Carbonylation of olefins by carbon monoxide and alcohols in the presence of Pd-complex catalytic system

Kairzhan Shalmagambetov,Nurbolat Kudaibergenov,Marat Bulybayev,Perizat Almatkyzy,Gulbanu Zhaksylykova,Arkhat Esenov,Diana Mamyrkhan,N.F Uvarov

doi:10.1051/matecconf/202134001023

Kairzhan Shalmagambetov, Nurbolat Kudaibergenov + Show 6 more

Open Access

https://doi.org/10.1051/matecconf/202134001023

Copy DOI

Abstract

In order to develop new, efficient and environmentally friendly methods for the preparation of practically valuable esters of carboxylic acids, studies of the hydroalkoxycarbonylation reaction of a number of terminal olefins of normal structure (hexene-1, heptene-1, octene-1, nonene-1) with carbon monoxide and alcohols in presence of metal complex catalysts based on palladium phosphine complexes at low carbon monoxide pressures (≤ 20 atm).Two-and three-component systems based on PdCl2 and Pd(Acac)2, PdCl2(PPh3)2, Pd(PPh3)4 complexes containing a free ligand (PPh3) as a stabilizer and Bronsted acid (TsOH) as a promoter were studied as catalysts. It was shown that only the three-component systems PdCl2-PPh3-TsOH, PdCl2(PPh3)2-PPh3-TsOH, Pd(Acac)2-PPh3-TsOH, and Pd(PPh3)2-PPh3-TsOH have the highest catalytic activity in the studied reactions. It was found that the reaction of hydroalkoxycarbonylation of α-olefins proceeds with the formation of a mixture of linear and branched products. The influence of various conditions of the reaction (the ratio of the initial reagents and the components of the catalytic systems, temperature, CO pressure, duration) on the course of the process and on the yield of the target products was investigated. The optimal parameters of the studied reactions have been found.

Highlights

A careful analysis of the achievements of catalytic chemical synthesis in recent years makes it possible to assert with great confidence that the future of laboratory and industrial organic synthesis will largely be determined by the success of the development of homogeneous catalysis, more precisely, by the success in the development of homogeneous metal complex catalysts
We have carried out systematic studies of the hydroalkoxycarbonylation reaction of αolefins with carbon monoxide and alcohols in the presence of catalytic systems based on palladium phosphine complexes
The reaction of hydroethoxycarbonylation of a number of α-olefins with carbon monoxide and alcohols in the presence of various two- and three-component systems based on the complexes Pd (Acac)2, PdCl2(PPh3)2 and Pd(PPh3)4 at low pressures of carbon monoxide (≤ 20 atm) [23-25]

Summary

Introduction

A careful analysis of the achievements of catalytic chemical synthesis in recent years makes it possible to assert with great confidence that the future of laboratory and industrial organic synthesis will largely be determined by the success of the development of homogeneous catalysis, more precisely, by the success in the development of homogeneous metal complex catalysts. The development of homogeneous metal complex catalysis makes another way of the synthesis of esters promising - hydroalkoxycarbonylation of alkenes (alkynes) with carbon monoxide and alcohols in the presence of metal complex catalysts. The advantage of this method for the synthesis of esters is the one-step process, the availability of the starting reagents and the possibility of influencing the course of the reaction by varying the conditions of the process and the nature of the metal complex catalyst. We have carried out systematic studies of the hydroalkoxycarbonylation reaction of αolefins with carbon monoxide and alcohols in the presence of catalytic systems based on palladium phosphine complexes. This paper provides a brief overview of the research carried out

Experimental

Results and discussion

Conclusions