Metal-ligand complex catalyzed processes

Details Metal-ligand complex catalyzed processes Metal-ligand complex catalyzed processes

1999-07-27

2001-06-26

Padmanabhan, Sreeni (Department: 1621)

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

Organic compounds

Oxygen containing

C568S451000, C568S431000, C568S320000, C568S426000, C514S678000, C514S690000, C514S693000, C514S699000

Reexamination Certificate

active

06252121

ABSTRACT:

BRIEF SUMMARY OF THE INVENTION
TECHNICAL FIELD
This invention relates to improved metal-organophosphorus ligand complex catalyzed processes. More particularly this invention relates to metal-organophosphorus ligand complex catalyzed processes in which the desired product can be selectively separated from the reaction product fluid by phase separation.
BACKGROUND OF THE INVENTION
It is known in the art that various products may be produced by reacting one or more reactants in the presence of an metal-organophosphorus ligand complex catalyst. However, stabilization of the catalyst and organophosphorus ligand remains a primary concern of the art. Obviously catalyst stability is a key issue in the employment of any catalyst. Loss of catalyst or catalytic activity due to undesirable reactions of the highly expensive metal catalysts can be detrimental to the production of the desired product. Moreover, production costs of the product obviously increase when productivity of the catalyst decreases.
For instance, a cause of organophosphorus ligand degradation and catalyst deactivation of metal-organophosphorus ligand complex catalyzed hydroformylation processes is due in part to vaporizer conditions present during, for example, in the vaporization employed in the separation and recovery of the aldehyde product from the reaction product mixture. When using a vaporizer to facilitate separation of the aldehyde product of the process, a harsh environment of a high temperature and a low carbon monoxide partial pressure than employed during hydroformylation is created, and it has been found that when a organophosphorus promoted rhodium catalyst is placed under such vaporizer conditions, it will deactivate at an accelerated pace with time. It is further believed that this deactivation is likely caused by the formation of an inactive or less active rhodium species. Such is especially evident with organophosphites when the carbon monoxide partial pressure is very low or absent. It has also been observed that the rhodium becomes susceptible to precipitation under prolonged exposure to such vaporizer conditions.
For instance, it is theorized that under harsh conditions such as exist in a vaporizer, the active catalyst, which under hydroformylation conditions is believed to comprise a complex of rhodium, organophosphorus ligand, carbon monoxide and hydrogen, loses at least some of its coordinated carbon monoxide, thereby providing a route for the formation of such a catalytically inactive or less active rhodium. Accordingly, a successful method for preventing and/or lessening such degradation of the organophosphorus ligand and deactivation of the catalyst as occur under harsh separation conditions in a vaporizer would be highly desirable to the art.
DISCLOSURE OF THE INVENTION
It has now been discovered that in metal-organophosphorus ligand complex catalyzed processes, the desired product can be selectively separated from the reaction product fluid by phase separation. By the practice of this invention, it is now possible to separate the desired product from the reaction product fluid without the need to use vaporization separation and the harsh conditions associated therewith. This invention provides a highly desirable separation method which prevents and/or lessens degradation of the organophosphorus ligand and deactivation of the catalyst as occur under harsh conditions with vaporization separation. It has been discovered that in a reaction system containing a non-polar solvent, the introduction of certain hydrocarbon groups, e.g., an aldehyde group, onto the ring structure of certain cyclic reactants imparts to the cyclic products produced therefrom sufficient polarity to make the cyclic products immiscible with the non-polar solvent. Phase separation may occur spontaneously or may be induced by a change in temperature or pressure or the addition of an additive, e.g., salt, or combinations thereof. The addition of an external polar solvent to induce phase separation is not required by this invention.
This invention relates in part to a process for separating one or more cyclic products from a reaction product fluid comprising one or more cyclic reactants, a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand, a non-polar solvent and said one or more cyclic products, wherein said process comprises: (1) reacting said one or more cyclic reactants in the presence of said metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent to form a multiphase reaction product fluid; and (2) separating said multiphase reaction product fluid to obtain a non-polar phase comprising said one or more cyclic reactants, metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent and a polar phase comprising said one or more cyclic products.
This invention further relates in part to a process for producing one or more cyclic products comprising: (1) reacting one or more cyclic reactants in the presence of a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and a non-polar solvent to form a multiphase reaction product fluid; and (2) separating said multiphase reaction product fluid to obtain a non-polar phase comprising said one or more cyclic reactants, metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent and a polar phase comprising said one or more cyclic products.
This invention yet further relates in part to a process for producing one or more cyclic aldehydes comprising: (1) reacting a cyclic olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of a metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and a non-polar solvent to form a multiphase reaction product fluid; and (2) separating said multiphase reaction product fluid to obtain a non-polar phase comprising said cyclic olefinic unsaturated compound, metal-organophosphorus ligand complex catalyst, optionally free organophosphorus ligand and non-polar solvent and a polar phase comprising said cyclic aldehydes.
DETAILED DESCRIPTION
General Processes
The processes of this invention may be asymmetric or non-asymmetric, the preferred processes being non-asymmetric, and may be conducted in any continuous or semi-continuous fashion. The product/catalyst separation is a critical feature of this invention and may be conducted as described herein. The processing techniques used in this invention may correspond to any of the known processing techniques heretofore employed in conventional processes. Likewise, the manner or order of addition of the reaction ingredients and catalyst are also not critical and may be accomplished in any conventional fashion. As used herein, the term “reaction product fluid” is contemplated to include, but not limited to, a reaction mixture containing an amount of any one or more of the following: (a) a metal-organophosphorus ligand complex catalyst, (b) free organophosphorus ligand, (c) cyclic product(s) formed in the reaction, (d) unreacted reactant(s), and (e) solvent(s). As used herein, the term “cyclic” is contemplated to include, but not limited to, monocyclic, bicyclic, tricyclic and higher cyclic, e.g., polycyclic, substituents and compounds.
This invention encompasses the carrying out of known conventional syntheses in a conventional fashion and the carrying out of product/catalyst separations in accordance with this invention. By the practice of this invention, it is now possible to separate the desired cyclic product from the metal-organophosphorus ligand complex catalyst without the need to use vaporization separation and the harsh conditions associated therewith.
Illustrative processes include, for example, hydroformylation, hydroacylation (intramolecular and intermolecular), hydrocyanation, hydroamidation, hydroesterification, aminolysis, alcoholysis, hydrocarbonylation, hydroxycarbonylation, carbonylation, olefin isomerization, transf

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