First rhodium-catalyzed hydroformylation of cyclopentadiene

Behr, Arno; Levikov, Denys; Vogelsang, Dennis

doi:10.1016/j.molcata.2015.06.003

Cited by 8 publications

(3 citation statements)

References 15 publications

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“…Apparently, the amine has a synergistic effect on the hydroformylation of the 1,3‐dienes and accelerates the rate‐determining step. This was stated before with cyclopentadiene, although the effect was addressed to suppressed Diels–Alder dimerization …”

Section: Methodsmentioning

confidence: 90%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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A catalytic system was developed to enable the use of industrially available terpenes (e.g., β‐myrcene, β‐farnesene) in hydroaminomethylation to obtain renewable building blocks for surfactants in two steps. This homogeneously catalyzed tandem reaction includes both hydroformylation and enamine condensation steps, followed by hydrogenation. Under the optimized conditions, the Rh/1,2‐bis(diphenylphosphino)ethane catalytic system delivers products in high yields (70 %) after short reaction times (3 h) with unprecedentedly high turnover frequency (TOF) values for the hydroformylation of 1,3‐dienes of over 739 mol mol−1 h−1. This is the highest TOF reported to date for the hydroformylation of a 1,3‐diene. Furthermore, regioselectivities of 97 % and above were observed in the hydroformylation step, which is extraordinarily high for the conversion of 1,3‐dienes. The terpene‐derived amines obtained were further functionalized to quaternary ammonium compounds that were found to show surface activity quite similar to that of industrially available quaternary ammonium compounds. The hydroaminomethylation of terpenes achieves higher step efficiency than industrial means and makes use of an alternative, renewable feedstock to synthesize more environmentally friendly surfactants.

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Section: Methodsmentioning

confidence: 90%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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“…The addition of triethylamine has been very effective in suppressing dimerization in the hydroformylation/hydrogenation tandem reaction of cyclopentadiene to the corresponding saturated aldehyde . Without substantial dimerization of the starting material, the desired saturated mono‐ and dialdehydes were prepared instead of the dicyclopentadiene products (Figure ).…”

Section: C5 Moleculesmentioning

confidence: 99%

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

et al. 2018

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For many years, the efficient use of resources has been a major and permanent challenge for the chemical industry. The implementation of alternative resources such as renewables and carbon dioxide has been a subject of considerable discussion, but also the more efficient use of long known bulk chemicals is of great interest. Among them, 1,3‐dienes such as 1,3‐butadiene from the C4 cut of the naphtha cracker as well as isoprene, piperylene and cyclopentadiene from the corresponding C5 section are important substrates. These dienes are presently employed in various markets, with the greatest importance being in the production of polymers and copolymers. However, homogeneous transition metal catalysis has proven to be a versatile tool to functionalize these important 1,3‐dienes to low molecular weight fine chemicals by introducing, for example, nitrogen, oxygen or silicon. Hence, an upgraded use of the corresponding products as agrochemicals, pharmaceuticals, fragrances or special detergents is close at hand. The main approaches in the topic of homogeneous functionalization reactions of the industrially relevant 1,3‐dienes will be summarized and discussed within the present article. Besides that, novel applications including renewable 1,3‐dienes, for example β‐myrcene and β‐farnesene, as well as the application of CO2 in telomerization, will be critically discussed.

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“…In this manuscript, we report the solubilities of H 2 and CO (syngas components used in hydroformylation) in the presence of either propane or propylene in two typical hydroformylation solvents, toluene and 2,2,4‐trimethyl‐1,3‐pentanediol mono(2‐methylpropanoate), commonly denoted as NX‐795 . NX‐795 is used for hydroformylation because of its high boiling point and its inertness in the hydroformylation reaction mixture .…”

Section: Introductionmentioning

confidence: 99%

Enhanced solubility of hydrogen and carbon monoxide in propane‐ and propylene‐expanded liquids

2017

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Conventional propylene hydroformylation occurs in a gas‐expanded liquid phase. Reliable knowledge of the phase equilibria of such systems, including the solubilities of CO and H2 in propylene‐expanded solvents, is essential for rational process design and development. Herein, we report the vapor–liquid equilibrium (VLE) data of the following ternary systems involving CO, H2, propane, propylene, toluene and NX‐795 at temperatures from 70 to 90°C and pressures up to 1.5 MPa: propane/H2/toluene, propane/CO/toluene, propylene/H2/toluene, propylene/CO/toluene, propane/H2/NX‐795, propane/CO/NX‐795, propylene/H2/NX‐795 and propylene/CO/NX‐795. The solubilities of H2 and CO in either propane‐expanded or propylene‐expanded phases are observed to be greater than those in the neat organic solvents, by as high as 78% at 70°C and 1.5 MPa. By modeling the vapor and the liquid phases as pseudo‐binary systems, the Peng‐Robinson equation of state (PR‐EoS) with van der Waals’ mixing rules and binary interaction parameters is shown to satisfactorily predict the experimental VLE data. © 2017 American Institute of Chemical Engineers AIChE J, 64: 970–980, 2018

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First rhodium-catalyzed hydroformylation of cyclopentadiene

Cited by 8 publications

References 15 publications

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

Enhanced solubility of hydrogen and carbon monoxide in propane‐ and propylene‐expanded liquids

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