disulfide, experiment shows that the reduction reaction at room temperature under the protection of nitrogen can be effectively carried out. Subsequently, efficient anhydride be phosphorothioate esters, the yield is about 80%. The response of mild reaction conditions, the product of a single, simple experiment, thus Thiocarbonyl Synthesis provides a simple and effective method. At the same time, the uses of reducer and reaction temperature were all discussed.As follow, we explored the subsequent reduction of the product with theα-bromo carbonyl compounds reacted, the experimental results gave a good result, and obtained a series ofα-thiocarbonyl compounds, the yield is from 75% to 86%. The experiment to avoid the use of hard preparation, toxicity, and the stench of the reagents, the experimental operation and post-processing is simple, for theα-Thiocarbonyl Synthesis provides a simple and effective new method.Then we visited the reduction product with theα,β-unsaturated compound conjugate addition, laboratory synthesis of a series of highly efficientβ-Thiocarbonyl compounds, the yield is from 80% to 100%, the method is avoid direct use of a strong unpleasant smell of mercaptan etc, without alkali conditions, which is a better preparation ofβ-phenylthio-ester (β-phenylthio-ketones) or nitrile method.In view of previous studies, we explored the reduction product of the reaction with the aryl-high salt, but the experiment has not been the expected product of a single sulfide, but a new synthetic material 2 - thio tetrahydrofuran, the yield was about 70%. This article discusses the subsequent reaction mechanism of the experiment. This method is the product of a single, and simple post-processing reaction, easy separation of product, it is a good synthesis of 2 - thio tetrahydrofuran method.