1-Octene hydroformylation

Liquid Recycle is practical for octene hydroformylation. 1-Octene is readily soluble in organic based catalyst solutions, and product aldehyde and its condensation products can be separated by vaporization. 

Hydroformylation is also used for the manufacture of isononyl alcohol and other long-chain alcohols. Isononyl alcohol is made by first hydroformylating 1-octene to isononaldehyde and then hydrogenating the latter. The long-chain alcohols ( 10 to 20 carbon atoms) are used... 

Induced Phase Separation is also a good choice for octene hydroformylation. Octene can easily dissolve in the organic based catalyst solution, and with addition of small amounts of water, nonanal and its condensation products will readily separate from the sodium salt of a monosulfonated phosphine. To choose between Liquid Recycle and Induced Phase Separation would require a detailed technical and economic study that is outside the scope of this chapter. 

Grubbs and coworkers (35) while examining Rh and Co catalysts derived from 14 reported the loss of infrared CO stretches and visual darkening of the catalysts after use for hydrogenation of olefins, aldehydes or ketones, cyclohexene disproportionation to benzene and cyclohexane or the cyclotrimerization of a wide variety of acetylenes. Stille (36) using a rhodium catalyst prepared from 14 observed activity for the hydrogenation of benzene that increased with reuse, a phenomenon usually associated with metal crystallite formation. Rhodium catalysts of 15 and 16 used to hydroformylate octene-1 revealed a loss of carbonyl adsorptions and a loss in catalytic activity upon reuse (37). 

Process Design for Hydroformylating Octenes at the University of Kansas... 

Propjiene (qv) [115-07-1] is the predominant 0x0 process olefin feedstock. Ethylene (qv) [74-85-1J, as well as a wide variety of terminal, internal, and mixed olefin streams, are also hydroformylated commercially. Branched-chain olefins include octenes, nonenes, and dodecenes from fractionation of oligomers of C —C olefins as well as octenes from dimerization and codimerization of isobutylene and 1- and 2-butenes (see Butylenes). 

In this context, the use of ionic liquids with halogen-free anions may become more and more popular. In 1998, Andersen et al. published a paper describing the use of some phosphonium tosylates (all with melting points >70 °C) in the rhodium-catalyzed hydroformylation of 1-hexene [13]. More recently, in our laboratories, we found that ionic liquids with halogen-free anions and with much lower melting points could be synthesized and used as solvents in transition metal catalysis. [BMIM][n-CgHi7S04] (mp = 35 °C), for example, could be used as catalyst solvent in the rhodium-catalyzed hydroformylation of 1-octene [14]. 

As early as 1972 Parshall described the platinum-catalyzed hydroformylation of ethene in tetraethylammonium trichlorostannate melts [1]. [NEt4][SnCl3], the ionic liquid used for these investigations, has a melting point of 78 °C. Recently, platinum-catalyzed hydroformylation in the room-temperature chlorostannate ionic liquid [BMIM]Cl/SnCl2 was studied in the author s group. The hydroformylation of 1-octene was carried out with remarkable n/iso selectivities (Scheme 5.2-13) [66]. 

Scheme 5.2-13 Biphasic, Pt-catalyzed hydroformylation of 1-octene with a slightly acidic...

Moreover, these experiments reveal some unique properties of the chlorostan-nate ionic liquids. In contrast to other known ionic liquids, the chlorostannate system combine a certain Lewis acidity with high compatibility to functional groups. The first resulted, in the hydroformylation of 1-octene, in the activation of (PPli3)2PtCl2 by a Lewis acid-base reaction with the acidic ionic liquid medium. The high compatibility to functional groups was demonstrated by the catalytic reaction in the presence of CO and hydroformylation products. 

The results obtained in the biphasic hydroformylation of 1-octene are presented in Table 5.2-1. In order to evaluate the properties of the ionic diphosphine ligand... 

Table 5.2-1 Comparison of different phosphine ligands in the Rh-catalyzed hydroformylation of 1-octene in [BMIM][PFd.

Figure 5.2-5 Recycling experiments - Rh-catalyzed, biphasic 1-octene hydroformylation in...

Another interesting recent development is the continuous, Rh-catalyzed hydroformylation of 1-octene in the unconventional biphasic system [BMIM][PF6]/scC02, described by Cole-Hamilton et al. [84]. This specific example is described in more detail, together with other recent work in ionic liquid/scC02 systems, in Section 5.4. 

In the author s group, much lower-melting benzenesulfonate, tosylate, or octyl-sulfate ionic liquids have recently been obtained in combination with imidazolium ions. These systems have been successfully applied as catalyst media for the biphasic, Rh-catalyzed hydroformylation of 1-octene [14]. The catalyst activities obtained with these systems were in all cases equal to or even higher than those found with the commonly used [BMIM][PF6]. Taking into account the much lower costs of the ionic medium, the better hydrolysis stability, and the wider disposal options relating to, for example, an octylsulfate ionic liquid in comparison to [BMIM][PF6], there is no real reason to center future hydroformylation research around hexafluorophosphate ionic liquids. 

