Towards water-based recycling techniques: Methodologies for

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Towards water-based recycling techniques: Methodologies for homogeneous catalyst recycling in liquid/liquid multiphase media and their implementation in continuous processes Thorsten Rösler, Thiemo Alexander Faßbach, Marco Schrimpf, Andreas Johannes Vorholt, and Walter Leitner Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b04295 • Publication Date (Web): 26 Oct 2018 Downloaded from http://pubs.acs.org on October 29, 2018

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Industrial & Engineering Chemistry Research

Towards water-based recycling techniques: Methodologies for homogeneous catalyst recycling in liquid/liquid multiphase media and their implementation in continuous processes T. Rösler1, T. A. Faßbach1, M. Schrimpf1, A. J. Vorholt*1, W. Leitner1 1

Max-Planck-Institute for Chemical Energy Conversion, Stiftstraße 34, 45470 Mülheim an der Ruhr, Germany *+49 0208 306 3669, [email protected] Abstract: Biphasic water-based solvent systems offer the opportunity of efficient recycling of homogeneous catalysts. Water separates well from most organic solvents therefore; water-soluble catalysts can be immobilized in this phase. Furthermore, water can substitute hazardous and environmentally unfriendly organic solvents in these systems. Within industry only the Ruhrchemie/Rhône-Poulenc process uses plain water to immobilize the homogenous catalyst for the hydroformylation of propene. Yet for more hydrophobic substrates, no water-based system has been commercialized. This review will summarize recent developments in the field of water-based recycling systems. Topics in this field are: intensification of the mixing process, the use of thermomorphic solvent systems and the employment of several additives, like alcohols and surfactants. Continuous operated processes for these recycling strategies will be presented and discussed. Keywords: Catalyst recycling, biphasic systems, continuous processes, co-solvents, surfactants, activated carbon, cyclodextrines, thermomorphic solvent systems Introduction: In the last two centuries the ecological sustainability of our society and therefore also of the chemical value chain became a topic of public awareness.1 The new task for researchers to develop efficient and sustainable processes is known as “Green Chemistry”2,3. With the help of catalysis, a lot of energy and waste can be saved. Today in Europe about 30% of all produced goods and over 80% of products in the chemical sector involve the help of catalysis.4 In this context especially homogeneous catalysis with transition metal complexes is known to generate products with high efficiency and selectivity.5 One of the main disadvantages still hampering the use of homogenous catalysis, is the difficult catalyst recycling.5 Since expensive metals like rhodium and palladium are commonly used, the loss of homogeneous catalysts cannot be tolerated for industrial processes. This is why the effective recycling of homogeneous catalysts has to be one of the main goals when it comes to the development of sustainable processes. Commonly used recycling techniques like distillation or extraction are energy consuming and demanding for the catalyst.6 Very efficient for homogeneous catalyst recycling are biphasic solvent systems in which the catalyst is immobilized in one phase and the product distributes into the other phase. This allows for an intrinsic separation of catalyst and product. Water as the polar phase is especially helpful for separation. To illustrate this in Figure 1 four different cases depending on catalyst and product polarity are displayed.

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Figure 1: Possible combinations of catalyst and product/substrate polarities.

Since a lot of substrates have nonpolar characteristics case three is most commonly used for biphasic separation. In this case, water is especially suitable as the polar phase. It has a high polarity and density, taking care of a very effective separation from most organic solvents. Furthermore, water can also be employed in case one where most polar organic solvents fail. Even when dealing with products of medium polarity water still has a high polarity to achieve a biphasic separation from the polar product phase. Water as reaction media offers several other advantages regarding economic as well as environmental aspects:  

It is nonhazardous and nonflammable It is readily available



It has an E-factor (Environmental factor=

 

It has a high heat capacity It has a high difference in density compared to most organic solvents for fast separation

kg waste 1 ) kg product

of almost zero

The combination of good separation and environmental characteristics makes water the solvent of choice for future sustainable processes. For an effective immobilization of catalysts in the water phase, ligands with polar groups like sulfonyl-, acid-, or ammonium groups are used.7,8 By now several water soluble ligands are commercially available. Figure 2 shows a selection of them:


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Figure 2: Commercially available water soluble ligands.

The feasibility of water based recycling techniques has been shown already. A prime example of a successful process in which a water-based recycling technique has been used is the Ruhrchemie-RhônePoulenc process for the hydroformylation of propene 9,10 In the Ruhrchemie-Rhône-Poulenc process, the water-soluble Rhodium/TPPTS catalyst is immobilized in water, while the product butanal together with propene separates as an organic phase. Because the substrate propene is soluble in water to a certain extent, reaction rates for this process are high. Going to more hydrophobic substrates the solubility drops significantly and mass transfer of substrate into the aqueous catalyst phase becomes the limiting factor, resulting in low reaction rates. As an example: the solubility of 1-octene compared to propene is approximately 75 times lower at room temperature.11 Extensive research has been made to utilize easy homogeneous catalyst recycling in biphasic media while keeping up high reaction rates for hydrophobic substrates at the same time. In this review, the focus will be on water-based recycling systems and their development. Several examples of continuously operated miniplants with these recycling strategies are presented. The goal of this review is to give an insight into possible solutions and to compare different classified recycling techniques in literature with each other. Expansion of surface area in biphasic media: One basic idea is to expand the surface area between the water phase containing the catalyst and the non-polar substrate phase. A larger surface area contributes to a larger contact zone between catalyst and substrate. Acceleration of the reaction is achieved simply by physically bringing catalyst and substrate



together. Two different concepts, an intensified mixing and the addition of activated carbon will be discussed. The group of Vorholt investigated the acceleration of the hydroformylation of 1-octene in biphasic media. By optimizing the process in a small plant, operating on a kilogram scale (miniplant), a remarkable acceleration of the reaction was achieved without the addition or modification of any components. First the hydroformylation of 1-octene in a biphasic water/1-octene system catalyzed by a water-soluble Rh/TPPTS was investigated in a continuously stirred tank reactor (CSTR).12,13 The catalytic system and important parameters were first tested on the laboratory scale. In these preceding investigations a big influence of the catalyst concentration and ligand excess was observed. A very low catalyst concentration of 0.005 mol·L-1 increased the turnover frequency (TOF >1600 h-1) and the space-time-yield (STY >30 · 10-2 molL-1h-1) significantly. Afterwards, the reaction was transferred into a CSTR with a volume of 3.6 L. The influence of different stirrer geometries and energy inputs was investigated. A logarithmic dependency of the reaction rate on the power input by the stirrer was observed. At the same time, the interfacial area was correlated to the power input, indicating that a higher power input leads to a higher surface area. The TOF almost linearly increases with the surface area, showing that the reaction indeed most likely takes place at the surface and not in the bulk of one of the phases. This is an important realization because the reaction rate can be increased just by increasing the surface area without manipulating the solubility of one of the reactants. Best results were obtained with the stirrer-type Rushton turbine. By optimizing the power input with the stirrer type and speed the reaction rate was doubled compared to laboratory scale experiments, leading to a high TOF of about 3250 h-1. The limitation of the hydroformylation by the surface area led to the conclusion that special reactor types allowing for a very high surface areas might be beneficial. The miniplant setup was expanded by a jet-loop-reactor (JLR) displayed in Figure 3.14

Figure 3: Principle of a jet-loop-reactor (JLR).14

In a jet-loop-reactor at the bottom a mixture of both phases is sucked into a loop and cycled to the top. By reinserting the mixture and the gas through a narrow nozzle the impact takes care of a very fine dispersion of all three phases and a high surface area. The jet-loop-reactor was optimized regarding phase fraction and energy input and then compared to the CSTR reactor. With the jet-loop-reactor very high catalytic activity was achieved with a TOF up to 10,960 h-1, in the case of very low fractions of water/catalyst phase. This is the highest TOF for the biphasic hydroformylation of 1-octene in literature


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so far. During the investigations with another set of optimizations also the TOF in CSTR was raised to 4550 h-1. Even with much higher TOF numbers for the JLR, the CSTR reactor enables a higher space-timeyield of 12.6·10-5 kmol m-3s-1 and has lower investment cost making it the economically favored choice. The jet-loop-reactor was operated over a timescale of 15 hours with a total turnover number (TTON) of >58,000. At this point it should be mentioned whenever dealing with biphasic water based reaction media one has to keep in mind that the reaction can be heavily influenced by the pH of the water phase. For example a severe influence of the pH on the hydroformylation of 1-octene was investigated back in 1997.15 When going from a neutral reaction medium of pH 7 to a more basic medium of pH 10 it was shown that trends otherwise observed in the hydroformylation of 1-octene do not apply and reaction rates drop significantly. In the previous example, the surface area was extended by improving the mixing characteristics. This does not require any additives but a higher energy input. Recently, the group of Monflier developed a concept, which seems rather different on first sight but builds on the same principle. Water suspended activated carbon (AC) was discovered as an efficient additive for several reactions in biphasic media.16 Since activated carbon has a mesoporous structure, the surface area can be loaded with non-polar substrate. The loaded AC will be also build a suspension in water. For example, the commercially available activated carbon Nuchar® WV-B has a surface area of 1690 m2g-1. Because the activated carbon surface is relatively hydrophobic, substrate is adsorbed and transported into the catalyst phase. This ensures a close contact between substrates and catalyst and physically enlarges the surface area by several orders of magnitude (Figure 4).

