Hydroformylation Of Dicyclopentadiene Research Articles

Highly efficient Rh(I)/tris-H8-binaphthyl monophosphite catalysts for hydroformylation of dicyclopentadiene to dialdehydes

Novel catalytic systems for the Rh-catalyzed hydroformylation of dicyclopentadiene have been developed using tris-H8-binaphthyl monophosphite as ligands containing different ester substituents at the 2'-binaphthyl position (OCOMe, OCOPh, OCOAdamantyl and OCOPhCl). The catalysts exhibited high activity (S/C = 4000, TON = 3286) with good to excellent selectivity towards dialdehydes. Remarkably, the Rh(I) complex bearing the ligands with chlorophenyl ester substituents led to 99.9% conversion and 98.7% selectivity for dialdehydes under relatively mild conditions (6 MPa, 120 °C).

SiO2-Supported Co–Rh Bimetallic Catalysts for Dicyclopentadiene Hydroformylation: Relationships Between Catalytic Performance and Structure of the Catalysts

In this work, SiO2-supported Co–Rh bimetallic catalysts were prepared by adopting a method of impregnation and were used to catalyse the hydroformylation of dicyclopentadiene (DCPD) to diformyltricyclodecanes. Firstly, the hydroformylation of DCPD was carried out and three reaction stages were observed. In the first stage, a sharp decrease of reaction pressure was observed within 4 minutes. In the next stage, almost no reaction pressure decrease was detected over a relatively longer reaction time (70 minutes). In the final stage, the reaction pressure decreased at a relatively gentle rate, with barely any decrease of reaction pressure being observed at 460 minutes. Secondly, the hydroformylation of monoformyltricyclodecenes (MFTD) with various reaction times was carried out; the catalyst that was used at various reaction times was also recovered. Finally, the catalyst that had been used at various reaction times was characterised and analysed and the relationship between the catalytic performance and the structure of the catalysts was confirmed. In addition, combined with triphenylphosphine, the influence of pressure on the activity of Co–Rh bimetallic catalysts was investigated for the hydroformylation of MFTD.

Hydroformylation of Dicyclopentadiene to Monoformyltricyclodecenes over Supported Ultra-Low Content Rh Catalysts

Five types of 0.006 wt% Rh catalyst supported on the surfaces of Al2O3, ZnO, TiO2(rutile), TiO2(anatase) and CeO2 were prepared by the incipient wetness method and used to catalyse the conversion of dicyclopentadiene (DCPD) to monoformyltricyclodecenes (MFTD). The 0.006 wt% Rh/ZnO catalyst showed the highest performance of the catalysts investigated and a 95.5% MFTD yield with 100% MFTD selectivity could be achieved. This suggested that there may be a key role for the carrier on the catalytic performance in the DCPD hydroformylation. Furthermore, the kinetic profiles for DCPD hydroformylation over the 0.006 wt% Rh/ZnO catalyst have been examined systematically to explore the effect of reaction temperature on the catalytic performance. These data collectively suggested that a specific reaction temperature might enhance DCPD hydroformylation, possibly owing to agglomeration of the active sites at higher reaction temperatures.

Kinetics of Dicyclopentadiene Hydroformylation over Rh–SiO2 Catalysts

The hydroformylation of dicyclopentadiene (DCPD) to monoformyltricyclodecenes (MFTD) represents a key intermediate step in the conversion of the C5 fraction derived from the petrochemical process to value-added fine chemicals, for example, diformyltricyclodecanes and tricyclodecanedimethylol. Although both heterogeneous and homogeneous catalysts can catalyse this reaction, the heterogeneously catalysed pathway has received significantly less attention due to its lower catalytic activities. We demonstrate in this work that a low Rh loaded heterogeneous 0.1% Rh–SiO2 catalyst can present a similar performance relative to the homogeneous Rh(PPh3)Cl, a reference catalyst for this reaction. Furthermore, an extensive kinetic study of DCPD hydroformylation to MFTD using heterogeneous 0.1% Rh–SiO2 catalysts has been performed. A series of kinetic experiments was carried out over a broad range of conditions (temperature: 100–120 °C; pressure: 1.5–5 MPa; catalyst-to-reactant mass ratio: 0.02–0.05; PPh3 concentration: 5–12.5 g L−1). A kinetic analysis was carried out, indicating the activation energy for the reaction to be 84.7 kJ mol−1. DCPD conversion and MFTD yield could be optimised to be as high as 99% at 0.1% Rh loading, a DCPD/catalyst mass ratio of 25, a PPh3 concentration of 10 g L−1, a reaction time of 4 h and a reaction pressure of 4 MPa.

