Hydroformylation table

With rhodium and (—)-DIOP as the chiral ligand, the chirality of the antipode preferentially reacted is opposite in hydrogenation ([Rh(NBD)Cl]2 as the catalyst precursor) compared to hydroformylation (Table 5). 

Tables l.I2a and 2.12b offer a variety of economic data concerning the production of hydrogen from different feedstocks, as ell as that of synthesis gas in an H CO molar ratio ranging from 1 1 to 3 1. In fact, the techniques employed to produce pure hydrogen can be exploited to adapt the composition of Hj/CO gas mixtures, so as to use them in specific conversions like those giving rise to certain alcohols (see Sections 9.3 and 9.4) by olefin hydroformylation. Table 1.12c gives details about processes for the elimination of add gases obtained starting with natural gas and coal.

Scheme 4 shows a platinum catalyst 1 containing such a bis-SPO bidentate ligand anion, designed for the hydroformylation of ethylene and of 1-heptene, and various other, similarly built, platinum catalysts. Catalyst 1 has an activity comparable to that of the commercial cobalt catalysts that were used at the time and displays a higher selectivity for linear products than the cobalt-containing catalysts (66). Like the latter, the platinum complex exhibits hydrogenation activity to give, in part, alcohols in addition to aldehydes and also produces alkanes (an undesired reaction that implies a loss of feedstock). The catalysts are also active for isomerization, as are the cobalt complexes, and for internal heptene hydroformylation (Table 1), with formation of 60% linear products. 

In order to integrate Equation (1.5.20), Cg and Cc must be related to Ca and this can be done by the use of Equation (1.2.5). Therefore, analysis of a trimolecular process is a straightforward extension of bimolecular processes. If trimolecular processes are rare and give slow rates, then the question arises as to how reactions like hydroformylations (Table 1.4.1) can be accomplished on a commercial scale (Vignette 1.5.1). The hydroformylation reaction is for example (see Table 1.4.1) ... 

CH3CH=CH(CH2)3CH3 (2-heptene) Comparison of cis- and Irans- hydrocarboxylation rates 14.6.4.3. Relative rate of hydroformylation (table) 14.6.3.2. 

The series of new diphosphines have been tested in the rhodium-catalyzed hydroformylation (Table 1) of 1-octene. The reaction rates for the catalysts derived from the pyridyl-modified ligands 10-12 and POPpy are higher than those of BISBI and 13, which is consistent with earlier observations made for the pyridyl-modified triphenylphosphines [19]. 

Recently, Dupont et al. [76] have reported the hydroformylation of olefins in neat conditions using unmodified or Xantphos-modified Rh(0) nanoparticles, prepared by simple hydrogenation reduction of the chloride salts in imidazolium ionic liquids. They have shown that the particle size has a strong influence on the selectivity of the hydroformylation (Table 11.13). 

Formation of isomerized olefin in the case of cobalt catalysts occurs with a higher rate than hydroformylation only at low partial pressures (<5 MPa) of carbon monoxide in the temperature range of 80-120°C. At higher partial pressures (>5 MPa) of carbon monoxide, the rate of olefin isomerization become slower than the rate of olefin hydroformylation. Tables 5 and 6 show relevant product composition in pentene hydroformylation at two different carbon monoxide partial pressures using unmodified cobalt catalyst. 

I 6 Synthesis of Special Products via Hydroformylation Table 6.3 Hydroformylation of different 1-aryl-prop-1-enes. 

The calculated natural bite angles of ligands 13,14,15, and 16 are 110°, 113°, 111°, and 102°, respectively. Ligands 13-16 were tested in the platinum/tin-catalyzed hydroformylation (Table 1.3). In the hydroformylation of 1-octene, the arsine-based ligands 14 and 15 proved to give more efficient catalysts than the parent xantphos ligand 13. The... 

In addition to rhodium(III) oxide, cobalt(II) acetylacetonate or dicobalt octacarbonyl has been used by the submitters as catalyst precursors for the hydroformylation of cyclohexene. The results are given in Table I. 

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... 

It is noteworthy that a clear enhancement of selectivity for the linear hydro-formylation product is observed only with cdpp (Table 5.2-1, entry e). With all other ligands, the n/iso ratios are in the 2 to 4 range. While this is in accordance with known results in the case of PPI13 (entry a) and dppe (entry c) (in comparison to monophasic hydroformylation [69]) and also with reported results in the case of Natppts (entry b in comparison to the biphasic hydroformylation of 1-pentene in [BMIM][PF(3] [46]), it is more remarkable for the bidentate metallocene ligand dppf... 

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

When water-miscible ionic liquids are used as solvents, and when the products are partly or totally soluble in these ionic liquids, the addition of polar solvents, such as water, in a separation step after the reaction can make the ionic liquid more hydrophilic and facilitate the separation of the products from the ionic liquid/water mixture (Table 5.3-2, case e). This concept has been developed by Union Carbide for the hydroformylation of higher alkenes catalyzed by Rh-sulfonated phosphine ligand in the N-methylpyrrolidone (NMP)/water system. Thanks to the presence of NMP, the reaction is performed in one homogeneous phase. After the reaction. 

Ziegler-Natta catalyst for polymerization of alkenes. Considerable attention has been directed to double-bonded Fischer carbenes of Cr and W, the Schrock carbenes of Ta and Ti, and cyclic polyene ligands of Fe, Co, Cr, and U. Carbonyls of transition metals from groups 6 to 10 of the periodic table include both the monomeric compounds such as Cr(CO)g, Fe(CO)5, Ni(CO)4 and those with two metal groups such as Mn2(CO)io and Co2(CO)s, which is used industrially for hydroformylation. Although their source has not been identified, it has been shown that volatile compounds from landfills contain carbonyls of Mo and W (Feldmann and Cullen 1997). 

The results obtained are reported in Table 5. Under the hydroformylation conditions, 1,3-butadiene is converted... 

Table 5. Hydroformylation of open-chain conjugated dienes by rhodium/mesitylene co-condensate, catalyst A . Substrate...

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.

Hydroformylation of a range of 1,1-di- and 1,1,2-trisubstituted unsatur-ated esters yields quaternary aldehydes (Table 1, entries 1-8). Hence, the regiochemistry-directing influence of the electron-withdrawing ester function overcompensates Keuleman s rifle. Furthermore, hydroformylation of 1,2-disubstituted unsaturated esters occurred with high a-selectivity and chemoselectivity (Table 1, entries 9 and 10). As a side reaction hydrogenation of the alkene has been observed [41]. 

Table 1 Results of branched-selective hydroformylation of a.fi-unsaturated esters with a rhodium/phosphaadamantane (1) catalyst...

Table 2 Results of room-temperature/ambient-pressure hydroformylation of functionalized terminal alkenes with the rhodium/6-DPPon (10) catalyst...

Table 3 4x4 ligand matrix of aminopyridine (4a-d)/isoquinolone (5a-d) derived self-assembled bidentate ligands in the [Rh]-catalyzed hydroformylation of l-octenea... 

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

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