Figure 4: Surface area expansion by activated carbon.

Activated carbon is furthermore chemically and physically inert under the reported reaction conditions and easy to separate. It was introduced in the Pd/TPPTS catalyzed Tsuji-Trost cleavage of allylalkylcarbonates in a water/heptane biphasic mixture shown in Scheme 1.



Scheme 1: Tsuji-Trost cleavage of allylalkylcarbonates supported by activated carbon.16

Depending on the alkyl chain length, the addition of Nuchar® WV-B accelerates the reaction significantly. With a chain length of just four carbon atoms no increase was observed while with increasing chain length up to sixteen carbon atoms an acceleration of about 470 times compared to the initial reaction rate was shown. In a recycling study the catalyst was reused in five consecutive runs with no decrease in activity. Activated carbon was also used in the hydroformylation of unsaturated methyl-oleate in Scheme 2.17

Scheme 2: Hydroformylation of methyl-oleate supported by activated carbon.17

In a biphasic water/methyl oleate mixture with a Rh/TPPTS catalyst no conversion at all was observed without additives. In contrast, addition of activated carbon leads to 77% conversion within six hours and a very high selectivity towards the aldehyde of 98%. In this study activated carbon was also compared to other additives like the co-solvent ethanol, cyclodextrines and the surfactant cetyltrimethylammoniumbromide (CTAB). Even the addition of ethanol or cyclodextrines was not successful in this case. CTAB on the other hand boosted the reaction even further than activated carbon but formed an emulsion, abolishing the biphasic system. Comparing the jet-loop-reactor concept and the activated carbon method, both use rather different approaches but have the same purpose: accelerating the reaction by increasing the surface area. While intensification of the mixing always means an increased energy input, activated carbon can circumvent this. As an additional component in the reaction system the solid activated carbon has to be separated afterwards. Altering substrate solubility with co-Solvents: One of the first described attempts to accelerate reaction rates in biphasic water based media was the use of co-solvents. Co-solvents act as mediators for the substrate between the organic and the catalyst phase and therefore increase the reaction rate as displayed in Figure 5.


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Figure 5: Increasing substrate solubility with the help of co-solvents.

By increasing the miscibility of the water phase into the organic phase a higher catalyst leaching is intrinsically favored because the catalyst can also move to the product phase. Furthermore, for product purification the co-solvent is another component, which needs to be separated. The concept was shown in the hydroformylation of 1-octene (Scheme 3).18

Scheme 3: Acceleration of the hydroformylation of 1-octene with co-solvent ethanol.18

Using a 1:1-mixture of ethanol and water lead to an increase of solubility of 1-octene in the range of 104. In addition, the solubility of carbon monoxide and hydrogen was increased too. To prevent the formation of acetal side products by reaction of ethanol with the product heptanal, a buffer solution of sodium carbonate and bicarbonate was added. Studies regarding catalyst recycling have not been evaluated at this stage. Over the years, besides ethanol other co-solvents have been described as useful additives, like acetonitrile18,19, acetone19 and methanol.19–21 Due to increasing catalyst leaching and higher separation effort, this approach has not been the focus of research during the last decade. Thermomorphic Solvent Systems (TMS): In previous examples, alcohols were used as additives for biphasic mixtures. Even though under those conditions alcohols influence the solubility, the reaction mixture stays biphasic. If alcohols are used not as an additive to the water phase but as a solvent for a second phase, at high temperatures a thermomorphic phase behavior can be observed as shown in Figure 6. At low temperatures the system is biphasic. Reaching a certain temperature, full miscibility and a monophasic reaction mixture can be



observed. This temperature dependent miscibility gap of two or more solvents is known as Thermomorphic Solvent Systems (TMS). The principle of TMS can be displayed effectively in the example of a three component system in the ternary phase diagram (Gibbs triangle) in Figure 6. While at low temperatures the miscibility of the solvents is limited and the mixing point M of the components lies outside the boundaries of the binodal curve for a monophasic reaction mixture. When the temperature is raised, the miscibility of the solvents also increases and therefore the binodal curve shifts towards higher concentrations. At a certain temperature the binodal curve exceeds the mixing point and full miscibility of the components is achieved. Above this temperature, the reaction can be performed in a monophasic reaction mixture without masstransport-limitations. After reaction, the mixture is cooled down until demixing occurs. By simple phase separation the catalyst can be separated from the product. For this concept, the catalyst has to be distributed almost exclusively in one phase, usually the polar phase, and the product needs to distribute mostly in the non-polar phase.

Figure 6: Principle of a Thermomorphic Solvent Systems in the example of a three component solvent system.

The difficulty is to find a set of appropriate conditions because the chosen solvents need to fulfill a number of pre-requirements, which are:     

Poor miscibility at low temperatures and full miscibility at reaction temperature High reaction rates of the designated reaction in the chosen solvents Strong support of the catalyst in the polar phase High distribution coefficients for the product in the apolar phase No side reaction or catalyst deactivation by the chosen solvents


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The concept of TMS for the recycling of homogenous catalysts was first described by the group of Behr in 1999.22 Some of the early work deals with hydroaminomethylation23, oligomerization24,25, codimerization26, hydroamination27, metathesis28,29, hydroformylation30,31 and telomerization32,33 reactions in TMS media. While in early TMS systems three component systems, consisting of a highly polar, a highly apolar and a mildly polar mediator are used, most TMS in recent years focus on the employment of TMS with just two components 34. At this point it needs to be said that because of the challenges described above most examples in literature use organic polar solvents like DMF35–37 or acetonitrile38. The following examples will focus on the development of water based TMS systems. An example for an TMS based on methanol as polar solvent is the isomerization/hydroesterification of methyl-oleate.39 With a palladium/XantPhos catalyst and methane sulfonic acid as additive conversions up to 90% were generated. The selectivity of terminal n-products and internal branched products can be adjusted by the reaction parameters with the highest selectivity achieved for linear products of 64%. The reaction was first tested in a single phase reaction mixture (methanol) and then transferred to a TMS for catalyst recycling purposes. In a TMS consisting of methanol as the catalyst phase and decane as the product phase comparable conversions and low catalyst leaching of three ppm was measured in two consecutive runs. Since methanol is already one of the educts just one solvent had to be added. Later, the same reaction was investigated with 1,2 Bis(di-tert-butylphosphinomethyl)benzene (DTBPMB or sometimes referred to as DTBPX) as a ligand.40 To better compare the activity of the different catalysts the reaction time was lowered to five hours. Under optimized conditions 36% yield of the linear product with DTBPMB and 22% with XantPhos was possible within five hours (Scheme 4).

Scheme 4: isomerization/hydroesterification of methyl-oleate in a methanol/decane TMS.40



During catalyst recycling studies DTBPMB and XantPhos showed a leaching of approximately 2 ppm but DTBPMB proved to be much more sensitive to the acid concentration, making XantPhos a more robust ligand. Because methyl oleate is an attractive component for the synthesis of polymer building blocks based on renewables also the hydroaminomethylation of methyl-oleate was investigated in TMS recently.38,41 The TMS consisting of DMF/decane has been thoroughly investigated for the hydroformylation of 1-dodecene (Scheme 5). It was the starting point for the first TMS consisting of water.

Scheme 5: Continuous process for the hydroformylation of 1-dodecene in TMS media.

