Highly selective tandem isomerization–hydroformylation reaction of trans-4-octene to n-nonanal with rhodium-BIPHEPHOS catalysis

Behr, Arno; Obst, Dietmar; Schulte, Christian; Schosser, Thorsten

doi:10.1016/s1381-1169(03)00461-8

Cited by 91 publications

(50 citation statements)

References 12 publications

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“…Rhodium-catalyzed tandem isomerization-hydroformylation of middle-chain alkenes (<10 C) has been widely studied over the last two decades, generally with bulky ligands [7,8]. Regioselectivities in the range l/b = 95:5-98:2 were obtained with 2-alkenes (e.g., 2-hexene, 2-octene) [9][10][11][12][13][14], while with 4-octene regioselectivities up to l/b = 89:11 were observed [15,16]. On the other hand, the hydroformylation of long-chain alkenes (>10 C), with a C=C bond in a deep internal position (>5 C away), remains poorly documented.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

et al. 2018

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Tandem isomerization-hydroformylation of oleonitrile (an 18-carbon nitrile with a remote internal (9-)C=C bond) has been studied using Rh-bisphosphite catalyst systems, targeting formation of the linear aldehyde. The best compromise between regioselectivity (l/b = 58:42) and chemoselectivity (60%) was obtained at 120 • C and 10 bar CO/H 2 (1:1) with a catalyst based on Biphephos at a 0.5 mol % catalyst load and a low ligand excess (2 equiv. versus Rh). These values stand among the better reported ones for the tandem isomerization-hydroformylation of long chain olefins with a single-component catalyst system.

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Section: Introductionmentioning

confidence: 99%

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

et al. 2018

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“…The feedstock has low concentration of alkenes (1.5% 1-butene and 28.5% cis/trans-2-butene) and 70% inert saturated n-butane (Scheme 3). The authors chose BiphePhos as ligand, which was known to be capable of performing the isomerizationhydroformylation process [49]. The Rh-BiphePhosSILP catalyst was able to convert up to 81% of butenes, providing n-pentanal with selectivity greater than 92%, with a residence time of 155 s. The performance of the catalytic system remained stable for over 500 h on-stream.…”

Section: Supported Ionic Liquid-phase Catalysismentioning

confidence: 99%

Recent Advances in Continuous Rhodium-Catalyzed Hydroformylation

Wang¹

2015

J Flow Chem

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“…2 Apart from the desired linear aldehyde product, double bond isomerization of the olefin coordinated to the catalyst occurs as a side reaction by which undesired branched aldehydes are being produced. [3][4][5][6] This lowers the overall yield of the preferred main linear product. HRh(CO)(BiPhePhos) is an advanced hydroformylation (see Fig.…”

Section: Introductionmentioning

confidence: 99%

The thermochemistry of long chain olefin isomers during hydroformylation

Kohls

Stein

2017

New J. Chem.

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Rhodium-catalysed hydroformylation is the major industrial process to obtain aldehyde products from olefins. The isomerization of the olefin at the catalyst is the most prominent side reaction and lowers the overall yield of the process. We here investigate whether the olefin isomer distribution obtained from batch experiments using Rh(BiPhePhos) as a catalyst and n-decene as the olefin reaches the thermodynamic equilibrium and computational quantum chemical approaches are able to accurately reproduce the experimental olefin isomer distribution. The relative energies of cis/trans configurational and double bond positional isomers of long chain n-decene were calculated using Hartree-Fock, DFT and correlated ab initio methods. Results were compared to experimental data. Electron correlation was found to be critical for the description of cis-isomer relative energies. Dispersion corrections in the DFT calculations partially compensate for deficiencies and generally improve the agreement with experiment. Adding thermodynamic corrections suffers from the neglect of certain contributions to the entropy of flexible molecules. Accounting for the entropy of mixing of multiple conformers significantly reduces the deviation from experiment. The equilibrium distribution of long chain olefins is reasonably described by correlated QM and also some density functional methods. Computational thermochemistry has thus reached a state where it provides reliable parameters for complex reaction network models and process engineering.

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Highly selective tandem isomerization–hydroformylation reaction of trans-4-octene to n-nonanal with rhodium-BIPHEPHOS catalysis

Cited by 91 publications

References 12 publications

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Rhodium-Biphephos-Catalyzed Tandem Isomerization–Hydroformylation of Oleonitrile

Recent Advances in Continuous Rhodium-Catalyzed Hydroformylation

The thermochemistry of long chain olefin isomers during hydroformylation

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