Continuous Gas‐Phase Hydroaminomethylation using Supported Ionic Liquid Phase Catalysts

Abstract

Gasphasen‐Aminsynthese mit SILP‐Katalysatoren: Die Hydroaminomethylierung von Ethylen mit Diethylamin zu Diethylpropylamin wurde als kontinuierliche Gasphasenreaktion (siehe Bild) mit einer trägerfixierten ionischen Katalysatorlösung eines Rh‐Xantphos‐Homogenkatalysators durchgeführt. Dieser SILP‐Katalysator arbeitete hoch selektiv und war über 18 Tage stabil, wenn eine ionische Flüssigkeit mit möglichst geringer Basizität und Lipophilie in Kombination mit einem porösen Aktivkohleträger eingesetzt wurde.

Tandem Catalytic Amine Synthesis from Alkenes in Continuous Flow Enabled by Integrated Catalyst Recycling

“…Thus, various concepts have been presented for the separation and recovery of homogeneous catalysts in general . For HAM, Wasserscheid and co-workers reported a continuous process using supported ionic liquid phase catalysts (SILP) . However, this approach is limited to gaseous substrates and products.…”

“…16 For HAM, Wasserscheid and co-workers reported a continuous process using supported ionic liquid phase catalysts (SILP). 17 However, this approach is limited to gaseous substrates and products. Other methods have to be considered because of their high boiling points to synthesize higher aliphatic amines.…”

Aqueous Biphasic Hydroaminomethylation Enabled by Methylated Cyclodextrins: Sensitivity Analysis for Transfer into a Continuous Process

“…By combing the process development knowledge from that reaction with first experience in the HAM of eugenol using a similar catalytic system, 33 we considered that a transfer of hydroaminomethylation mediated by CDs into a continuous process would be eventually a big step forward for an efficient and sustainable conversion of higher alkenes to valuable amine products. Especially, to date, only two continuous processes (thermomorphic multiphase system 38 + ionic liquid 21 ) have ever been reported for the HAM and none of them were based on an aqueous solvent system. Therefore, we optimized and scaled up for the first time the catalytic system Rh(acac)(CO) 2 /SulfoXantphos/ RAME-β-CD for aqueous biphasic hydroaminomethylation.…”

“…Various concepts have been presented in the last few decades for the separation and recovery of homogenous catalysts for batch and flow processes in general. − In 2018, Kalck and Urrutigoity examined these methods and several reaction pathways more closely for hydroaminomethylation. Key reaction and separation systems discussed were, among others, thermomorphic solvent systems, supercritical CO 2 , and ionic liquids. − In addition, biphasic systems were discussed as the topic of interest. Especially, since water is formed as a coproduct in hydroaminomethylation, aqueous separation concepts were reviewed as a potential green alternative.…”

Synthesis of tetracationic organic salt from 4,4'-bipyridine

“…This is due to the potential to change their structural features simply by: varying the nature of the cation and/or the anion; tuning them by introducing small structural changes in the constituting ions, or of the spacers separating them provides the opportunity to obtain materials with sets of desired properties suitable for different applications. They have been applied as a chemical anchorage on a solid support [10], starting materials for the synthesis of molecular devices [11,12], reaction media or catalysts, immobilization of catalysts [9], reaction media for high-temperature organic reactions [13,14], catalysts [15], receptors for anion recognition [16], low-molecular-weight gelators [17], fluorescent organic salts [18,19], energetic materials [20,21], for use in the preparation of solid films for organic electronic applications [22] and electrowetting materials [23]. Heteromolecules including imidazole, 1,10-phenanthroline, pyridine and others have been used as the starting materials for the synthesis of polycationic organic salts.…”