Figure 5.4-1 Continuous flow apparatus as used for the hydroformylation of 1-octene in the...

Buchmeiser and Nuyken [20], Weberskirch [21] and co-workers, examined the hydroformylation of 1-octene with a series of compounds of the formula [RhX(COD)(NHC)] (Fig. 9.1). The choice of halogen does not affect the reactivity, implying an active catalyst of the general formula [RhH(CO)3(NHC)]. Also, significant differences were observed in the initial TOF between catalysts (8,9) and (10,11) bearing iV- Pr and iV-Mes groups, respectively. Complex 11 exhibited a TOF of 1 480 h , whereas under identical conditions, 9 only turned over at a frequency of... 

Llewellyn, Green, and Cowley isolated the Co-H complex [CoH(CO)3(IMes)] 26, a relatively stable complex under inert conditions [31], The authors examined the hydroformylation activity of 1-octene with Co-hydride complex 26. With 8 atm of syngas (H /CO) at 50°C for 17 h and 1 mol% 26, the conversion to aldehyde products was 47% with a l b of 0.78. However, 83% of the product was the internal aldehyde 2-methyl-octanal, indicating isomerisation competed with hydroformylation and the rate of isomerisation occurred faster than hydroformylation. 

The product is 2,7-octadien-l-oI which can be dehydrogenated/hydrogenated internally to give 7-octenal, which can be hydroformylated to the dialdehyde, nonadialdehyde, and then hydrogenated to nonadiol. The initial product can be hydrogenated to 1-octanol the dialdehyde can be oxidized to the diacid. The catalyst used is Pd modified with the Li salt of monosulphonated triphenylphosphine. 

Thermomorphic solvent mixtures have been tested for hydroformylation of 1-octene and 1-dodecene to determine the ease of product recovery and catalyst recycling. Using both batch and continuous reactors, we demonstrated the efficacy of a biphasic, thermomorphic, system that had the following advantages ... 

Batch Experiments with Thermomorphic Systems. As a reference, we tested the hydroformylation of 1-octene in a completely homogeneous system using the same rhodium triphenylphosphine catalyst that is used for hydroformylation of lower aldehydes. This is sample R39 in Table 28.1, and gives us a baseline to compare the performance of our systems in terms of conversion and selectivity. To maintain consistency, we performed all the reactions at 100°C using the same amounts of reactants, catalysts and solvents. Under these conditions we only detected aldehyde products no alcohol or alkene isomers were formed. 

Table 28.3. Comparison of water-soluble solvents on biphasic hydroformylation of 1-octene.

In summary, what we have found is that the combination of a thermomorphic system and a surfactant is very effective for the hydroformylation of 1-octene and 1-dodecene. We believe that although a 90 10 ethanol/water and heptane system becomes miscible at 70°C, the additional water in a 50 50 ethanol/water and heptane system raises the miscibility temperature to >100°C. When a surfactant is added, the miscibility temperature is lowered and the biphasic solution becomes monophasic below the reaction temperature, resulting in good reaction rates. In addition, the presence of the surfactant also enhances the selectivity compared to the completely homogeneous system from 1.8 to 5.3 L/B... 

We have developed a thermomorphic catalyst system for the hydroformylation of higher alkenes. We have built a bench-scale continuous reactor and have used it to determine the long-term performance of the thermomorphic catalyst system. Longterm results (>400 h) using 1-octene and 1-dodecene show that the catalyst has high selectivity and no measurable loss in activity. 

In another interesting area in the study of hydroformylation, Davis developed the concept of supported aqueous phase (SAP) catalysis.175 A thin, aqueous film containing a water-soluble catalyst adheres to silica gel with a high surface area. The reaction occurs at the liquid-liquid interface. Through SAP catalysis, the hydroformylation of very hydrophobic alkenes, such as octene or dicyclopentadiene, is possible with the water-soluble catalyst [HRh(CO)(tppts)3]. 

Table 5 Regioselectivities of rhodium-catalyzed hydroformylation of 1-octene using toluene and MeOH as solventsa...

Ligand self-assembly through coordinative bonding has been used to increase the bulkiness of a monodentate tris-3-pyridyl phosphine ligand employing the zinc porphyrin/pyridine interaction (Scheme 33) [95-97]. The corresponding rhodium catalyst allowed for regioselective hydroformylation of2-octene [95]. 

A catalyst used for the u-regioselective hydroformylation of internal olefins has to combine a set of properties, which include high olefin isomerization activity, see reaction b in Scheme 1 outlined for 4-octene. Thus the olefin migratory insertion step into the rhodium hydride bond must be highly reversible, a feature which is undesired in the hydroformylation of 1-alkenes. Additionally, p-hydride elimination should be favoured over migratory insertion of carbon monoxide of the secondary alkyl rhodium, otherwise Ao-aldehydes are formed (reactions a, c). Then, the fast regioselective terminal hydroformylation of the 1-olefin present in a low equilibrium concentration only, will lead to enhanced formation of n-aldehyde (reaction d) as result of a dynamic kinetic control. 

Chart 1 Ligands used for isomerizing hydroformylation of internal octenes and 2-pentene. 

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