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Six Co-Rh/Fe3O4 catalysts with different cobalt loadings were prepared by the co-precipitation of RhCl3, Co(NO3)2, and Fe(NO3)3 using Na2CO3 as the precipitant. These catalysts were tested for dicyclopentadiene (DCPD) hydroformylation to monoformyltricyclodecenes (MFTD) and diformyltricyclodecanes (DFTD). The results showed that the MFTD formation rate increased with increasing cobalt loading, whereas the DFTD formation rate initially increased and then decreased when the cobalt loading was greater than twice that of Rh. The DFTD selectivity was only 21.3% when monometallic Rh/Fe3O4 was used as the catalyst. In contrast, the selectivity was 90.6% at a similar DCPD conversion when the bimetallic 4Co-2Rh/Fe3O4 catalyst was employed. These catalysts were characterized by temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), and thermogravimetric and differential thermal analyses (TG-DTA). The results obtained by these complimentary characterization techniques indicated that adding cobalt to the Rh/Fe3O4 catalyst enhanced the Rh reducibility and dispersion; the Rh reducibility was easily altered, and increasing the cobalt loading improved the Rh dispersion. It was concluded that the enhanced catalytic performance with increasing cobalt loading might be due to the formation of a more reactive Rh species with a different Rh–phosphine interaction strength on the catalyst surface.

Hydroformylation of Dicyclopentadiene over Rh Catalysts Supported on Fe2O3, Co3O4 and Fe2O3–Co3O4 Mixed Oxide

Rh catalysts supported on Fe2O3, Co3O4 and Fe2O3–Co3O4 mixed oxide were prepared by the co-precipitation method. The effect of the support on the performance of the Rh catalysts for the hydroformylation of dicyclopentadiene was investigated using X-ray photoelectron spectroscopy, H2-temperature-programmed reduction, H2-temperature-programmed desorption and Brunauer–Emmett–Teller analysis techniques. The results indicated that the Fe2O3–Co3O4 supported catalyst had a higher dispersion of Rh and thus more Rh+ sites. As a result, the Fe2O3–Co3O4 supported Rh catalyst exhibited higher activity compared with counterparts supported on Fe2O3 and Co3O4.

P.6.c.010 - Antidepressant and anticonvulsant effects of complexes of SnCl4 with benzaldehyde and 4-bromobenzaldehyde salicyloyl hydrazones

Rhodium-catalyzed hydroformylation of dicyclopentadiene using different kinds of mono- and bidentate phosphorus ligands was studied. The results demonstrated that the electronic and steric properties of ligand could influence the catalytic activity and the selectivity towards dialdehyde products. High conversion (99.9%) and good selectivity (95.0%) to dialdehydes were achieved under optimized reaction conditions in the presence of Rh/mixed mono- and bidentate phosphorus ligand complex (bidentate ligand: 2,2′-bis(dipyrrolylphosphinooxy)-1,1′-(±)-biphenyl (L1) and monodentate ligand: tri-(4-methoxylphenyl)phosphine (L8) (L1/L8 molar ratio 1/2)), which offers an easy approach to prepare dialdehydes from hydroformylation of cyclopentadiene under mild conditions (5.0 MPa, 100 °C).

Magnetically Separable Fe<SUB>3</SUB>O<SUB>4</SUB> Supported Co–Rh Bimetallic Catalysts for Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals

Magnetically Separable Fe<SUB>3</SUB>O<SUB>4</SUB> Supported Co–Rh Bimetallic Catalysts for Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals

The Effect of Metal‐Ligand Affinity on Fe3O4_Supported Co–Rh Catalysts for Dicyclopentadiene Hydroformylation

ABSTRACTThe catalytic performances of Co‐Rh/Fe3O4 catalysts modified with phosphine ligands (PPh3) and its analogues on dicyclopentadiene hydroformylation were evaluated. Among these catalysts, Co‐Rh/Fe3O4 modified with tris(p‐trifluoromethylphenyl)phosphine was determined to be effective for monoformyltricyclodecanes production, whereas Co‐Rh/Fe3O4 modified with PPh3 or tri‐p‐tolylphosphine was effective for the diformyltricyclodecanes production. To investigate the ligand effects, the complex catalyst system (Co‐Rh/Fe3O4 and phosphine ligand) was subjected to pretreatment with syngas and then characterized by thermogravimetry and differential thermal analysis (TG‐DTA). It was determined that the threshold decomposition temperature reflected the corresponding Rh‐phosphine interaction strength, affecting the catalytic selectivity toward different products. A weak Rh‐phosphine interaction was desirable to produce monoformyltricyclodecanes with fast reaction kinetics, whereas a strong Rh‐phosphine complex was required for the synthesis of diformyltricyclodecanes. In addition to the selectivity rule shown in the PPh3 series, experiments with other ligands also demonstrated similar selectivity trends.