Several articles deal with the development ranging from reaction and process design to kinetic and phase distribution studies. In early studies the reaction system was investigated and a catalytic system based on Rhodium/BiPhePhos was derived. The influence of different parameters was tested to identify optimal reaction conditions and crucial parameters to prevent side reactions.42,43 Furthermore, in an extensive study the phase behavior of DMF/decane was investigated.44,45 The experiments in this study also considered the effect of the educt 1-dodecene and the product tridecanal on the TMS. It was shown that 1-dodecene has a mild, but tridecanal a rather strong solubilizing effect, limiting the possible load of substrate for a TMS. Shortly thereafter a continuous miniplant setup consisting of a continuously stirred tank reactor and a settler unit for phase separation (Figure 7 left) was developed and implemented.46–48

Figure 7: Process flow diagram of the continuous process for 1-dodecene hydroformylation (left). Reprinted with permission from (47). Copyright 2014 Elsevier 47 And yields for the 200 hour continuous operation (right). Reprinted with permission from (49). Copyright 2016 Elsevier. 49

Subsequent publications deal with further investigation of phase equilibria50, kinetic studies of the reaction pathway51 and ultimately optimization of the process in the miniplant.52–54 After optimization of


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the miniplant process, a 200 hour long steady state operation was accomplished (Figure 7 right) with a constant yield of tridecanal amounting for 64%. A rhodium leaching between 3 and 5 ppm was detected which was compensated by constant ligand and rhodium replenishment.49,55 Because the catalyst leaching was still too high for industrial applications a combination of recycling techniques was considered. One approach also tested and confirmed in the miniplant setup was the combination of TMS and organic solvent nanofiltration (OSN).56 Altogether very low catalyst leaching of >1 ppm rhodium was achieved in a first steady state operation for 50 hours.56,57 To widen the scope of the TMS approach, substrates beside long chain olefins were employed. Within the DMF/decane system, it was not possible to separate hydroformylation products from the fatty acid methyl-10-undecenoate (UME) and from the catalyst, since the polarity of the product was too high. To achieve effective separation a new approach was to use water as a solvent with even higher polarity in a TMS. Until now this is one of the few examples of a TMS based on water, and at the same time the only example of a continuous process based on a water/1-butanol TMS (Scheme 6).58

Scheme 6: Continuous Hydroformylation of methyl-10-undecenoate in water based TMS media.58

The combination of the hydrophilic SulfoXantPhos ligand together with water as the polar phase proved to be very effective. It has to be noted that at the reaction temperature of 140 °C the system only reaches full miscibility with lower loading of the substrate. This is why it was classified as “narrow TMS” for higher loadings of substrate. The reaction was transferred to a miniplant with a continuously stirred tank reactor (CSTR) and a separator and tested in a 21 hour continuous operation (Figure 8).58

Figure 8: Process flow diagram for the continuous hydroformylation of 10-undecenoate (left) and aldehyde yields in a 21 hour continuous operation (right). Reprinted with permission from (58). Copyright 2016 John Wiley and Sons.58



During this time, a high yield of 73% to the linear product was achieved in steady state. The catalyst leaching during the process amounted to 15 ppm, which is higher than in previous batch experiments and still requires some optimization. Nonetheless, the combination of polar renewable resources and a solvent system utilizing water and 1-butanol makes this an excellent example of a highly sustainable process. Surfactant based systems: The addition of surfactants to achieve higher reaction rates in water based media has been studied for a broad range of reactions. Surfactants are amphiphilic molecules with a polar head-group and long nonpolar tails. Because of the hydrophobic effect, by adding surfactants in concentrations above the cmc (critical micelle concentration), micelles are formed: nanoscale and three dimensional agglomerates of amphiphiles (Figure 9). The hydrophobic effect describes the tendency of nonpolar substances to agglomerate in water. In this way the contact zone between water and nonpolar substances is minimized.

Figure 9: Micellar media at the example of an oil in water emulsion.

Micelles act as a kind of nanoreactor.59,60 Because of the hydrophobic surroundings in the core of the micelles, hydrophobic reactants migrate into the micelles leading to a very high local concentration of substrate, enabling very fast reaction rates inside the micelles.61 Furthermore in aqueous media and because the catalyst is in close contact with the surfactant also the chemo- and stereoselectivity of reactions can be greatly influenced.62 The stability and lifetime of the micelles formed highly depend on the surfactant concentration and on the surfactant itself. Micellar media are differentiated in emulsions and microemulsions. Emulsions are not thermodynamically stable and need sheer forces (e.g. mixing) to be maintained.63 Microemulsions on the other hand are thermodynamically stable and offer different opportunities regarding phase separation and catalyst recycling. There are three different types of microemulsions, which are classified by their phase behavior. Their dependency on concentration and temperature are displayed in the Kahlweit´s fish diagram in Figure 10. Below the critical micelle concentration (cmc) the amphiphilic components mix with the solvents and a simple two phase system without micelles is obtained. With increasing surfactant concentration above the cmc the states 1, 2 and 3 are formed. For low temperatures oil in water emulsions are formed with oil bearing micelles in the water phase (2). For high temperatures reverse water in oil emulsions are formed with water bearing micelles in the oil phase (2̅). Between those two phases a temperature area with a three phasic systems exists (3). In this area a surfactant rich middle phase is formed with both types of micelles. Increasing the surfactant concentration


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further up to a certain point leads to a monophasic system with complete solubilization of both solvents (1).

Figure 10: Kahlweit´s fish diagram for the phase behavior in microemulsion systems. Reprinted with permission from (64). Copyright 2016 Elsevier.64

The choice of the right surfactant is probably the most important factor in the design of micellar reaction systems for a number of reasons. Since the micelle interior is a defined volume on the nanoscale, the



surfactant is in close contact with the reactants and can influence reaction rate and selectivity. A short list of important surfactants used in catalysis is given in Figure 11.

Figure 11: List of common and commercially available surfactants.

In the past, the replacement of organic solvents with water based micellar media has been investigated for a number of organic reactions. An extensive review on the topic of catalysis in micellar was released by the group of Scarso in 2015.62 Because they offer a simple tool for reaction rate enhancement and because they can be demixed simply by interrupting the stirring, emulsions are often favored for organic reactions on a smaller scale. The


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product separation is usually achieved by extraction with an organic solvent or in case of solid products by filtration. Several organic reactions e.g. Friedel-Crafts65,66, Stille67, Diels-Alder68,69 hydration70, nucleophilic aromatic substitutions71, indol functionalization72,73, alkyne hydroboration74, hydroaminomethylation75, isomerization76, hydrogenation77, C-H functionalization78, C-O bond formation79,80 or metathesis81,82 were successfully carried out in micellar emulsions. Suzuki and related Heck coupling reactions are some of the most important reactions for C-C bond formation with special importance in the synthesis of pharmaceuticals. Furthermore, the use of precious palladium catalysts and the need for nontoxic and clean products in the medical sector make catalyst recycling especially important. In 2016 Handa et al. introduced a new ligand called HandaPhos for the palladium catalyzed Suzuki-Miyuara-Coupling.83 Together in micellar media with the recently designed84 nonionic surfactant Nok a broad range of substrates were used with very good product yields up to 98% (Scheme 7).

Scheme 7: Suzuki-Miyaura coupling in micellar media with Nok.83

Only very low catalyst loadings ≤ 0.1 mol% are necessary and the reaction occurs at ambient temperature for most substrates tested. To recycle the catalyst the crystalline product was filtered off and the water phase was reused for five consecutive runs with no decrease in yield. Mattiello and coworkers developed



a strategy for the Suzuki-Coupling of complex pigments with thiophene boronates at room temperature under aerobic conditions in water (Scheme 8).85

Scheme 8: Suzuki coupling of pigments.85

Key to success was the use of the surfactant Kolliphor EL. Kolliphor EL is a mixture of several nonionic amphiphiles, which are synthesized by reacting castor oil with ethylene oxide. In the micellar interior of Kolliphor EL an oxygen free reaction environment exists, enabling good reactions rates and keeping the catalyst active while with other surfactants catalyst degradation occurred. Product isolation and catalyst recycling was possible by simple filtration in case of this crystalline products. In another publication on the topic the addition of 10% of volume toluene as co-solvent lead to the formation of a water/toluene emulsion drastically increasing product yield.86 The effects of co-solvents was also recently investigated by the group of Lipshutz.87 Another important class of reactions are oxidizations. Recently oxidations in micellar media have been under investigation. At the example of several oxidations the influence of water/surfactant based media


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on the stereoselectivity of reactions was shown.88–90 A good example is the epoxidation of alkenes with hydrogen peroxide as oxidizing agent and the help of a chiral Pt(II) catalyst (Scheme 9).91

Scheme 9: Epoxidation of olefins in micellar media.91

In the epoxidation of 4-methylpentene with comparable yields the enantiomeric excess (ee) was raised from 58% in 1,2-Dichloroethane to 82% in a water/substrate mixture with Triton-X114 as the surfactant. A big influence on the activity of the reaction was observed when testing several surfactants of the Triton family and changing the surfactant concentration. Indeed NMR 2D-NOESY spectroscopy revealed that a strong interaction between the catalyst and the hydrophobic moieties of the surfactant exists. This indicates that the catalyst is concentrated in the micelle interior and the micelles indeed act as



nanoreactors. After extraction of the product with hexane, the catalyst was successfully recycled in three consecutive runs with no decrease in yield and enantiomeric excess (ee). A good example of successful recycling studies is given by the palladium catalyzed coupling of nitroalkenes with arylhalogenides (Scheme 10).92

Scheme 10: Coupling of nitroalkanes with arylhalogenides in micellar media.92

For this reaction a new nonionic amphiphilic compound named FI-750-M was designed to form micelles with a slightly polar inner core, substituting organic solvents like DMF and 1,4-dioxane. For recycling experiments, the product was extracted with MTBE and the catalyst phase was reused. The catalyst was


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active for five consecutive runs with a high activity leading to 90-92% product yield. An E-factor of 5.3 has been evaluated for each reaction step. Another attempt was made in the gold catalyzed cycloisomerization of allenes and alkynes. In 2016 the groups of Weberskirch and Krause proved that several cycloisomerization reactions can be run in water with different poly(2-oxazolines) block co-polymers as the nonionic amphiphilic compound (Scheme 11).93

Scheme 11: Cycloisomerization with blockcopolymer amphiphiles.93



It was possible to reuse the catalyst phase for three consecutive runs although the reaction time had to be adjusted because of a decreasing catalyst activity. Product separation was achieved by extraction with n-pentane/Et2O. The potential of emulsions for the design of environmental friendly processes was recently illustrated in the example of a multistep synthesis for a pharmaceutical ingredient (referred to as API).94 The exact structure of the components was kept a secret in the publication.

