The Appliation Of Ferrocenyl Imidazoline Palladacycles In Heck Reation

The synthesis of ferrocenyl imidazoline-palladacycles was carried out and the palladacycles complexes have been applied in Heck reaction. There are four parts in the thesis as follow:First, the latest development of the catalysts in Heck reaction was reviewed.Second, two serieses of the ferrocenyl imidazoline ligands derived from valinol and phenylalaninol were synthesized in considering the property and structure effect of ferrocene. According to the electronic effect of the ferrocenyl imidazolines, the ortho-palladateds were performed and depolymerization of monomers were synthesized successfully by triphenylpho -sphine. At the same time, depolymerizations of single crystal monomer compounds 100b,100d,100h were also gained, which were characterized by X-ray single crystal diffraction.Third, Heck reaction could be successfully catalyzed by more and more palladacycle com -pounds in recent development. Using the synthesized palladacycles as catalyst, two Heck rea t -ions were researched. One was the reaction of methyl acrylate with haloaromas, the other wa -s the reaction of styrene with haloaromas. The effection of different catalysts, the other was different sovents, different bases, different temperature and different substrats on Heck reation were discussed respective. According to the experimental results, the optimal condation was as follow:10^-5mol loading of catalyst 99b was choosed as the catalyst which afforded the high -est efficiency in the coupling processes. The temperature was 140℃. DMF was used as solv -ent. 1.5 equivalent K₃PO₄·3H₂O was added as base.1.5 equivalent n-Bu4NBr was used as the additive. All the reactions were performed under normal condition without the protection of inactive gas. As result, coupled products were obtained in excellent yields. Haloaromas which were used in the reactions were shown as follow: Finally, three single crystal monomers derived from depolymerization were also gained, which were characterized by X-ray single crystal diffraction and the structure of ferrocenyl imidazolines-palladacycles were further determined by single crystal X-ray diffraction in this paper. 17 different haloaromas were catalyzed by the ferrocenyl imidazolines-palladacycles complexes in Heck reation.Meanwhile, 30 different compounds were synthesized and applica -ted in the research and their structure characterization were also performed by IR, ¹H NMR,¹³C NMR.