Organic compounds -- part of the class 532-570 series – Organic compounds – Carbohydrates or derivatives
Patent
1999-01-27
2000-07-11
Padmanabhan, Sreeni
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbohydrates or derivatives
536120, 5361231, 568451, 568454, C08B 3716, C07C 4550
Patent
active
060874813
DESCRIPTION:
BRIEF SUMMARY
This is the U.S. National Stage Application of PCT/EP97/04117 filed Jul. 29, 1997.
FIELD OF THE INVENTION
The present invention relates to a process for the hydroformylation of terminal and internal olefins in a two-phase system using novel metal catalysts. The two-phase system consists of an aqueous and an organic phase. The metals belong to group VIII of the Periodic Table, e.g., Rh, Ru, Ir, Co or Pd. The ligands for the metals are novel phosphane-modified .beta.-cyclodextrins which are water-soluble.
The aldehydes formed in the hydroformylation are industrially useful compounds which are either used directly, e.g., as aromatic principles, or as intermediates for the production of other classes of substances, as in the preparation of solvents, detergents, perfumes, pharmaceutical agents or plasticizers [K. Weissermel, H. J. Arpe, Industrial Organic Chemistry, VCH, Weinheim, 1993].
BACKGROUND OF THE INVENTION
Commercially, the cobalt catalysts introduced by Roelen, e.g., Co.sub.2 (CO).sub.8, are used at 150-180.degree. C./150-200 atm, conditions which lead to side-reactions, such as hydrogenation, isomerization and aldehyde condensation. In the so-called low pressure oxo process, rhodium complexes which are soluble in organic solvents, such as HRh(CO) (PPh.sub.3).sub.3, are used as catalysts, working at 90-110.degree. C./20 atm and thus yielding less undesirable side-products. This process as well as other homogeneously catalyzed hydroformylations are mainly used for the production of butyric aldehyde and other low-boiling aldehydes. However, with homologous or higher-boiling aldehydes, the distillative separation from the catalyst is problematic [G. W. Parshall, S. D. Itell, Homogeneous Catalysis, Wiley, New York, 1992]. For this reason, attempts are being made in the industry world-wide to perform hydroformylations in a two-phase system [B. Cornils, in New Syntheses with Carbon Monoxide (J. Falbe, ed.), Springer Publishers, New York, 1980; B. Cornils, E. Wiebus, Chemtech. 1995, 33]. To this end, water-soluble phosphanes, e.g., P(C.sub.6 H.sub.4 SO.sub.3 Na).sub.3, are used as ligands for the rhodium (TPPTS-Rh system). The Rh catalyst is present in the aqueous phase whereas the olefin and the product (aldehyde) are present in the organic phase. In this way, Hoechst/Rhone-Poulenc produce n-butyric aldehyde from propene [B. Cornils, E. Wiebus, Chem. Ing. Tech. 66 (1994), 916; W. A. Herrmann et al., J. Mol. Catal. 97 (1995), 65]. Unfortunately, this simple process is limited to ethylene and propene, which have a water solubility which, although low, is yet sufficiently high to be reacted in the aqueous or catalyst-containing phase. Homologous olefins, such as n-hexene or n-octene, are virtually not or but poorly reacted in this system. Therefore, there have been many attempts to solve this problem, e.g., using surfactants or phase-transfer catalysts, especially ligands or solvents, but only with limited success as recently reviewed by E. Monflier [Angew. Chem. 107 (1995), 2450; Tetrahedron Lett. 36 (1995), 9481]. An improvement is described by E. Monflier [supra] according to which .beta.-cyclodextrin derivatives (.beta.-CD derivatives) are added to the two-phase system, serving as solubilizers. In the case of longer-chain olefins, such as 1-octene or 1-decene, the activity of the catalyst system is increased thereby by a maximum of about 10fold so that reasonable yields of the corresponding aldehydes are obtained, i.e., with n/iso ratios of about 2:1. However, the chemical selectivity is only 85-90% as a rule, i.e., 10-15% of side-products is obtained. Internal (i.e., non-terminal) olefins, such as 5-decene, are virtually not hydroformylated at all (only 3% conversion), i.e., the catalyst system is not very active. In addition, a great disadvantage is the fact that a large excess of .beta.-cyclodextrin derivative is necessary; typically, the ratio of Rh:P(C.sub.6 H.sub.4 SO.sub.3 Na).sub.3 :.beta.-cyclodextrin derivative is about 1:8:14. The advantage of a moderate increase in activity by the use of
REFERENCES:
E. Monflier et al. "A Further Breakthrough . . . Catalysts", Tetrahedron Letters, Bd, 36, Nr. 52, Dec. 25, 1995, pp. 9481-9484.
Reetz Manfred T.
Waldvogel Siegfried
Padmanabhan Sreeni
Studiengesellschaft Kohle MBH
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