Scheme 12: Reaction cascade for the synthesis of pharmaceutical ingredient (API) in water based media.94

The reaction cascade consisting of five reactions (Scheme 12) was successfully transferred to water/surfactant based media with the designer surfactant TPGS-750-M and compared to the established reaction sequence using organic solvents. The overall yield was raised by 5% from 43% to 48%. More importantly, by employing water-based media the consumption of organic solvents was lowered by a significant amount leading to approximately 30% less waste generated during the whole process. Besides


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the environmental footprint, also the process was simplified and an evaluation of the process cost revealed that overall a reduction of about 17% can be achieved (Figure 12).

Figure 12: cost reduction by using a water based solvent system compared to organic solvents in the five step synthesis of a pharmaceutical ingredient.94

The reaction was executed on a kilogram scale thus showing the feasibility for typical scale production of pharmaceutical products. By replacing organic solvents not only the environmental impact was lowered but also the reaction in water is economically favored. In contrast to previously mentioned examples, microemulsion systems do not require the extraction of products after the reaction since temperature differences can be used to separate the catalyst from products. As displayed in the fish diagram (Figure 10) for product isolation the microemulsion can be segregated by a simple temperature shift. The hydrophilic catalyst remains in the water phase and can be reused. There are examples in the past including, for example, hydrogenations.95,96 The topic of reactions in microemulsion systems has been recently reviewed by Schwarze et al.97 The hydroformylation of long chain olefins with the help of surfactants has been under investigation within the last fifteen years.98 The group of Schomäcker has been able to successfully develop a system for the hydroformylation of 1-dodecene in microemulsion media.99,100 First, the catalytic system has been studied and a rhodium catalyst with water soluble SulfoXantPhos as ligand proved to be suitable for the reaction.101 Not only has the surfactant significant influence on the reaction itself but in case of microemulsions the surfactant also dictates the temperature range in which the reaction and separation can be executed when a certain phase behavior is obliged (as displayed in the Kalweit´s fish diagram Figure 10). Phase behavior of the reaction was studied using different surfactants of the nonionic Marlipal type. Marlipal surfactants consist of an alkyl- linked to polyethyleneglycol-chains of various lengths. It was stated that for an efficient separation of the catalyst it is important to operate in a type (3) kind of microemulsion in the separator. Type (3) kind of microemulsions have a narrow temperature window but within this temperature the surfactant is held in a water/oil mixed middle phase while the rest of the water and oil separate as individual phases. The product just as the water/catalyst phase can be withdrawn comparably easy from the top and bottom as displayed in Figure 11. Especially in the case of type (3) microemulsions the designated temperature range is within small limits before the phase behavior changes, abolishing phase separation. Another problem arises with the increasing concentration of aldehyde during the reaction. The aldehyde concentration influences the phase behavior and shifts the



temperature range for efficient phase separation. A miniplant was designed with a stirred tank reactor and a settler unit for phase separation (Figure 13).99,100

Figure 13: Miniplant concept in the hydroformylation of 1-dodecene.

In miniplant scale the catalyst recycling was tested. When the designated three phase state in the settler was held the catalyst recycling worked as intended but during the process even little disturbances in reaction control led to a disturbance of the phases in the separator and high rhodium leaching occurred.64 Finally, after implementing an automated optic process control a successful continuous operation for a time of 150 hours was completed. During this time several operation modes were tested with different flow rates and recycle streams. A steady state with a low residence time of 0.5 h and very efficient catalyst recycling for over 70 hours was accomplished (Figure 14 case one). A rhodium leaching of approximately 100 ppb was detected. After that in case two an operation mode with a full recycle stream was tested with the goal to reach high overall yields. For case three and four a higher residence time of 2.8 h was set. Case three represents the time to adjust to this and reach steady state operation. For lower flow rates the product was received in a yield of 21% during steady state operation (case four).102


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Figure 14: Tridecanal yield in the continuous hydroformylation of dodecene in micellar media.102 Reprinted with permission from (102). Copyright 2016 American Chemical Society.

The successful implementation in a continuous process with such a low catalyst leaching clearly indicates the potential of microemulsion systems for homogenous catalyst recycling. The long road to establish this reaction also shows the complexity and challenges for potential applications. For a successful process and catalyst recycling clear knowledge of the phase behavior with all components during the reaction and a very precise process control to stay within the boundaries of separation conditions is necessary and has to be adjusted according to the reaction. Addition of cyclodextrines (CDs): Cyclodextrines (CDs) are a complex class of amphiphiles. They consist of a number of -glucopyranose units forming a cyclic macrocycle with an inner cavity (Figure 15).

Figure 15: Structural formula (left) and supramolecular structure (right) of cyclodextrines.

The polar hydroxyl groups of the -glycopyranose point into the surrounding medium while the inner cavity mostly faces the alkyl-backbone. The hydrophilic outer sphere is responsible for a good solubility in polar media while the inner cavity can uptake hydrophobic molecules. In this way, CDs act as shuttle for hydrophobic substrate molecules into the polar catalyst phase. Other than the surfactants described



before, cyclodextrines have no CMC above which micelles are formed. Although the phase transfer properties of CDs are known since the 1980s103,104, the group of Monflier was the first one to utilize modified CDs with great success in the mid 1990s105–107. By methylation of -CD highly effective randomly methylated cyclodextrines (RAME-CDs) can be synthesized. RAME-CDs are commercially available and show an enhanced catalytic activity depending on the grade of methylation.108 For example, RAME-CDs are able to increase the hydroformylation rate of 1-decene in a water/1-decene biphasic mixture from 10% conversion in eight hours to 100% conversion in six hours (Scheme 13).105

Scheme 13: Hydroformylation of 1-decene in biphasic media with the help of cyclodextrines.105

In later experiments, the group of Monflier was able to show that -CDs not only act as a phase transfer agent for insoluble substrates into the water phase but are furthermore able to encapsulate the catalyst ligand and therefore can alternate the equilibrium between catalyst species or increase catalyst concentration near the surface area.109,110 Advancing on the possibilities of modification of CDs also ligandmodified-CDs111 and polymer-bound-CDs112,113 have been utilized (Figure 16).

Figure 16: Principle of Ligand modified Cyclodextrines (left) and Polymer bound cylcodextrines for the uptake of long chain substrates at the example of hexadecane (right).

In the hydroformylation with just RAME-CDs, olefins in the range of 8-12 carbon atoms can be converted with a high efficiency. For very long chain olefins (> C12) the reaction rate decreases because one CD moiety is not able to fully uptake the substrate molecule anymore. When using polymer bound RAMECDs with a molecular weight of 8000 g mol-1 two CD units in close range to each other can uptake one substrate molecule. For example the hydroformylation of long chain hexadecane with just RAME-CDs in a biphasic water/hexadecane medium leads to only 23% yield after one hour whereas with polymer bound RAME-CDs the reaction can be enhanced to 52% (Scheme 14).112


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Scheme 14: Hydroformylation of 1-hexadecene in biphasic media with the help of polymer supported cyclodextrines.112

Recently CDs have been used in the hydroformylation of more demanding substrates such as the renewables eugenol, estragole and anethole (Scheme 15).114

Scheme 15: Hydroformylation of eugenol with cyclodextrines.114

In a biphasic system consisting of terpenes and water catalyzed by Rh/TPPTS several cyclodextrines have been investigated with the best results obtained for RAME--CD. Under optimized conditions between 94-97% conversion within six hours and good selectivities towards the aldehyde up to 89% are possible. The high regioselectivity of 87% for the linear aldehyde from eugenol using monodentate phosphine ligands is quite unusual. As an explanation, it was proposed that the sterically demanding methyl groups at the six position pointing into the cavity are sterically demanding and therefore favor the formation of the linear product. The catalyst was recycled in five consecutive runs without a decrease in activity and Inductively Coupled Plasma (ICP) analysis showed a catalyst leaching below the detection level of 0.1 ppm. A more fluid point of view on recycling techniques in biphasic media Several different methodologies have been presented in this review for the enhancement of mass transfer in aqueous biphasic media. While the intensification of mixing and the use of activated carbon as additive have the goal to increase the surface area of the substrate phase in water, additives like alcohols and cyclodextrines influence the substrate concentration in the water phase. Surfactants increase both the substrate concentration in the polar phase and the surface area. By forming a monophasic reaction mixture at higher temperatures in thermomorphic solvent systems the surface area can be regarded near infinite (Figure 17).



