Hydroformylation catalyst comprising a complex with ligands...

Details Hydroformylation catalyst comprising a complex with ligands... Hydroformylation catalyst comprising a complex with ligands...

2002-02-13

2003-10-28

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S451000, C568S480000, C568S633000, C568S638000, C568S017000, C568S021000, C568S022000, C502S162000

Reexamination Certificate

active

06639114

ABSTRACT:

The present invention relates to a process for the hydroformylation of ethylenically unsaturated compounds, in which the hydroformylation catalyst used comprises at least one complex of a metal of transition group VIII with at least one phosphorus-containing compound as ligand, where this compound in each case comprises two groups containing P atoms and bound to a molecular skeleton derived from bisphenol A. The invention further relates to novel compounds of this type and catalysts comprising at least one complex of a metal of transition group VIII with at least one such compound as ligand.
Hydroformylation or the oxo process is an important industrial process and is employed for preparing aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can, if desired, be hydrogenated by means of hydrogen in the same process to produce the corresponding oxo alcohols. The reaction itself is strongly exothermic and generally proceeds under superatmospheric pressure and at elevated temperatures in the presence of catalysts. Catalysts used are Co, Rh, Ir, Ru, Pd or Pt compounds or complexes which may be modified with N- or P-containing ligands to influence the activity and/or selectivity. Owing to the possible addition of CO at each of the two carbon atoms of a double bond, the hydroformulation reaction results in the formation of mixtures of isomeric aldehydes. In addition, it is possible for double bond isomerization, i.e., a shift of internal double bonds to a terminal position and vice versa, to occur.
Owing to the considerably greater industrial importance of &agr;-aldehydes, optimization of the hydroformylation catalysts so as to achieve a very high hydroformylation activity combined with a very low tendency to form aldehyde groups which are not in the &agr; position is desirable. In addition, there is a need for hydroformylation catalysts which lead to good yields of &agr;-aldehydes, in particular n-aldehydes, even when internal linear olefins are used as starting materials. Here, the catalyst has to make possible the establishment of an equilibrium between internal and terminal double bond isomers and also very selectively catalyze the hydroformylation of the terminal olefins.
The use of phosphorus-containing ligands for stabilizing and/or acvtivating the catalyst metal in rhodium-catalyzed low-pressure hydroformylation is known. Suitable phosphorus-containing ligands are, for example, phosphines, phosphinites, phosphonites, phosphites, phosphoramidites, phospholes and phosphabenzenes. The most widely used ligands at present are triarylphosphines, e.g. triphenylphosphine and sulfonated triphenylphosphine, since these have sufficient stability under the reaction conditions. However, these ligands suffer from the disadvantage that very high excesses of ligands are generally necessary to achieve satisfactory yields, particularly of linear aldehydes.
In Eur. J. Inorg. Chem. 2001, 247-255, C. G. Arena et al. describe metallamacrocycles of Pd, Pt and Cu complexes of the ligands [{p-(Ph
2
PO)C
6
H
4
}
2
CMe
2
], [{2-Ph
2
PO-3,5-(Me
3
C)
2
C
6
H
2
}
2
S] and [{p-[(C
10
H
6
O)
2
PO]C
6
H
4
}
2
CMe
2
]. Use in hydroformylation is not described.
In Angew. Chem. Int. Ed. 39, 1639 (2000), D. Selent et al. describe the isomerizing hydroformylation of internal olefins in the presence of rhodium catalysts in which oxyfunctionalized bisphenylmonophosphonites are used as ligands. A disadvantage of these catalysts is their low n-selectivity. Thus, the hydroformylation of isomeric n-octenes gave n-nonanal in a yield of not more than 47.9%.
WO-A-98/43935 describes the use of chelating ligands in catalysts for hydroformylation.
In Organometallics 1995, 14, pp. 3081-3089, M. Kranenburg et al. describe chelating phosphines such as bis(2-(diphenylphosphino)-phenyl) ether and ones having a xanthene skeleton and their use for regioselective rhodium-catalyzed hydroformylation. A disadvantage of these chelating phosphines is that they are not suitable for the isomerizing hydroformylation of internal olefins with high &agr;- or n-selectivity.
In Organometallics 1999, 18, pp. 4765-4777, van der Veen et al. describe the use of phosphacyclic diphosphines having a xanthene skeleton as ligands for rhodium-catalyzed hydroformylation. A disadvantage of these catalysts is their very low activity which makes their use in industrial processes uneconomical.
WO 95/30680 describes bidentate phosphine ligands in which the phosphorus atoms are bridged by ortho-fused ring systems comprising two aryl groups and also describes the use of these ligands in catalysts for hydroformylation. A disadvantage of these catalysts is that they are not suitable for the isomerizing hydroformylation of internal olefins with good &agr;- or n-selectivity.
EP-A-0982314 describes bidentate carbocyclic or heterocyclic phosphine ligands and a process for preparing linear aldehydes by hydroformylation of internal olefins using such ligands. A disadvantage of these ligands is their very low activity which makes their use in industrial processes uneconomical.
DE-A-19827232 describes catalysts based on monodentate, bidentate or polydentate phosphinite ligands in which the phosphorus atom and oxygen atom of the phosphinite group are part of a 5- to 8-membered heterocycle and also describes their use for hydroformylation and hydrocyanation. The bidentate ligands can, inter alia, have a xanthene skeleton. A disadvantage of these ligands is that the &agr;- or n-selectivity in the isomerizing hydroformylation of internal olefins is in need of improvement.
U.S. Pat. No. 4,694,109, No. 4,755,624, No. 4,851,581 and No. 4,904,808 describe chelating ligands for hydroformylation which have a skeleton based on two aryl groups bound directly to one another via a single bond.
U.S. Pat. No. 5,332,846 describes bisphosphines in which two phosphine groups are bound via substituted or unsubstituted methylene groups to a molecular skeleton comprising two arylene groups joined via a single bond. These are suitable as ligands for hydroformylation catalysts.
The unpublished German patent application P 100 05 794.2 describes compounds of phosphorus, arsenic and antimony based on diaryl-fused bicyclo[2.2.n] skeletons and their use as ligands for hydroformylation catalysts.
The unpublished German patent application P 100 46 026.7 describes a hydroformylation process in which the catalyst used comprises at least one complex of a metal of transition group VIII with at least one phosphorus-, arsenic- or antimony-containing compound having a xanthene-like molecular skeleton as ligand.
The unpublished German patent applications 100 23 471.2 and 101 01 939.4 describe a hydroformylation process in which the hydroformylation catalyst used is a complex of a metal of transition group VIII with at least one ligand comprising two triaryl groups, where each of the triaryl groups comprises a phosphorus-, arsenic- or antimony-containing radical and one aryl radical of each of the two triaryl groups is bound via a single bond to a nonaromatic 3- to 8-membered carbocyclic or heterocyclic bridging group.
None of the abovementioned documents describes phosphorus-containing compounds having a skeleton derived from bisphenol A and their use as ligands in hydroformylation catalysts.
It is an object of the present invention to provide an improved process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond. In the hydroformylation of &agr;-olefins, it should preferably achieve a very high proportion of &agr;-aldehydes or &agr;-alcohols (&agr;-selectivity). In particular, the process should be suitable for the hydroformylation of internal linear olefins with high regioselectivity to terminal product aldehydes. A further object of the invention is to provide novel compounds and novel catalysts which comprise at least one complex of a metal of transition group VIII with such a compound as ligand.
We have found that this object is achieved by a hydroformylatio

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