Method for preparing olefin metathesis catalysts with high thermal stability and application of olefin metathesis catalysts with high thermal stability

Abstract

The invention relates to a method for preparing a series of novel phosphinimine ruthenium carbine complexes with high thermal stability and application of the novel phosphinimine ruthenium carbine complexes to the metathesis reaction of olefin, and mainly overcomes the disadvantages that the asymmetric transformation exists and the reaction still cannot be effectively realized at high temperature in the metathesis reaction for forming tetrasubstituted olefin under the catalysis of a ruthenium carbine complex, the ruthenium carbine complex is not applicable to basic functional groups (such as NH2- and CN-) and the initiation rate and increment rate are low in the previous literature. The problems can be well solved by adopting the technical scheme of metal ruthenium carbine complex ligands which have a general formula of Ru(=CHAr)Cl2L(R<1>P=NR<2>) and the synthesis thereof, wherein Ar is (C6-C14) aryl; L is an uncharged electron donor, namely a phosphino or aza five-membered ring carbine ligand; R1 is phenyl, cyclohexyl, tert-butyl, ortho-pyridyldiphenyl, and ortho-furyldiphenyl; and R2 is aryl, pyridyl and picolyl.

Description

technical field [0001] The invention relates to the synthesis of a novel ruthenium carbene phosphinoimine olefin metathesis reaction catalyst with high temperature resistance and its application in ring-closing metathesis reaction and ring-opening metathesis polymerization reaction. [0002] Yves Chauvin in France proposed the basic mechanism of olefin metathesis reaction; Richard R. Schrock and Robert H. Grubbs in the United States inherited and developed Chauvin’s olefin metathesis reaction mechanism, and developed effective and practical catalysts. Based on this foundation, academia and industry have set off an upsurge in the study of olefin metathesis reactions and the design and synthesis of new organic substances. The new synthesis process is simpler and quicker, with higher production efficiency, fewer by-products, and less harmful waste, which is conducive to protecting the environment and is a model of "green chemistry". It has great application potential in the chem...

AI Technical Summary

Problems solved by technology

In 1992, Professor Grubbs obtained the first metal ruthenium catalyst with a definite structure; in 1995, the modified "first-generation Grubbs catalyst" came out. It has mild reaction conditions, has a very wide range of functional group applicability, and is stable and easy to prepare. , even if stored in the air for several weeks, it will not decompose, and has high chemoselectivity, but its activity is slightly lower than that of Schrock catalysts, and it is also limited in application; in 1999, "Second The first-generation Grubbs catalyst" was launched and commercialized. While inheriting the advantages of the "first-generation Grubbs catalyst", the reactivity increased by two orders of magnitude.