Figure 17: classification of recycling techniques by their principle of function.

Until now, the methodologies are mostly divided into different categories and regarded as independent approached to solve the problem of homogeneous catalyst recycling. However, on a closer look they seem to merge and overlap. They all build up on few principles. Especially at the example of alcohols it is obvious that the transitions between some of the approaches are rather fluid. By increasing the concentration, the chain length and the complexity of alcohols, one can switch between some of those concepts dynamically. Beginning with methanol as a co-solvent going to alcohol based thermomorphic solvent systems over long chain alcohol surfactants and ending with cyclodextrines (polyols). Conclusion: Recycling of homogenous catalysts is one of the most important tasks in homogenous catalysis for industrial application. Catalyst separation in biphasic water-based media is a very efficient and environmentally friendly approach, but until now not practical for hydrophobic substrates. Herein, different methodologies are presented to overcome this limitation. The intensification of the mixing and the addition of activated carbon pursue the goal of accelerating the reaction by increasing the surface area. Utilizing a jet-loop-reactor a significant increase in reaction rate in the hydroformylation of 1-octene was observed. Other additives like co-solvents surfactants and cyclodextrines increase the concentration of the substrate in the water phase to overcome mass transfer limitations. While cosolvents offer a simple approach an increased catalyst leaching is often a consequence. Surfactants and cyclodextrines are both very efficient. For surfactants a continuous process for the hydroformylation of 1dodecene was established. Because of the challenging design of TMS setups until now only one application based on water is known. The continuous hydroformylation of methyl-10-undecenoate is a good example for a possible sustainable process. At the example of alcohols it is shown that the strict subdivision of some of these recycling methodologies is shrinking.


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List of Abbreviations: Abbreviation AC cmc CSTR CTAB DMF DTBPMB ee ICP JLR MTBE OSN RAME-CD TMS TOF TPPTS (T)TON UME

Meaning Activated carbon Critical micelle concentration Continously stirred tank reactor Cetyltrimethylammonium bromide Dimethylformamide 1,2-Bis(di-tert-butylphosphinomethyl)benzene Enantiomeric excess Inductively coupled plasma Jet-loop-reactor Methyl tert-butyl ether Organic solvent nanofiltration Randomly methylated cyclodextrine Thermomorphic solvent system Turnover frequency [h-1] Triphenylphosphine-tri-sulfonate (Total) Turnover number Undecenoic methyl ester

References:

(1)

Sheldon, R. A. The E Factor 25 Years on: The Rise of Green Chemistry and Sustainability. Green Chem. 2017, 19 (1), 18–43.

(2)

Horváth, I. T.; Anastas, P. T. Introduction: Green Chemistry. Chem. Rev. 2007, 107 (6), 2167–2168.

(3)

Jessop, P. G.; Trakhtenberg, S.; Warner, J. The Twelve Principles of Green Chemistry. ACS Symp. Ser. 2009, 401–436.

(4)

Catlow, C. R.; Davidson, M.; Hardacre, C.; Hutchings, G. J. Catalysis Making the World a Better Place. Philos. Trans. R. Soc., A 2016, 374 (2061), 20150089.

(5)

Behr, A.; Neubert, P. Applied Homogeneous Catalysis, 2nd ed.; Wiley-VCH: Weinheim, 2012.

(6)

Cole-Hamilton, D. J. Homogeneous Catalysis--New Approaches to Catalyst Separation, Recovery, and Recycling. Science 2003, 299 (5613), 1702–1706.

(7)

Schaper, L.-A.; Hock, S. J.; Herrmann, W. A.; Kühn, F. E. Synthesis and Application of Water-Soluble NHC Transition-Metal Complexes. Angew. Chem., Int. Ed. 2013, 52 (1), 270–289.



(8)

Herrmann, W. A.; Kohlpaintner, C. W. Water-Soluble Ligands, Metal Complexes, and Catalysts: Synergism of Homogeneous and Heterogeneous Catalysis. Angew. Chem., Int. Ed. Engl. 1993, 22, 1524–1544.

(9)

Hibbel, J.; Wiebus, E.; Cornils, B. 75 Jahre Hydroformylierung - Oxoreaktoren Und Oxoanlagen der Ruhrchemie AG und der Oxea GmbH von 1938 bis 2013. Chem. Ing. Tech. 2013, 85 (12), 1853–1871.

(10)

Kohlpaintner, C. W.; Fischer, R. W.; Cornils, B. Aqueous Biphasic Catalysis: Ruhrchemie/Rhône-Poulenc Oxo Process. Appl. Catal., A 2001, 221 (1–2), 219–225.

(11)

McAuliffe, C. Solubility in Water of Paraffin, Cycloparaffin, Olefin, Acetylene, Cycloolefin, and Aromatic Hydrocarbons. J. Phys. Chem. 1966, 70 (4), 1267–1275.

(12)

Warmeling, H.; Koske, R.; Vorholt, A. J. Procedural Rate Enhancement of Lean Aqueous Hydroformylation of 1-Octene without Additives. Chem. Eng. Technol. 2017, 40 (1), 186– 195.

(13)

Warmeling, H.; Hafki, D.; von Söhnen, T.; Vorholt, A. J. Kinetic Investigation of Lean Aqueous Hydroformylation – An Engineer’s View on Homogeneous Catalysis. Chem. Eng. J. 2017, 326, 298–307.

(14)

Warmeling, H.; Janz, D.; Peters, M.; Vorholt, A. J. Acceleration of Lean Aqueous Hydroformylation in an Innovative Jet Loop Reactor Concept. Chem. Eng. J. 2017, 330, 585–595.

(15)

Deshpande, R. M.; Purwanto; Delmas, H.; Chaudhari, R. V. Effect of pH on Rate and Selectivity Behavior in Biphasic Hydroformylation of 1-Octene. J. Mol. Catal. A: Chem. 1997, 126 (2–3), 133–140.

(16)

Kania, N.; Léger, B.; Fourmentin, S.; Monflier, E.; Ponchel, A. Activated Carbon as a MassTransfer Additive in Aqueous Organometallic Catalysis. Chem. - Eur. J. 2010, 16 (21), 6138–6141.

(17)

Ponchel, A.; Monflier, E.; Souvraz, R. J. Rhodium-Catalyzed Hydroformylation of Unsaturated Fatty Esters in Aqueous Media Assisted by Activated Carbon. Eur. J. Lipid Sci. Technol. 2012, 114, 1439–1446.

(18)

Purwanto, P.; Delmas, H. Gas-Liquid-Liquid Reaction Engineering: Hydroformylation of 1-


Page 28 of 39

Page 29 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Octene Using a Water Soluble Rhodium Complex Catalyst. Catal. Today 1995, 24 (1–2), 135–140. (19)

Monteil, F.; Queau, R.; Kalck, P. Behavior of Water-Soluble Dinuclear Rhodium Complexes in the Hydroformulation Reaction of Oct-1-Ene. J. Organomet. Chem. 1994, 480, 177– 184.

(20)

Dabbawala, A. A.; Parmar, D. U.; Bajaj, H. C.; Jasra, R. V. CoCl2(TPPTS)2 Catalyzed Hydroformylation of 1-Octene and 1-Decene in the Presence of Surfactant and CoSolvents in a Biphasic Medium. J. Mol. Catal. A: Chem. 2008, 282 (1–2), 99–106.

(21)

Dabbawala, A. A.; Bajaj, H. C.; Bricout, H.; Monflier, E. Biphasic Hydroformylation of 1Octene Catalyzed by Cobalt Complex of Trisulfonated Tris(Biphenyl)Phosphine. Appl. Catal., A 2012, 413–414, 273–279.

(22)

Behr, A.; Toslu, N. Einphasige und zweiphasige Reaktionsführung der Hydrosilylierungsreaktion. Chem. Ing. Tech. 1999, 71 (5), 490–493.

(23)

Behr, A.; Roll, R. Hydroaminomethylation in Thermomorphic Solvent Systems. J. Mol. Catal. A: Chem. 2005, 239 (1–2), 180–184.

(24)

Behr, A.; Fängewisch, C. Rhodium-Catalysed Synthesis of Branched Fatty Compounds in Temperature-Dependent Solvent Systems. J. Mol. Catal. A: Chem. 2003, 197 (1–2), 115– 126.

(25)

Behr, A.; Miao, Q. A New Temperature-Dependent Solvent System Based on Polyethylene Glycol 1000 and Its Use in Rhodium Catalyzed Cooligomerization. J. Mol. Catal. A: Chem. 2004, 222 (1–2), 127–132.

