Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Reexamination Certificate
2003-06-04
2004-05-18
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
Reexamination Certificate
active
06737539
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns the use of catalyst compositions comprising a Group VIII metal and a multidentate phosphonite ligand for olefinic hydrocyanation and isomerization processes.
BACKGROUND OF THE INVENTION
Certain phosphonites have been used as a part of hydrocyanation catalyst systems. U.S. Pat. No. 5,817,850 discloses the use of a catalyst composition in hydroformylation and hydrocyanation reactions. WO9843935 discloses the use of certain phosphonite ligands as part of a catalyst system in a process for producing an aldehyde. WO9946044 relates to a hydroformylation process using phosphonite ligands as part of the catalyst system for hydroformylation reactions. U.S. Pat. No. 6,242,633 discloses a process for the production of nitriles using catalysts containing phosphonite ligands. Further, WO9964155 discloses use of catalysts containing phosphorous ligands in hydrocyanation reactions.
Despite the disclosure of various ligands in hydrocyanation and hydroformylation processes. Catalyst compositions comprising certain multidentate phosphonite ligands show effectiveness and/or higher performance and achieve improvements in rapidity, selectivity, efficiency or stability.
SUMMARY OF THE INVENTION
A hydrocyanation process, said process comprising: contacting an ethylenically unsaturated olefin compound with HCN in the presence of a catalyst composition, wherein said catalyst composition comprises a Group VIII metal and a phosphonite ligand wherein the ligand having a structure selected from the group consisting of:
wherein the X groups are either the same or different unbridged organic aromatic groups as described in Formula I, wherein Q is a substituted or unsubstituted divalent aromatic or non aromatic hydrocarbon radical. The substituent on the Q groups is independently selected from the group consisting of C1 to C12 alkyl, cycloalkyl, alkoxy, alkylaryl, aryl, hetero aryl, cyano or
The use of a catalyst based on a ligand of structure II for the hydrocyanation and/or the positional isomerization or double bond isomerization of olefins.
DETAILED DESCRIPTION
The present invention describes a hydrocyanation process comprising: contacting an ethylenically unsaturated olefin compound with HCN in the presence of a catalyst composition, wherein the catalyst composition comprises a Group VIII metal and a phosphonite ligand having a structure selected from the group consisting of:
wherein the X groups are either the same or different unbridged organic aromatic groups as described in Formula I, wherein Q is a substituted or unsubstituted divalent aromatic or non aromatic hydrocarbon radical; and when Q is substituted, the substituent on the Q group is independently selected from the group consisting of C1 to C12 alkyl, cycloalkyl, alkoxy, alkylaryl, aryl, hetero aryl, cyano.
Typical X for structure II include but are not limited to:
The hydrocyanation process described herein may be carried out in the presence of a catalyst precursor composition comprising a Group VIII metal and at least one multidentate phosphonite ligand having a structure II I as described above and optionally a Lewis acid.
Generally, a Group VII metal or a compound thereof is combined with at least one of the ligand structure II to provide the catalyst. Among the Group VII metal compounds, nickel, cobalt, and palladium compounds are preferred for hydrocyanation catalysts. A nickel compound is more preferred, and a zero-valent nickel compound having a ligand that can be chemically displaced by the ligand structure of the present invention is the most preferred source of Group VIII metal or Group VIII metal compound.
Zero-valent nickel compounds that can be used for preparing the catalyst of the present invention are disclosed in the art. The preferred zero-valent nickel compounds are Ni(COD)
2
(COD is 1,5-cyclooctadiene), Ni(P(O-o-C
6
H
4
CH
3
)
3
)
3
and Ni{P(O-o-C
6
H
4
CH
3
)
3
}
2
(C
2
H
4
), all of which are known in the art.
The catalyst of the present invention is prepared by combining the zero-valent nickel compound with at least one molar equivalent of the ligand of structure II of the present invention in a ratio of nickel:bidentate ligand of 1:1. The ligand may be combined with nickel in a solvent, or preferably in the substrate medium. Suitable solvents include, but are not limited to, hydrocarbons such as benzene, xylene, or combinations thereof; ethers such as tetrahydrofuran (THF); nitriles such as acetonitrile, benzonitrile, adiponitrile, or combinations of two or more thereof. The unsaturated olefin used in the hydrocyanation process may itself serve as the solvent. The catalyst preparation may be done at room temperature, or at a temperature that is appropriate for the solvent being used, or the hydrocyanation process conditions.
Alternatively, divalent nickel compounds can be combined with a reducing agent, to serve as a source of zero-valent nickel in the reaction. Suitable divalent nickel compounds include compounds of the formula NiZ
2
2
where Z
2
is halide, carboxylate, or acetylacetonate. Suitable reducing agents include metal borohydrides, metal aluminum hydrides, metal alkyls, Li, Na, K, Zn or H
2
.
The divalent nickel compound is combined with the ligand structure II of the present invention in a suitable solvent, preferably the unsaturated olefin, in a ratio of 1:1, or preferably at least 2:1. The combination is then combined with a suitable reducing agent at room temperature, or at a temperature that is appropriate for the solvent being used, or the hydrocyanation process conditions being used. The resulting catalyst composition may be isolated, if desired.
Hydrocyanation Using Phosphorus-Containing Ligands of the Present Invention:
The catalyst compositions of the present invention may be used with or without a Lewis acid in the hydrocyanation of organic compounds. The hydrocyanation process comprises contacting, in the presence of the catalyst, an olefinic unsaturated organic compound with a hydrogen cyanide-containing fluid under conditions sufficient to produce a nitrile, wherein the catalyst comprises a Group VIII metal, at least one of the ligands described above, and optionally a Lewis acid as a promoter. As used herein, the term “fluid” means gas, a liquid, or a combination of these. Any fluid containing about 1 to 100% HCN can be used.
A particularly significant use of the ligands of the present invention is in the hydrocyanation of olefins. In such a process, an olefinic compound such as a diolefinic compound can be converted to a nitrile or a dinitrile, or a combination thereof. The hydrocyanation process can be carried out, for example, by charging a suitable vessel with an olefin, catalyst composition, and solvent, if used, to form a reaction mixture. Hydrogen cyanide can be combined initially with other components to form the mixture. However, it is preferred that HCN be added slowly to the mixture after other components have been combined. Hydrogen cyanide can be delivered as a liquid or as a vapor to the vessel. As an alternative, a cyanohydrin can be used as the source of HCN. See, for example, U.S. Pat. No. 3,655,723, incorporated herein by reference.
Another suitable technique is to charge the vessel with the catalyst and the solvent (if any) to be used, and feed both the unsaturated compound and the HCN slowly to the reaction mixture.
The molar ratio of ethylenically unsaturated olefin compound to catalyst can be varied from about 10:1 to about 10000:1. The molar ratio of HCN to catalyst generally is varied from about 10:1 to 100,000:1, preferably 100:1 to 5,000:1, for a batch operation. In a continuous operation, such as when using a fixed bed catalyst type of operation, a higher proportion of catalyst can be used such as a molar ratio of about 5:1 to about 100,000:1, and preferably about 100:1 to about 5,000:1, HCN to catalyst.
Preferably, the reaction mixture is agitated, for example, by stirring or shaking. The reaction product can be recovered by conventional techniques such as distillation. The process can be run e
Lenges Christian P.
Lu Helen S. M.
Ritter Joachim C.
Deitch Gerald E.
E. I. DuPont de Nemours and Company
McKane Joseph K.
Shiao Robert
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