Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-05-30
2003-09-23
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S523000, C549S531000, C549S533000, C549S534000, C549S536000
Reexamination Certificate
active
06624318
ABSTRACT:
The present invention relates to a process for the epoxidation of at least one organic compound with oxygen or an oxygen-delivering compound, in the presence of at least one catalyst containing a metal-organic framework material comprising pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. Further, the present invention is directed to the products being obtainable by the process according to the invention.
Reactions of organic compounds with oxidizing agents as hydroperoxides are well known in the prior art, for example from DE 100 55 652.3 and further patent applications of the present applicant, such as DE 100 32 885.7, DE 100 32 884.9 or DE 100 15 246.5.
The state of the art for catalysts used in epoxidation reactions is given by materials containing zeolites, in particular catalysts which comprise a titanium-, vanadium-, chromium-, niobium- or zirconium-containing zeolite as a porous oxidic material. Such catalysts are described, for example, in WO 00/07965.
In a promising novel and alternative strategy to create micro- and/or mesoporous catalytically active materials, metal ions and molecular organic building blocks are used to form so-called metal-organic frameworks (MOFs). The metal-organic framework materials as such are described, for example, in. U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al.,
J. Sol. State Chem
., 152 (2000) p. 3-20, H. Li et al.,
Nature
402 (1999) p. 276 seq., M. Eddaoudi et al.,
Topics in Catalysis
9 (1999) p. 105-111,B. Chen et al.,
Science
291 (2001) p. 1021-23. Among the advantages of these novel materials, in particular for applications in catalysis, are the following:
(i) larger pore sizes can be realized than for the zeolites used presently
(ii) the internal surface area is larger than for porous materials used presently
(iii) pore size and/or channel structure can be tailored over a large range
(iv) the organic framework components forming the internal surface can be functionalized easily.
However, these novel porous materials have only been described as such. The use of these catalytically active materials in reactions of technical importance, in particular for epoxidation reactions, has not been disclosed yet.
It is an object of the present invention to provide a catalyst for the reaction of organic compounds with oxygen and/or oxygen-delivering compounds, wherein the catalyst for said reaction contains a novel material, in addition to, or instead of, catalytic materials according to the prior art, particularly in addition to, or instead of, zeolites.
This object is solved by providing a process for the epoxidation of at least one organic compound with oxygen and/or at least one oxygen-delivering compound in the presence of a catalyst, wherein said catalyst contains a metal-organic framework material comprising pores and at least one metal ion and at least one at least bidentate organic compound, which is coordinately bound to said metal ion.
As epoxidation agents, oxygen and oxygen-delivering compounds can be used. This includes but is not limited to ozone, water, oxidizing enzymes, reactive oxides, such as permanganates, chromic oxide, nitric oxide and the like. If oxygen is used, the gas may be mixed with other reactive gases and/or inert gases. Preferred are hydroperoxides known from the prior art which are suitable for the reaction of the organic compound. Mixtures of at least two of the aforementioned epoxidation agents are included as well. The generic formula of a hydroperoxide can be given as R—O—O—H. In principle, any organic or inorganic entity known to the expert in the field may be used as the group “R”. Examples of such hydroperoxides are tertbutyl hydroperoxide, ethylbenzene hydroperoxide, and cumenehydroperoxide. In the present invention, preference is given to using hydrogen peroxide as hydrol peroxide. The present invention therefore also provides a process as described above, in which the hydroperoxide used is hydrogen peroxide. Preference is given to using an aqueous hydrogen peroxide solution. The hydrogen peroxide, or any hydroperoxide for that matter, can be either prepared outside the reaction or by starting from hydrogen and oxygen, or other suitable components, in situ within the reaction.
With respect to epoxidation reactions, DE 100 55 652.3, DE 100 32 885.7, DE 100 32 884.9, DE 100 15 246.5, DE 199 36 547.4, DE 199 26 725.1, DE 198 47 629.9, DE 198 35 907.1, DE 197 23 950.1 are fully encompassed within the content of the present application with respect to their respective content.
Other known processes for epoxidation reactions are not excluded from the present application, and are, for example, described in Weissermel, Arpe “Industrielle Organische Chemie”, publisher VCH, Weinheim, 4
th
Ed., pages 288 to 318 and in U. Onken, Anton Behr, “Chemische Prozesskunde”, Vol. 3, Thieme, 1996, pages 303 to 305 as well as Weissernel, Arpe “Industrial Organic Chemistry”, 5
th
Ed., Wiley, 1998, pages 159 to 181.
Among the reactions which are possible in the process of the present invention, the following are mentioned by way of example and without limiting the general scope of the present invention:
the epoxidation of olefins, e.g. the preparation of propylene oxide from propylene and H
2
O
2
or from propylene and mixtures which provide H
2
O
2
in situ;
hydroxylations such as the hydroxylation of monocyclic, bicyclic or polycyclic aromatics to give monosubstituted, disubstituted or higher-substituted hydroxyaromatics, for example the reaction of phenol and H
2
O
2
, or of phenol and mixtures which provide H
2
O
2
in situ, to form hydroquinone;
oxime formation from ketones in the presence of H
2
O
2
, or mixtures which provide H
2
O
2
in situ, and ammonia (ammonoximation), for example the preparation of cyclohexanone oxime from cyclohexanone;
the Baeyer-Villiger oxidation.
In the process of the present invention, organic compounds which have at least one C—C double bond are epoxidized.
Examples of such organic compounds having at least one C—C double bond are the following alkenes: ethene, propene, 1-butene, 2-butene, isobutene, butadiene, pentene, piperylene, hexenes, hexadienes, heptenes, octenes, diisobutene, trimethylpentene, nonenes, dodecene, tridecene, tetradecene to eicosene, tripropene and tetrapropene, polybutadienes, polyisobutenes, isoprenes, terpenes, geraniol, linalool, linalyl acetate, methylenecyclopropane, cyclopentene, cyclohexene, norbornene, cycloheptene, vinylcyclohexane, vinyloxiran, vinylcyclohexene, styrene, cyclooctene, cyclooctadiene, vinylnorbornene, indene, tetrahydroindene, methylstyrene, dicyclopentadiene, dinvinylbenzene, cyclododecene, cyclododecatriene, stilbene, diphenylbutadiene, vitamin A, beta-carotene, vinylidene fluoride, allyl halides, crotyl chloride, methallyl chloride, dichlorobutene, allyl alcohol, methallyl alcohol, butenols, butenediols, cyclopentenediols, pentenols, octadienols, tridecenols, unsaturated steroids, ethoxyethene, isoeugenol, anethole, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, vinylacetic acid, unsaturated fatty acids such as oleic acid, linoleic acid, palmitic acid, naturally occurring fats and oils.
The process of the present invention is preferably carried out using alkenes having from 2 to 8 carbon atoms. Particular preference is given to reacting ethene, propylene and butene.
As has been mentioned above, metal-organic framework materials as such are described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709 253, M. O'Keeffe et al.,
J Sol. State Chem
., 152 (2000) p. 3-20, H. Li et al.,
Nature
402 (1999) p. 276 seq., M. Eddaoudi et al.,
Topics in Catalysis
9 (1999) p. 105-111, B. Chen et al.,
Science
291 (2001) p. 1021-23. An inexpensive way for the preparation of said materials is the subject of DE 10111230.0. The content of these publications, to which reference is made herein, is fully incorporated in the content of the present application.
The catalyst used in the p
Eddaoudi Mohamed
Hesse Michael
Lobree Lisa
Möller Ulrich
Yaghi Omar M.
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