(26)

Behr, A.; Miao, Q. Selective Rhodium Catalysed Synthesis of Trans-1,4-Hexadiene in Polyethylene Glycol 1000-Water Solvent Systems. Green Chem. 2005, 7 (8), 617–620.

(27)

Behr, A.; Johnen, L.; Vorholt, A. J. Novel Palladium-Catalysed Hydroamination of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems. Adv. Synth. Catal. 2010, No. 352, 2062–2072.

(28)

Behr, A.; Gomes-Jelonek, J.; Witte, H. Katalysatorrecycling in Der Homogenkatalysierten Kreuzmetathese von Ölsäuremethylester und 4-Octen. Chem. Ing. Tech. 2012, 84 (12), 2174–2181.



(29)

Huang, S.; Bilel, H.; Zagrouba, F.; Hamdi, N.; Bruneau, C.; Fischmeister, C. Olefin Metathesis Transformations in Thermomorphic Multicomponent Solvent Systems. Catal. Commun. 2015, 63, 31–34.

(30)

Shaharun, M. S.; Dutta, B. K.; Mukhtar, H.; Maitra, S. Hydroformylation of 1-Octene Using Rhodium-Phosphite Catalyst in a Thermomorphic Solvent System. Chem. Eng. Sci. 2010, 65 (1), 273–281.

(31)

Behr, A.; Brunsch, Y.; Lux, A. Rhodium Nanoparticles as Catalysts in the Hydroformylation of 1-Dodecene and Their Recycling in Thermomorphic Solvent Systems. Tetrahedron Lett. 2012, 53 (22), 2680–2683.

(32)

Behr, A.; Roll, R. Temperaturgesteuerte Mehrkomponenten-Lösungsmittelsysteme Für Homogene Übergangsmetallkatalysierte Reaktionen. Chem. Ing. Tech. 2005, 77 (6), 748– 752.

(33)

Behr, A.; Johnen, L.; Vorholt, A. J. Telomerization of Myrcene and Catalyst Separation by Thermomorphic Solvent Systems. ChemCatChem 2010, 2 (10), 1271–1277.

(34)

Behr, A.; Henze, G.; Johnen, L.; Awungacha, C. Advances in Thermomorphic Liquid/Liquid Recycling of Homogeneous Transition Metal Catalysts. J. Mol. Catal. A: Chem. 2008, 285 (1–2), 20–28.

(35)

Gaide, T.; Jörke, A.; Schlipköter, K. E.; Hamel, C.; Seidel-Morgenstern, A.; Behr, A.; Vorholt, A. J. Isomerization/Hydroformylation Tandem Reaction of a Decene Isomeric Mixture with Subsequent Catalyst Recycling in Thermomorphic Solvent Systems. Appl. Catal., A 2017, 532, 50–56.

(36)

Jörke, A.; Gaide, T.; Behr, A.; Vorholt, A.; Seidel-Morgenstern, A.; Hamel, C. Hydroformylation and Tandem Isomerization–hydroformylation of N-Decenes Using a Rhodium-BiPhePhos Catalyst: Kinetic Modeling, Reaction Network Analysis and Optimal Reaction Control. Chem. Eng. J. 2017, 313, 382–397.

(37)

Vogelsang, D.; Faßbach, T. A.; Kossmann, P. P.; Vorholt, A. J. Terpene-Derived Highly Branched C30-Amines via Palladium-Catalysed Telomerisation of β-Farnesene. Adv. Synth. Catal. 2018, 360 (10), 1984–1991.

(38)

Vorholt, A. J.; Immohr, S.; Ostrowski, K. A.; Fuchs, S.; Behr, A. Catalyst Recycling in the


Page 30 of 39

Page 31 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Hydroaminomethylation of Methyl Oleate: A Route to Novel Polyamide Monomers. Eur. J. Lipid Sci. Technol. 2017, 119 (5), 1600211. (39)

Behr, A.; Vorholt, A. J.; Rentmeister, N. Recyclable Homogeneous Catalyst for the Hydroesterification of Methyl Oleate in Thermomorphic Solvent Systems. Chem. Eng. Sci. 2013, 99, 38–43.

(40)

Gaide, T.; Behr, A.; Terhorst, M.; Arns, A.; Benski, F.; Vorholt, A. J. Katalysatorvergleich Bei Der Hydroesterifizierung von 10-Undecensäuremethylester in Thermomorphen Lösungsmittelsystemen. Chem. Ing. Tech. 2016, 88 (1–2), 158–167.

(41)

Behr, A.; Seidensticker, T.; Vorholt, A. J. Diester Monomers from Methyl Oleate and Proline via Tandem Hydroaminomethylation-Esterification Sequence with Homogeneous Catalyst Recycling Using TMS-Technique. Eur. J. Lipid Sci. Technol. 2014, 116 (4), 477– 485.

(42)

Brunsch, Y.; Behr, A. Temperature-Controlled Catalyst Recycling in Homogeneous Transition-Metal Catalysis: Minimization of Catalyst Leaching. Angew. Chem., Int. Ed. 2013, 52 (5), 1586–1589.

(43)

Markert, J.; Brunsch, Y.; Munkelt, T.; Kiedorf, G.; Behr, A.; Hamel, C.; Seidel-Morgenstern, A. Analysis of the Reaction Network for the Rh-Catalyzed Hydroformylation of 1Dodecene in a Thermomorphic Multicomponent Solvent System. Appl. Catal., A 2013, 462–463, 287–295.

(44)

Schäfer, E.; Brunsch, Y.; Sadowski, G.; Behr, A. Hydroformylation of 1-Dodecene in the Thermomorphic Solvent System Dimethylformamide/Decane. Phase Behavior–Reaction Performance–Catalyst Recycling. Ind. Eng. Chem. Res. 2012, 51 (31), 10296–10306.

(45)

Rost, A.; Brunsch, Y.; Behr, A.; Schomäcker, R. Comparison of the Activity of a RhodiumBiphephos Catalyst in Thermomorphic Solvent Mixtures and Microemulsions. Chem. Eng. Technol. 2014, 37 (6), 1055–1064.

(46)

Hentschel, B.; Peschel, A.; Freund, H.; Sundmacher, K. Simultaneous Design of the Optimal Reaction and Process Concept for Multiphase Systems. Chem. Eng. Sci. 2014, 115, 69–87.

(47)

Zagajewski, M.; Behr, A.; Sasse, P.; Wittmann, J. Continuously Operated Miniplant for the



Rhodium Catalyzed Hydroformylation of 1-Dodecene in a Thermomorphic Multicomponent Solvent System (TMS). Chem. Eng. Sci. 2014, 115, 88–94. (48)

Kaiser, N. M.; Jokiel, M.; McBride, K.; Flassig, R. J.; Sundmacher, K. Optimal Reactor Design via Flux Profile Analysis for an Integrated Hydroformylation Process. Ind. Eng. Chem. Res. 2017, 56 (40), 11507–11518.

(49)

Dreimann, J.; Lutze, P.; Zagajewski, M.; Behr, A.; Górak, A.; Vorholt, A. J. Highly Integrated Reactor–separator Systems for the Recycling of Homogeneous Catalysts. Chem. Eng. Process. Process Intensif. 2016, 99, 124–131.

(50)

Merchan, V. A.; Wozny, G. Comparative Evaluation of Rigorous Thermodynamic Models for the Description of the Hydroformylation of 1-Dodecene in a Thermomorphic Solvent System. Ind. Eng. Chem. Res. 2016, 55 (1), 293–310.

(51)

Kiedorf, G.; Hoang, D. M.; Müller, A.; Jörke, A.; Markert, J.; Arellano-Garcia, H.; SeidelMorgenstern, A.; Hamel, C. Kinetics of 1-Dodecene Hydroformylation in a Thermomorphic Solvent System Using a Rhodium-Biphephos Catalyst. Chem. Eng. Sci. 2014, 115, 31–48.

(52)

Hentschel, B.; Kiedorf, G.; Gerlach, M.; Hamel, C.; Seidel-Morgenstern, A.; Freund, H.; Sundmacher, K. Model-Based Identification and Experimental Validation of the Optimal Reaction Route for the Hydroformylation of 1-Dodecene. Ind. Eng. Chem. Res. 2015, 54 (6), 1755–1765.

(53)

McBride, K.; Sundmacher, K. Data Driven Conceptual Process Design for the Hydroformylation of 1-Dodecene in a Thermomorphic Solvent System. Ind. Eng. Chem. Res. 2015, 54 (26), 6761–6771.

(54)

Dreimann, J. M.; Warmeling, H.; Weimann, J. N.; Künnemann, K.; Behr, A.; Vorholt, A. J. Increasing Selectivity of the Hydroformylation in a Miniplant: Catalyst, Solvent, and Olefin Recycle in Two Loops. AIChE J. 2016, 62 (12), 4377–4383.

