Process for carbonylation of epoxide derivatives

Details Process for carbonylation of epoxide derivatives Process for carbonylation of epoxide derivatives

1999-08-25

2002-02-19

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C556S001000, C556S028000, C556S136000, C556S137000, C548S402000, C546S002000, C544S225000, C502S152000, C502S155000, C502S166000

Reexamination Certificate

active

06348611

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for carbonylation of epoxide derivatives, in which the reactivity, selectivity and the yield are superior. More specifically, the present invention relates to a process for hydroformylation of an epoxide derivative in which there is utilized a transition metal catalyst having a cyclopentadienyl radical, thereby improving the reactivity and selectivity. Further, the present invention relates to a process for hydroesterification of an epoxide derivative, in which a proper catalyst is selected, and the reaction temperature and pressure are adjusted within proper ranges in the presence of a cobalt catalyst, thereby improving the product selectivity and the yield.
BACKGROUND OF THE INVENTION
The epoxide derivatives can be easily converted into difunctional compounds through a carbonylation reaction. These difunctional compounds are used as an intermediate of useful organic compounds. Among them, the typical compounds are the 3-hydroxyaldehyde derivatives and the 3-hydroxyester derivatives, the former being synthesized by a hydroformylation of epoxide derivatives, and the latter being synthesized by a hydroesterification of an epoxide derivative. In the 3-hydroxyaldehyde derivatives which are synthesized by the hydroformylation, aldehyde group is converted into an alcohol radical through a hydrogenation, thereby obtaining alkanediol. Among the alkanediol derivatives, 1,3-propanediol is known to be an intermediate for synthesizing the polyester which is used for making fibers and films. Further, it is also used as an intermediate for coating materials and for organic synthesis. Meanwhile the 3-hydroxyester derivatives which are obtained by the hydroesterification of the epoxide derivatives have two active radicals, respectively. Therefore, they are known to be useful as solvents, resins and coating materials. Further, they can be converted into other compounds, so that they can be used in the medical field. Further, they are also used as an intermediate for synthesizing the alkanediols. In a known process for synthesizing the 3-hydroxyaldehyde showing a high selectivity under a low temperature and a low pressure, there are used a cobalt catalyst and phosphine oxide ligand as a promoter. However, when phosphine oxide ligand is used as a promoter, the recovery and regeneration of the catalyst become complicated.
U.S. Pat. Nos. 5,770,776, 5,723,389 and 5,731,478 disclose processes in which ethylene oxide is hydroformylated, and a hydrogenation of aldehyde group is adopted. In these processes, a cobalt catalyst is used, and another metal compound or ligand is used as the promoter instead of the phosphine oxide ligand, thereby improving the activity and the selectivity of the cobalt catalyst.
U.S. Pat. Nos. 5,135,901 and 4,973,741 disclose another process for obtaining the 3-hydroxyester derivative from the epoxide derivatives. In this process, there is synthesized methyl 3-hydroxypropionate from ethylene oxide by using rhodium and ruthenium as catalysts in the presence of carbon monoxide and alcohol. However, in this process, in spite of the use of expensive catalysts, the yield of the 3-hydroxypropionate is as low as 60%, and by-products are produced in considerable amounts. Further, there is another known process for obtaining a 3-hydroxyester by hydroesterification of the epoxide. In this process also, the yield is as low as 40-60%. [(1) Dalcanali, E.; Foa, M. Synthesis 1986, 492. (2) Heck, R. F., J. Am. Chem. Soc., 1963, 85, 1460. (3) Eismann, J. L.; Yamartino, R. L.; Howard, Jr. J. F., J. Org. Chem. 1961, 2102.]. The reason why the yield is so low is that the isomerization reaction of the starting material readily occurs.
Meanwhile, U.S. Pat. Nos. 5,310,948 and 5,359,081 relate to a carbonylation of the epoxide, in which the epoxide and carbon monoxide are reacted in the presence of cobalt and pyridine derivatives. The final product is mainly -lacton, and the by-product is the 3-hydroxyester.
As described above, there has not yet been found an effective process for synthesizing the 3-hydroxyester derivative, in which economy is ensured.
Therefore, the present inventors have conducted studies on the carbonylation of epoxides for obtaining an intermediate which is useful for synthesizing an organic compound and alkanediol. For this purpose, a transition metal compound in which a cyclopentadiene radical had been coupled to a 9th group transition metal was made to react with a compound having one or more active radicals. The compound thus obtained was used as a catalyst in the presence of a cobalt compound to obtain 3-hydroxyaldehyde derivatives with a high reactivity and selectivity, thereby establishing a process for hydroformylation. Further, an epoxide derivative was made to react with carbon monoxide and alcohol in the presence of a proper solvent and a cobalt catalyst, and the reaction temperature and pressure were adjusted to proper levels to obtain a 3-hydroxyester derivative with a high yield, thereby establishing a process for hydroesterification.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide transition metal catalysts which show superior reactivity and selectivity in the hydroformylation of epoxide derivatives.
It is another object of the present invention to provide transition metal catalysts which show superior recovery and regeneration characteristics in the hydroformylation of epoxide derivatives.
It is still another object of the present invention to provide a process for hydroformylation of epoxide derivatives, in which a cobalt compound and a transition metal compound with superior reactivity and selectivity are used, thereby synthesizing a 3-hydroxyaldehyde derivative with high selectivity and yield.
It is still another object of the present invention to provide a process for hydroesterification of epoxide derivatives, in which a proper solvent and a cobalt catalyst are used, and the reaction temperature and pressure are adjusted to proper ranges, thereby synthesizing 3-hydroxyester derivatives with a high yield.
In the present invention, there is provided a process for carbonylation of epoxide derivatives for synthesizing 3-hydroxyaldehyde derivatives and 3-hydroxyester derivative which are the useful intermediates are used for synthesizing organic compounds and alkanediols.
In achieving the above objects, the present invention is characterized as follows. That is, the 3-hydroxyaldehyde derivatives are synthesized by a hydroformylation of epoxide derivatives. The hydroformylation reactions are carried out in the following manner. A cobalt compound and a transition metal compound having a cyclopentadienyl radical (which is separately synthesized) are dissolved in a non-aqueous solvent. Then, an epoxide derivative is added, then carbon monoxide and hydrogen (CO/H
2
) are introduced into the reactor, and then, the reactor is put into an oil bath which is maintained at a desired temperature. Alternatively, a transition metal compound having the above mentioned cyclopentadienyl radical is synthesized in a non-aqueous solvent, and then, the hydroformylation process is carried out without any separating step.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The mole ratios of the cobalt compound to the transition metal having the cyclopentadienyl radical are preferably 1000:1~1:5, and more preferably 100:1~1:2. The mole ratio of CO/H
2
which are supplied for the hydroformylation is preferably 3/1~1/10, and more preferably 2/1~1/5. The total pressure is preferably 100~3000 psi, and more preferably 500~2000 psi. The temperature is raised from the normal temperature to 30 degrees C.~120 degrees C., and more preferably to 60~100 degrees C. in proceeding the hydroformylation.
Now the catalyst, the solvent and the epoxide derivatives which are used in the hydroformylation of the present invention will be described in detail.
The transition metal catalysts which are used in the hydroformylation are transition metal compounds which are prepared by bonding the 9th group trans

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