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Multiphase Catalysis in Temperature-Dependent Multi-Component Solvent (TMS) Systems

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Regulated Systems for Multiphase Catalysis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 23))

Abstract

The use of temperature-dependent multi-component solvent-systems (TMS) as a new recycling conceptwas investigated. The temperature dependency of the solvent systems and suitable compositions for variousreactions were determined by cloud titrations. The results were summarized in an expert system for thesolvent selection. Appropriate thermomorphic solvent systems were applied to different C − Cbond-forming reactions: the telomerization of butadiene with ethylene glycol or with carbon dioxide, theisomerizing hydroformylation of trans-4-octene and the hydroaminomethylationof 1-octene with morpholine. In further investigations the carboxytelomerization and the synthesis of 4-nitrodiphenylaminewere examined. Especially, if the polarity of the reaction mixture remains constant, high conversions ofthe substrates and high selectivities can be achieved. Thus, for the hydroformylation the conversion reachesa level of 99% and a selectivity to n-nonanal of about 80%in the TMS system propylene carbonate (PC)/dodecane/N-methylpyrrolidone(NMP). Similar results are obtained for the hydroaminomethylation: if N-octylpyrrolidoneis used as a mediator the conversion of 1-octene and the selectivity of the corresponding amines reach92%. For both reactions the catalyst can be easily recovered by a simple phase separation with onlymarginal loss of rhodium catalyst.

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Abbreviations

acac:

acetylacetonate

ad:

adamantyl

bis-mes-IM:

1,3-bis(mesitylene)imidazolium chloride

cod:

cyclooctadiene

CST:

critical solution temperature

DMF:

dimethylformamide

DMSO:

dimethyl sulfoxide

dvds:

1,3-divinyltetramethyldisiloxane

EC:

ethylene carbonate

HSP:

Hansen solubility parameter

ICP-OES:

inductively coupled plasma optical emission spectroscopy

IPA:

isopropyl alcohol

MCH:

methylcyclohexyl

MDPP:

methyl polyethylene glycol diphenylphosphine

MA:

maleic anhydride

NBP:

N-benzylpyrrolidone

NCP:

N-cyclohexylpyrrolidone

NEP:

N-ethylpyrrolidone

NMP:

N-methylpyrrolidone

NOP:

N-octylpyrrolidone

OAc:

acetate

PC:

propylene carbonate

PEG:

polyethylene glycol

PETPPO:

polyethylene glycol triphenylphosphine oxide

PF:

perfluoro-prod., product

PVC:

polyvinyl chloride

rpm:

rotations per minute

Rf x :

-C x F2 x +1

THF:

tetrahydrofuran

TMS system:

temperature dependent or thermomorphic multi-component solvent system

TPPMS:

triphenylphosphine-3-sulfonic acid lithium salt

TPPTS:

triphenylphosphine-3,3′,3′′-trisulfonic acid trisodium salt

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Acknowledgments

We would like to thank Prof. Dr. Leitner (RWTH Aachen) for the supply of PEG-modified ligands and Prof. Dr. Gladysz (University of Erlangen-Nürnberg) and Prof. Dr. Dinjus (FZ Karlsruhe) for the donation of fluorous ligands.

We are very grateful to Umicore AG and Co. KG for the supply of the rhodium and palladium catalysts and to BASF AG for the donation of carbon monoxide and syngas. We also thank Celanese AG and European Oxo GmbH for the supply of TPPTS solution. We would like to thank the Bundesministerium für Bildung und Forschung (ConNeCat-project “Smart Solvents—Smart Ligands”) and the “Fonds der Chemischen Industrie” for financial support.

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Authors and Affiliations

  1. Universität Dortmund, Fachbereich Bio- und Chemieingenieurwesen, Lehrstuhl für Technische Chemie A, Emil-Figge-Straße 66, 44227, Dortmund, Germany

    Arno Behr, Barbara Turkowski, Reina Roll, René Schöbel & Guido Henze

Authors
  1. Arno Behr
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  2. Barbara Turkowski
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  3. Reina Roll
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  4. René Schöbel
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  5. Guido Henze
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Corresponding author

Correspondence to Arno Behr .

Editor information

Walter Leitner Markus Hölscher

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Behr, A., Turkowski, B., Roll, R., Schöbel, R., Henze, G. (2006). Multiphase Catalysis in Temperature-Dependent Multi-Component Solvent (TMS) Systems. In: Leitner, W., Hölscher, M. (eds) Regulated Systems for Multiphase Catalysis. Topics in Organometallic Chemistry, vol 23. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2006_057

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