(55)

Zagajewski, M.; Dreimann, J.; Behr, A. Verfahrensentwicklung Vom Labor Zur Miniplant: Hydroformylierung von 1-Dodecen in Thermomorphen Lösungsmittelsystemen. Chem. Ing. Tech. 2014, 86 (4), 449–457.

(56)

Dreimann, J. M.; Hoffmann, F.; Skiborowski, M.; Behr, A.; Vorholt, A. J. Merging


Page 32 of 39

Page 33 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Thermomorphic Solvent Systems and Organic Solvent Nanofiltration for Hybrid Catalyst Recovery in a Hydroformylation Process. Ind. Eng. Chem. Res. 2017, 56 (5), 1354–1359. (57)

McBride, K.; Kaiser, N. M.; Sundmacher, K. Integrated Reaction–extraction Process for the Hydroformylation of Long-Chain Alkenes with a Homogeneous Catalyst. Comput. Chem. Eng. 2017, 105, 212–223.

(58)

Gaide, T.; Dreimann, J. M.; Behr, A.; Vorholt, A. J. Overcoming Phase-Transfer Limitations in the Conversion of Lipophilic Oleo Compounds in Aqueous Media-A Thermomorphic Approach. Angew. Chem., Int. Ed. 2016, 55 (8), 2924–2928.

(59)

Vriezema, D. M.; Aragonès, M. C.; Elemans, J. A. A. W.; Cornelissen, J. J. L. M.; Rowan, A. E.; Nolte, R. J. M. Self-Assembled Nanoreactors. Chem. Rev. 2005, 105 (4), 1445–1489.

(60)

Sorrenti, A.; Illa, O.; Ortuño, R. M. Amphiphiles in Aqueous Solution: Well beyond a Soap Bubble. Chem. Soc. Rev. 2013, 42 (21), 8200.

(61)

Wang, L.; Chen, H.; He, Y. E.; Li, Y.; Li, M.; Li, X. Long Chain Olefin Hydroformylation in Biphasic Catalytic System - How the Reaction Is Accelerated. Appl. Catal., A 2003, 242 (1), 85–88.

(62)

La Sorella, G.; Strukul, G.; Scarso, A. Recent Advances in Catalysis in Micellar Media. Green Chem. 2015, 17 (2), 644–683.

(63)

Kale, S. N.; Deore, S. L. Emulsion Micro Emulsion and Nano Emulsion: A Review. Syst. Rev. Pharm. 2016, 8 (1), 39–47.

(64)

Pogrzeba, T.; Müller, D.; Illner, M.; Schmidt, M.; Kasaka, Y.; Weber, A.; Wozny, G.; Schomäcker, R.; Schwarze, M. Superior Catalyst Recycling in Surfactant Based Multiphase Systems – Quo Vadis Catalyst Complex? Chem. Eng. Process. Process Intensif. 2016, 99, 155–166.

(65)

Rajendar Reddy, K.; Rajanna, K. C.; Uppalaiah, K. Environmentally Benign Contemporary Friedel-Crafts Acylation of 1-halo-2-methoxynaphthalenes and Its Related Compounds under Conventional and Nonconventional Conditions. Tetrahedron Lett. 2013, 54 (26), 3431–3436.

(66)

Rosati, F.; Oelerich, J.; Roelfes, G. Dramatic Micellar Rate Enhancement of the Cu 2+ Catalyzed Vinologous Friedel-Crafts Alkylation in Water. Chem. Commun. 2010, 46 (41),



7804–7806. (67)

Lu, G. P.; Cai, C.; Lipshutz, B. H. Stille Couplings in Water at Room Temperature. Green Chem. 2013, 15 (1), 105–109.

(68)

Bica, K.; Gärtner, P.; Gritsch, P. J.; Ressmann, A. K.; Schröder, C.; Zirbs, R. Micellar Catalysis in Aqueous-Ionic Liquid Systems. Chem. Commun. 2012, 48 (41), 5013–5015.

(69)

Trentin, F.; Scarso, A.; Strukul, G. Micellar-Driven Substrate Selectivity in Cr(Salen)Cl Catalytic Diels-Alder Reaction in Water. Tetrahedron Lett. 2011, 52 (51), 6978–6981.

(70)

Rühling, A.; Galla, H.-J.; Glorius, F. A Remarkably Simple Hybrid Surfactant-NHC Ligand, Its Gold-Complex, and Application in Micellar Catalysis. Chem. - Eur. J. 2015, 21 (35), 12291– 12294.

(71)

Isley, N. A.; Linstadt, R. T. H.; Kelly, S. M.; Gallou, F.; Lipshutz, B. H. Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis. Org. Lett. 2015, 17 (19), 4734–4737.

(72)

Kitanosono, T.; Miyo, M.; Kobayashi, S. The Combined Use of Cationic Palladium(II) with a Surfactant for the C-H Functionalization of Indoles and Pyrroles in Water. Tetrahedron 2015, 71 (40), 7739–7744.

(73)

Kitanosono, T.; Miyo, M.; Kobayashi, S. Surfactant-Aided Chiral Palladium(II) Catalysis Exerted Exclusively in Water for the C-H Functionalization of Indoles. ACS Sustain. Chem. Eng. 2016, 4 (11), 6101–6106.

(74)

da Costa, J. S.; Braun, R. K.; Horn, P. A.; Lüdtke, D. S.; Moro, A. V. Copper-Catalyzed Hydroboration of Propargyl-Functionalized Alkynes in Water. RSC Adv. 2016, 6 (65), 59935–59938.

(75)

Behr, A.; Wintzer, A. Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System. Chem. Eng. Technol. 2015, 38 (12), 2299–2304.

(76)

Sperni, L.; Scarso, A.; Strukul, G. Micellar Promoted Alkenes Isomerization in Water Mediated by a Cationic Half-Sandwich Ru(II) Complex. Inorg. Chim. Acta 2017, 455, 535– 539.

(77)

Stathis, P.; Stavroulaki, D.; Kaika, N.; Krommyda, K.; Papadogianakis, G. Low TransIsomers Formation in the Aqueous-Phase Pt/TPPTS-Catalyzed Partial Hydrogenation of


Page 34 of 39

Page 35 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Methyl Esters of Linseed Oil. Appl. Catal. B Environ. 2017, 209, 579–590. (78)

Álvarez, M.; Gava, R.; Rodríguez, M. R.; Rull, S. G.; Pérez, P. J. Water as the Reaction Medium for Intermolecular C–H Alkane Functionalization in Micellar Catalysis. ACS Catal. 2017, 7 (5), 3707–3711.

(79)

Ahanthem, D.; Laitonjam, W. S. C(sp2)−O Bond Formation through a Nickel-Catalyzed Cross-Coupling Reaction in Water Enabled by Micellar Catalysis. Asian J. Org. Chem. 2017, 6 (10), 1492–1497.

(80)

Li, X.-H.; Mi, C.; Liao, X.-H.; Meng, X.-G. Selective Oxidation of Aromatic Olefins Catalyzed by Copper(II) Complex in Micellar Media. Catal. Lett. 2017, 147 (10), 2508–2514.

(81)

Laville, L.; Charnay, C.; Lamaty, F.; Martinez, J.; Colacino, E. Ring-Closing Metathesis in Aqueous Micellar Medium. Chem. - Eur. J. 2012, 18 (3), 760–764.

(82)

Astruc, D.; Diallo, A. K.; Gatard, S.; Liang, L.; Ornelas, C.; Martinez, V.; Méry, D.; Ruiz, J. Olefin Metathesis in Nano-Sized Systems. Beilstein J. Org. Chem. 2011, 7, 94–103.

(83)

Handa, S.; Andersson, M. P.; Gallou, F.; Reilly, J.; Lipshutz, B. H. HandaPhos: A General Ligand Enabling Sustainable ppm Levels of Palladium-Catalyzed Cross-Couplings in Water at Room Temperature. Angew. Chem., Int. Ed. 2016, 55 (16), 4914–4918.

(84)

Klumphu, P.; Lipshutz, B. H. “nok”: A Phytosterol-Based Amphiphile Enabling TransitionMetal-Catalyzed Couplings in Water at Room Temperature. J. Org. Chem. 2014, 79 (3), 888–900.

(85)

Mattiello, S.; Rooney, M.; Sanzone, A.; Brazzo, P.; Sassi, M.; Beverina, L. Suzuki-Miyaura Micellar Cross-Coupling in Water, at Room Temperature, and under Aerobic Atmosphere. Org. Lett. 2017, 19 (3), 654–657.

(86)

Rooney, M.; Mattiello, S.; Stara, R.; Sanzone, A.; Brazzo, P.; Sassi, M.; Beverina, L. SuzukiMiyaura Cross-Coupling of Latent Pigments in Water/Toluene Emulsion under Aerobic Atmosphere. Dyes Pigm. 2018, 149 (September 2017), 893–901.

(87)

Gabriel, C. M.; Lee, N. R.; Bigorne, F.; Klumphu, P.; Parmentier, M.; Gallou, F.; Lipshutz, B. H. Effects of Co-Solvents on Reactions Run under Micellar Catalysis Conditions. Org. Lett. 2017, 19 (1), 194–197.

