The kinetic studies of hydroformylation of 1-butene to produce pentanal were investigated by using Rh/PPh 3 complex as homogeneous catalyst, valeraldehyde and its polycondensates as solvent. The experiment was carried out on small hydroformylation continuous reaction installation. The effects of reaction temperature, the concentration of 1-butene, the partial pressure of CO or H 2 and the concentration of rhodium of catalyst on the reaction rate were studied. Based on the reaction mechanism of hydroformylation and the latest research results of hydroformylation kinetics, the kinetic equation suitable for the hydroformylation of 1-butene was established. The parameters of the kinetic equation were regressed and verified with the experimental data. The relationship between the normal/isomeric ratio of pentanal and the partial pressure of CO was further explored.
Kuan Wang,Jie Lan,Zhen-Hong He,Zhe Cao,Weitao Wang,Yang Yang,Zhao-Tie Liu
The synthesis of benzyl alcohols (BAs) is highly vital for their wide applications in organic synthesis and pharmaceuticals. Herein, BAs was efficiently synthesized via hydroxymethylation of phenylboronic acids (PBAs) and paraformaldehyde over a simple Rh PPh 3 catalyst combined with an inorganic base (NaOH). A variety of BAs with the groups of CH 3 − , CH 3 O − , Cl − , Br − , and so on were obtained with moderate to good yields, indicating that the protocol had a good universality. Density functional theory (DFT) calculations proposed the Hayashi-type arylation mechanism involved the arylation step of PBA and Rh(OH)(PPh 3 ) 2 catalyst to form Rh(I)-bound aryl intermediates and the hydrolysis step of Rh(I)-bound aryl intermediates and HCHO to generate BA product (the rate-determining step). The present route provides a valuable and direct method for the synthesis of BAs and expands the application range of paraformaldehyde.
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