Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-08-29
2002-08-27
Lambkin, Deborah C. (Department: 1626)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C558S085000, C568S903000, C568S454000, C568S449000
Reexamination Certificate
active
06440891
ABSTRACT:
The present invention relates to a catalyst comprising a complex of a VIIIth transition group metal other than nickel with at least one bi- or more highly dentate phosphonite ligand wherein the phosphorus and one of the oxygen atoms of the phosphonite group are part of a from 5- to 8-membered heterocycle, and to a process for hydroformylating compounds containing at least one ethylenically unsaturated double bond in the presence of such a catalyst.
The hydroformylating or oxo process is widely used for the large scale production of aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes may optionally be hydrogenated with hydrogen in the same operation to form the corresponding oxo alcohols. The reaction itself is highly exothermic and generally takes place under elevated pressure and temperature in the presence of catalysts. The catalysts used are cobalt, rhodium or ruthenium compounds or complexes which may be promoted with amine or phosphine ligands. Additional promoters have hitherto not achieved any significance in the industry. The hydroformylation reaction gives rise to the formation of isomeric aldehyde mixtures because of the possible CO addition to each of the two carbon atoms of a double bond. In addition, if internal olefins are used, the double bond may isomerize from an internal into a terminal position. In these isomeric mixtures, the n-aldehyde is generally favored over the iso-aldehyde, but because of the significantly greater industrial importance of the n-aldehydes it is desirable to optimize the hydroformylation catalysts with regard to achieving a greater n-selectivity.
Beller et al., Journal of Molecular Catalysis A, 104 (1995), 17-85, describe phosphine-modified rhodium catalysts for the hydroformylation of low boiling olefins. The disadvantages with these catalysts are that they can only be prepared using organometallic reagents and that the ligands used are difficult and expensive to make. In addition, these phosphine-modified catalysts are very slow to hydroformylate internal, straight-chain and branched olefins and also olefins having more than 7 carbon atoms.
WO 95/30680 describes bidentate phosphine ligands where the two phosphine groups are both bonded to an aryl radical and these two aryl radicals form a doubly bridged, ortho-fused ring system in which one of the two bridges consists of an oxygen or a sulfur atom. Rhodium complexes based on these ligands are useful as hydroformylation catalysts, and the hydroformylation of terminal olefins provides a good n/iso ratio. The disadvantage of these chelated phosphines is their difficulty of preparation, so that industrial processes which rely on such chelated phosphine catalysts are at an economic disadvantage.
U.S. Pat. No. 4,169,861 describes a process for preparing terminal aldehydes by hydroformylating &agr;-olefins in the presence of a rhodium hydroformylation catalyst based on a bidentate ligand and a monodentate ligand. The preferred bidentate ligand is 1,1′-bis(diphenylphosphino)ferrocene. The monodentate ligand is preferably a phosphine, such as diphenylethylphosphine.
U.S. Pat. Nos. 4,201,714 and 4,193,943 have a similar disclosure content. The preparation of the bidentate phosphinoferrocene ligands requires the use of organometallic reagents, which are expensive to make, putting hydroformylation processes that employ these catalysts at an economic disadvantage.
U.S. Pat. No. 5,312,996 describes a process for preparing 1,6-hexanedial by hydroformylating butadiene in the presence of hydrogen and carbon monoxide. The hydroformylation catalysts used are rhodium complexes with polyphosphite ligands wherein the phosphorus and two of the oxygen atoms of the phosphite group are part of a 7-membered heterocycle.
JP-A 97/255 610 describes a process for preparing aldehydes by hydroformylation in the presence of rhodium catalysts comprising a monodentate phosphonite ligand.
None of the references cited above describes hydroformylation catalysts based on bi- or more highly dentate phosphonite ligands wherein the phosphonite group is part of a 5- to 8-membered heterocycle.
It is an object of the present invention to provide novel catalysts based on complexes of a metal of the VIIIth transition group. They shall be highly useful for hydroformylation and possess good catalytic activity.
We have found that this object is achieved, surprisingly, by catalysts based on complexes of a metal of the VIIIth transition group which comprise at least one bi- or more highly dentate phosphonite ligand wherein the phosphonite group is part of a from 5- to 8-membered heterocycle.
The present invention accordingly provides a catalyst comprising a complex of a VIIIth transition group metal other than nickel with a bi- or more highly dentate phosphonite ligand of the general formula I
where
m is 0 or 1,
A combines with that part of the phosphonite group to which it is attached to form a 5- to 8-membered heterocycle which may optionally be additionally singly, doubly or triply fused with cycloalkyl, aryl and/or hetaryl, in which case the fused-on groups may each bear one, two or three substituents selected from the group consisting of alkyl, alkoxy, halogen, nitro, cyano and carboxyl,
R
1
is a C
3
- to C
6
-alkylene bridge which may have one, two or three double bonds and/or may be singly, doubly or triply fused with aryl and/or hetaryl, in which case the aryl or hetaryl groups may bear one, two or three substituents selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cycloalkyloxy, aryloxy, halogen, trifluoromethyl, nitro, cyano, carboxyl and NE
1
E
2
, where E
1
and E
2
are identical or different and each is alkyl, cycloalkyl or aryl,
D has the meanings specified above for A,
or salts and mixtures thereof.
For the purposes of the present invention, alkyl denotes both straight-chain and branched alkyls. Alkyl is preferably straight-chain or branched C
1
-C
8
-alkyl, more preferably C
1
-C
6
-alkyl, particularly preferably C
1
-C
4
-alkyl. Examples of alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl.
Cycloalkyl is preferably C
5
-C
7
-cycloalkyl, such as cyclopentyl, cyclohexyl or cycloheptyl.
Substituted cycloalkyl preferably has 1, 2, 3, 4 or 5, especially 1, 2 or 3, substituents selected from the group consisting of alkyl, alkoxy and halogen.
Aryl is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl or naphthacenyl and especially phenyl or naphthyl.
Substituted aryl preferably has 1, 2, 3, 4 or 5, especially 1, 2 or 3, substituents selected from the group consisting of alkyl, alkoxy and halogen.
Hetaryl is preferably pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
Substituted hetaryl preferably has 1, 2 or 3 substituents selected from the group consisting of alkyl, alkoxy and halogen.
The above remarks concerning alkyl, cycloalkyl and aryl apply mutatis mutandis to alkoxy, cycloalkyloxy and aryloxy.
NE
1
E
2
is preferably N,N-dimethyl, N,N-diethyl, N,N-dipropyl, N,N-diisopropyl, N,N-di-n-butyl, N,N-di-t.-butyl, N,N-dicyclohexyl or N,N-diphenyl.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
In a preferred embodiment, the present invention provides catalysts comprising at least one phosphonite ligand of the formula I wherein A combines with that part of the phosphonite group to which it is attached to form a 5- or 6-membered heterocycle which may optionally be singly or doubly fused with aryl and/or hetaryl, in which case the fused-on groups may bear one, two or three of
Fischer Jakob
Maas Heiko
Paciello Rocco
Röper Michael
Siegel Wolfgang
BASF - Aktiengesellschaft
Keil & Weinkauf
Lambkin Deborah C.
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