Rh-based catalysts supported on MCM-41-type mesoporous silica for dicyclopentadiene hydroformylation

Impregnation method was used in this study to prepare five different Rh based catalysts supported on MCM-type mesoporous silica materials. These catalysts were evaluated based on their performance for the hydroformylation of dicyclopentadiene (DCPD) to produce diformyltricyclodecanes (DFTD). While a selectivity of DFTD was only 8.7% using monometallic Rh/MCM-41 as catalyst, the selectivity was enhanced to 76.2% at a similar DCPD conversion using bimetallic Co–Rh/MCM-41 catalyst, even when the Co loading was very low(25mol% relative to Rh). Extensive catalyst characterization including TPR, TPD, XRD, XPS, BET and TEM was performed to study the nature of metal modification on Rh/MCM-41. It was found that modification on the Rh/MCM-41 by Co addition could substantially enhance the selectivity towards DFTD. This improvement was likely attributed to the formation of a more reactive Rh species on the catalyst surface.

Highly efficient catalytic system for the formation of dialdehydes from dicyclopentadiene hydroformylation

Rhodium-catalyzed hydroformylation of dicyclopentadiene using different kinds of mono- and bidentate phosphorus ligands was studied. The results demonstrated that the electronic and steric properties of ligand could influence the catalytic activity and the selectivity towards dialdehyde products. High conversion (99.9%) and good selectivity (95.0%) to dialdehydes were achieved under optimized reaction conditions in the presence of Rh/mixed mono- and bidentate phosphorus ligand complex (bidentate ligand: 2,2′-bis(dipyrrolylphosphinooxy)-1,1′-(±)-biphenyl (L1) and monodentate ligand: tri-(4-methoxylphenyl)phosphine (L8) (L1/L8 molar ratio 1/2)), which offers an easy approach to prepare dialdehydes from hydroformylation of cyclopentadiene under mild conditions (5.0MPa, 100°C).

Dicyclopentadiene Hydroformylation in an Aqueous/Organic Two Phase System in the Presence of a Cationic Surfactant

Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCl(CO)(TPPTS) 2 (TPPTS: P(m-C 6 H 4 SO 3 Na) 3 ) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C 6 H 5 P(m-C 6 H 4 SO 3 Na) 2 ), and surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated by the addition of the cationic surfactant C 16 H 33 N(CH 3 ) 2 C n H 2 n +1 Br( n = 1, 8, 12, 16) but the accelerating effect was attenuated with an increase of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium concentration increased in the range of 0.05–5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant decrease in activity and regioselectivity. ： 研究了在阳离子表面活性剂存在下水/有机两相中水溶性铑配合物 RhCl(CO)(TPPTS) 2 (TPPTS: P(m-C 6 H 4 SO 3 Na) 3 ) 催化双环戊二烯氢甲酰化反应, 考察了反应温度、催化剂浓度、不同水溶性膦配体 TPPTS 和 TPPDS (C 6 H 5 P(m-C 6 H 4 SO 3 Na) 2 ), 以及表面活性剂结构对催化反应的影响. 结果表明, 配体 TPPTS 比 TPPDS 表现出更好的助催化效果; 阳离子表面活性剂 C 16 H 33 N(CH 3 ) 2 C n H 2 n +1 Br ( n = 1, 8, 12, 16) 的加入可大大加速反应, 但加速作用随着其中 C n H 2 n +1 Br ( n = 1, 8, 12, 16) 链长的增加而减弱; 在阳离子表面活性剂 (0.05-5.00 mmol/L) 存在下, 双环戊二烯的转化率随表面活性剂浓度的增加先增加后降低. 含催化剂的水相循环使用 4 次后, 催化活性和区域选择性没有明显下降. Catalysis system composed of RhCl(CO)(TPPTS) 2 -TPPTS and a cationic surfactant showed good catalytic activity for dicyclopentadiene hydroformylation

Dicyclopentadiene hydroformylation catalyzed by Rh xCo 4-x(CO) 12 (x = 4, 2-0)/tertiary amine catalysts [1

The hydroformylation of dicyclopentadiene (DCPD) has been examined using catalyst systems comprising Rh xCo 4-x(CO) 12(x= 4, 2-0) clusters bonded to tertiary amines or commercially available tertiary amine resins. Cluster composition effects the rate of the reaction only in the first few hours of catalyst life. While the rate determining step is initially the hydroformylation of the cyclopentene portion of the DCPD, aldehyde hydrogenation becomes rate limiting as the catalyst deactivates.