(88)

Dey, J.; Saha, M.; Pal, A. K.; Ismail, K. Regioselective Nitration of Aromatic Compounds in



an Aqueous Sodium Dodecylsulfate and Nitric Acid Medium. RSC Adv. 2013, 3 (40), 18609. (89)

Cavarzan, A.; Bianchini, G.; Sgarbossa, P.; Lefort, L.; Gladiali, S.; Scarso, A.; Strukul, G. Catalytic Asymmetric Baeyer-Villiger Oxidation in Water by Using Pt II Catalysts and Hydrogen Peroxide: Supramolecular Control of Enantioselectivity. Chem. - Eur. J. 2009, 15 (32), 7930–7939.

(90)

Scarso, A.; Strukul, G. Asymmetric Sulfoxidation of Thioethers with Hydrogen Peroxide in Water Mediated by Platinum Chiral Catalyst. Adv. Synth. Catal. 2005, 347 (9), 1227–1234.

(91)

Colladon, M.; Scarso, A.; Strukul, G. Towards a Greener Epoxidation Method: Use of Water-Surfactant Media and Catalyst Recycling in the Platinum-Catalyzed Asymmetric Epoxidation of Terminal Alkenes with Hydrogen Peroxide. Adv. Synth. Catal. 2007, 349 (6), 797–801.

(92)

Brals, J.; Smith, J. D.; Ibrahim, F.; Gallou, F.; Handa, S. Micelle-Enabled Palladium Catalysis for Convenient sp2-sp3 Coupling of Nitroalkanes with Aryl Bromides in Water Under Mild Conditions. ACS Catal. 2017, 7 (10), 7245–7250.

(93)

Lempke, L.; Ernst, A.; Kahl, F.; Weberskirch, R.; Krause, N. Sustainable Micellar Gold Catalysis - Poly(2-Oxazolines) as Versatile Amphiphiles. Adv. Synth. Catal. 2016, 358 (9), 1491–1499.

(94)

Gallou, F.; Isley, N. A.; Ganic, A.; Onken, U.; Parmentier, M. Surfactant Technology Applied toward an Active Pharmaceutical Ingredient: More than a Simple Green Chemistry Advance. Green Chem. 2016, 18 (1), 14–19.

(95)

Milano-Brusco, J. S.; Schomäcker, R. Catalytic Hydrogenations in Microemulsion Systems with Rh-TPPTS: Partial Hydrogenation of Sunflower Oil. Catal. Lett. 2009, 133 (3–4), 273– 279.

(96)

Milano-Brusco, J. S.; Schwarze, M.; Djennad, M.; Nowothnick, H.; Schomäcker, R. Catalytic Hydrogenation of Dimethyl Itaconate in a Water−Cyclohexane−Triton X-100 Microemulsion in Comparison to a Biphasic System. Ind. Eng. Chem. Res. 2008, 47 (20), 7586–7592.

(97)

Schwarze, M.; Pogrzeba, T.; Volovych, I.; Schomäcker, R. Microemulsion Systems for


Page 36 of 39

Page 37 of 39 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Catalytic Reactions and Processes. Catal. Sci. Technol. 2015, 5 (1), 24–33. (98)

Schwarze, M.; Pogrzeba, T.; Seifert, K.; Hamerla, T.; Schomäcker, R. Recent Developments in Hydrogenation and Hydroformylation in Surfactant Systems. Catal. Today 2015, 247, 55–63.

(99)

Rost, A.; Müller, M.; Hamerla, T.; Kasaka, Y.; Wozny, G.; Schomäcker, R. Development of a Continuous Process for the Hydroformylation of Long-Chain Olefins in Aqueous Multiphase Systems. Chem. Eng. Process. Process Intensif. 2013, 67, 130–135.

(100) Müller, M.; Kasaka, Y.; Müller, D.; Schomäcker, R.; Wozny, G. Process Design for the Separation of Three Liquid Phases for a Continuous Hydroformylation Process in a Miniplant Scale. Ind. Eng. Chem. Res. 2013, 52 (22), 7259–7264. (101) Hamerla, T.; Rost, A.; Kasaka, Y.; Schomäcker, R. Hydroformylation of 1-Dodecene with Water-Soluble Rhodium Catalysts with Bidentate Ligands in Multiphase Systems. ChemCatChem 2013, 5 (7), 1854–1862. (102) Illner, M.; Müller, D.; Esche, E.; Pogrzeba, T.; Schmidt, M.; Schomäcker, R.; Wozny, G.; Repke, J.-U. Hydroformylation in Microemulsions: Proof of Concept in a Miniplant. Ind. Eng. Chem. Res. 2016, 55 (31), 8616–8626. (103) Nikiforov, T. T.; Trifonov, A. Z. Cyclodextrins as Phase-Transfer Catalysts in a Nucleophilic Displacement Reaction. J. Mol. Catal. 1984, 24, 15–18. (104) Zahalka, H. A.; Januszkiewicz, K.; Alper, H. Olefin Oxidation Catalyzed by PalladiumChloride Using Cyclodextrins as Phase-Transfer Agents. J. Mol. Catal. 1986, 35, 249–253. (105) Monflier, E.; Fremy, G.; Castanet, Y.; Mortreux, A. Molecular Recognition between Chemically Modified β-Cyclodextrin and Dec-1-ene: New Prospects for Biphasic Hydroformylation of Water-Insoluble Olefins. Angew. Chem., Int. Ed. Engl. 1995, 34 (20), 2269–2271. (106) Monflier, E.; Tilloy, S.; Fremy, G.; Castanet, Y.; Mortreux, A. A Further Breakthrough in Biphasic, Rhodium-Catalyzed Hydroformylation: The Use of Per(2,6-Di-O-Methyl)-βCyclodextrin as Inverse Phase Transfer Catalyst. Tetrahedron Lett. 1995, 36 (52), 9481– 9484. (107) Monflier, E.; Blouet, E.; Barbaux, Y.; Mortreux, A. Wacker Oxidation of 1-Decene to 2-



Decanone in the Presence of a Chemically Modified Cyclodextrin System: A Happy Union of Host–Guest Chemistry and Homogeneous Catalysis. Angew. Chem., Int. Ed. Engl. 1994, 33 (20), 2100–2102. (108) Legrand, F.-X.; Sauthier, M.; Flahaut, C.; Hachani, J.; Elfakir, C.; Fourmentin, S.; Tilloy, S.; Monflier, E. Aqueous Hydroformylation Reaction Mediated by Randomly Methylated βCyclodextrin: How Substitution Degree Influences Catalytic Activity and Selectivity. J. Mol. Catal. A: Chem. 2009, 303 (1–2), 72–77. (109) Mathivet, T.; Méliet, C.; Castanet, Y.; Mortreux, A.; Caron, L.; Tilloy, S.; Monflier, E. Rhodium Catalyzed Hydroformylation of Water Insoluble Olefins in the Presence of Chemically Modified β-Cyclodextrins: Evidence for Ligand-Cyclodextrin Interactions and Effect of Various Parameters on the Activity and the Aldehydes Selectivity. J. Mol. Catal. A: Chem. 2001, 176 (1–2), 105–116. (110) Six, N.; Guerriero, A.; Landy, D.; Peruzzini, M.; Gonsalvi, L.; Hapiot, F.; Monflier, E. Supramolecularly Controlled Surface Activity of an Amphiphilic Ligand. Application to Aqueous Biphasic Hydroformylation of Higher Olefins. Catal. Sci. Technol. 2011, 1 (8), 1347–1353. (111) Hapiot, F.; Bricout, H.; Tilloy, S.; Monflier, E. Functionalized Cyclodextrins as First and Second Coordination Sphere Ligands for Aqueous Organometallic Catalysis. Eur. J. Inorg. Chem. 2012, 2012 (10), 1571–1578. (112) Potier, J.; Menuel, S.; Fournier, D.; Fourmentin, S.; Woisel, P.; Monflier, E.; Hapiot, F. Cooperativity in Aqueous Organometallic Catalysis: Contribution of CyclodextrinSubstituted Polymers. ACS Catal. 2012, 2 (7), 1417–1420. (113) Potier, J.; Menuel, S.; Mathiron, D.; Bonnet, V.; Hapiot, F.; Monflier, E. CyclodextrinGrafted Polymers Functionalized with Phosphanes: A New Tool for Aqueous Organometallic Catalysis. Beilstein J. Org. Chem. 2014, 10, 2642–2648. (114) Jagtap, S. A.; Monflier, E.; Ponchel, A.; Bhanage, B. M. Highly Regio-Selective Hydroformylation of Biomass Derived Eugenol Using Aqueous Biphasic Rh/TPPTS/CDs as a Greener and Recyclable Catalyst. Mol. Catal. 2017, 436, 157–163.


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