Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-01-13
2002-05-14
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S429000, C568S447000, C568S454000, C568S378000, C562S406000, C562S522000
Reexamination Certificate
active
06388141
ABSTRACT:
This application is a 371 of PCT/EP98/04319, which was filed on Jul. 11, 1998.
The present invention relates to processes for the preparation of oxo products by the hydroformylation of substrates having C═C double bonds using unmodified rhodium catalysts in a reaction mixture essentially consisting of the substrates, the catalyst and carbon dioxide in a supercritical state (scCO
2
). In particular, the invention relates to such processes for the preparation of products which contain substantial proportions of branched i-oxo products. Further, the invention relates to such processes for the hydroformylation of substrates which do not correspond to the general formula C
n
H
2n
. The invention further relates to such processes in which the separation of product and catalyst is effected using the special solvent properties of scCO
2
.
The transition metal catalyzed reaction of substrates containing C═C double bonds with a mixture of hydrogen (H
2
) and carbon monoxide (CO) is referred to as hydroformylation or oxo reaction; it is a technically important method for the preparation of aldehydes and alcohols (oxo products). More than 6 million tons per year of oxo products are produced by catalytic hydroformylation worldwide. These products are employed as plasticizers and modifiers for PVC and other polymers, in detergent production, and as fine chemicals and as intermediates for the production of agrochemicals, food additives and pharmaceuticals (C. D. Frohning, C. W. Kohlpaintner, in Applied Homogeneous Catalysis with Organometallic Compounds (editors: B. Cornils, W. A. Herrmann), VCH, Weinheim, 1996, Vol. 1, Section 2.1.1).
Depending on the reaction parameters, the catalysts and the substitution pattern at the C═C double bond of the substrate, linear (normal, n-) or branched (iso, i-) oxo products are produced more or less selectively in the hydroformylation. Of the oxo products of simple short-chain olefins of general formula C
n
H
2n
(n=2, 3), it is mainly the n-products which are economically important. Of the long-chain olefins C
n
H
2n
(n≧4), the branched i-oxo products are also economically important and are discussed, for example, as starting materials for the preparation of plasticizers in pure form or as mixtures with the n-oxo products. Above all, the i-oxo products are also particularly important for substrates with functionalized C═C double bonds, i.e., substrates which do not correspond to the general formula C
n
H
2n
. In particular, reference may be made herein to the technical synthesis of vitamin A described in U.S. Pat. No. 3,840,589, DE 2 03 078 and U.S. Pat. No. 4,124,619, which involves the formation of an i-aldehyde by the hydroformylation of substrates comprising allyl ester moieties. The formation of branched products in the hydroformylation of vinyl aromatics (e.g., styrene) is discussed as a possible route to &agr;-aryl-carboxylic acids, which are employed, inter alia, as analgetics and antirheumatics (e.g., Ibuprofen®, Naproxen®, Suprofen®).
The catalysts for hydroformylation can be classified into so-called “unmodified” and “modified” catalysts which are respectively preferred for particular processes or particular substrates according to the prior art (C. D. Frohning, C. W. Kohlpaintner, supra, p. 33ff). “Modified” systems means catalysts in which the catalytically active metal component contains additional ligands, usually phosphorus compounds, in addition to H and CO for increasing the useful life and for controlling activity or selectivity. The term “unmodified catalysts” denotes all other metal compounds which are capable of forming catalytically active hydrido-carbonyl compounds under the reaction conditions. Technical importance has been achieved to date mainly by catalysts based on the metals cobalt (Co) and rhodium (Rh). The separation of the products and recovery of the catalysts is an important factor in the technical realization of hydroformylation reactions.
Supercritical (“fluid”) carbon dioxide (scCO
2
), i.e., compressed carbon dioxide at temperatures and pressures beyond the critical point (T
c
=31.0° C., p
c
=73.75 atm, d
c
=0.467 g·ml
−1
) is employed as a reaction medium for hydroformylation in U.S. Pat. No. 5,198,589 and in German Application DE-A-197 02 025.9 (Jan. 23, 1997). Carbon dioxide in a supercritical state is an interesting solvent for performing catalytic reactions because it is toxicologically and ecologically safe, in contrast to conventional organic solvents. Further, scCO
2
has the property of being completely miscible with many gaseous reaction partners within wide limits, whereby limitation of the reaction rate by diffusion processes, which frequently occurs in gas/liquid phase reactions, is totally avoided. Further, due to the solvent properties of scCO
2
which vary as a function of pressure and temperature, separation of main or side products from the reaction mixture is possible in favorable cases when the external parameters are appropriately selected. A survey of catalytic reactions in scCO
2
is found in Science 1995, 269, 1065.
In DE-A-197 02 025.9, modified rhodium catalysts are employed for the hydroformylation in scCO
2
, specially developed phosphorus compounds ensuring high solubility of the catalysts in scCO
2
. Thus, the stated advantageous properties of scCO
2
can be fully utilized with modified rhodium catalysts, but the preparation of the phosphorus ligands is an additional cost factor in possible technical applications. In U.S. Pat. No. 5,198,589, unmodified cobalt catalysts are employed for the hydroformylation of simple olefins C
n
H
2n
in scCO
2
. As compared to conventional solvents, similar reaction rates are obtained with significantly higher selectivities in favor of the linear n-oxo products. This increase in selectivity in favor of the n-oxo products is attributed to the use of scCO
2
as the reaction medium.
We have now found that unmodified rhodium catalysts can be efficiently used for hydroformylation in scCO
2
to obtain, surprisingly, not only significantly higher reaction rates, but also significantly higher selectivities in favor of the branched i-oxo products than are obtained in conventional solvents.
Rhodium catalyzed hydroformylations in scCO
2
are conveniently performed by charging the catalyst or catalyst precursor and the substrate into a high-pressure reactor and then pressurizing with H
2
and CO, either as a mixture or successively, at room temperature up to the desired partial pressure. Then, the amount of CO
2
required to reach the desired density of the reaction medium is filled into the reactor. Then, heating to the desired reaction temperature is performed with stirring. After said temperature has been reached, the stirrer can be turned off due to the fast diffusion within the homogeneous supercritical phase. After the desired reaction time, the pressure is released from the reactor, during which the products can be isolated from the supercritical phase using appropriate known methods (K. Zosel, Angew. Chem. 1978, 90, 748; M. A. McHugh, V. J. Krukonis, Supercritical Fluid Extraction: Principle and Practice, Butterworths, Stoneham, 1994). Due to the fact that the solubilities of the metal species and the products are clearly different, the catalysts can be easily separated from the products and recycled.
As catalysts or catalyst precursors for the formation of unmodified Rh systems in scCO
2
, salts, complexes or cluster compounds of rhodium in any oxidation state can be employed. Compounds 1-8 are preferred examples of such catalysts or catalyst precursors, without intending to limit the choice of the catalyst to the structures shown. Particularly preferred catalysts are complex compounds of rhodium, 4-8, containing carbonyl ligands (CO) or ligands which can be readily replaced by CO under the reaction conditions. The amount of catalyst can be freely selected within a broad range depending on the reaction conditions and the reactivity of the substrates. Typical amounts of catalysts, based on the amount
Koch Daniel
Leitner Walter
Norris & McLaughlin & Marcus
Padmanabhan Sreeni
Studiengesellschaft Kohle mbH
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