Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Patent
1998-03-11
2000-04-25
Rotman, Alan L.
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
502164, 502210, 549531, B01J 3132, B01J 3134, B01J 3136, B01J 3138, C07D30112
Patent
active
060544074
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
The present invention relates to novel catalysts in the form of peroxo-containing metal complexes having amine oxide, phosphine oxide, arsine oxide, pyridine N-oxide or pyridine ligands, which catalysts are suitable for the epoxidation of olefins using aqueous hydrogen peroxide. Furthermore, the invention relates to a process for preparing these catalysts and a corresponding epoxidation process.
DESCRIPTION OF THE BACKGROUND
The epoxidation of olefins using aqueous hydrogen peroxide (H.sub.2 O.sub.2) is only successful in the presence of organic or inorganic activators or catalysts. The transfer of the oxygen atom from H.sub.2 O.sub.2 to the substrate can occur in a stoichiometric or catalytic reaction. However, in the case of the use of hydrogen peroxide, the disadvantage of the necessity of an activator or catalyst is more than compensated for by the ecological potential of hydrogen peroxide. In contrast to other oxidates, oxidation using H.sub.2 O.sub.2 gives only water as by-product. A further advantage is the high active oxygen content of hydrogen peroxide which, at 47%, is far above that of all other customary oxidates (except for O.sub.2).
Hydrogen peroxide has hitherto been used industrially mainly as an unselective oxidizing agent, for example for the bleaching of paper, textiles and cellulose or in wastewater treatment. A significant proportion of the world production of H.sub.2 O.sub.2 goes into the manufacture of inorganic peroxo compounds for detergents. Only about 10% are used for the preparation of organic chemicals such as percarboxylic acids or N-oxides, which is attributed not least to the lack of suitable selective activators or catalysts.
One of the most common methods for the stoichiometric activation of hydrogen peroxide is the reaction with carboxylic acids to give percarboxylic acids which can epoxidize a variety of olefins. However, a problem here is the acid-sensitivity of many epoxides, particularly in aqueous medium, and also the liability of the percarboxylic acids which leads to losses in yield.
Peroxo-containing transition metal complexes such as MO(O.sub.2).sub.2 L.sub.2 (M=Mo or W, L=H.sub.2 O, DMF (dimethylformamide) or HMPA (hexamethylphosphoramide)), which can easily be prepared from H.sub.2 O.sub.2 and the corresponding metal oxide MO.sub.3 are also able to epoxidize olefins, which corresponds to a stoichiometric activation of H.sub.2 O.sub.2. Compounds of this specific type have the advantage of being readily available.
For catalytic activation in the epoxidation of olefins using H.sub.2 O.sub.2, use is made, for example, of catalysts derived from the above-mentioned peroxo-containing transition metal complexes MO(O.sub.2).sub.2 L.sub.2. Thus, U.S. Pat. No. 3,953,362 (1) describes molybdenum complexes obtainable from MoO.sub.3, H.sub.2 O.sub.2 and tertiary amines whose three organic radicals are each C.sub.1 -C.sub.10 -alkyl or C.sub.6 -C.sub.10 -aryl groups, or the N-oxides of such tertiary amines, as catalysts for epoxidations using H.sub.2 O.sub.2.
EP-A 215 415 (2) relates to an oxidation process for converting olefins into aldehydes or ketones by means of oxodiperoxomolybdenum or tungsten complexes having phosphoramide and, inter alia, also amine oxide or phosphine oxide ligands. Examples of amine oxides mentioned are pyridine N-oxide, 4-picoline N-oxide, trioctylamine N-oxide and phenylpropylpyridine N-oxide; trimethylphosphine oxide is mentioned as an example of a phosphine oxide.
EP-A 097 551 (3) discloses the use of vanadium, niobium or tantalum complexes of the formula MO(O.sub.2).sub.2 L.sub.2 having phosphoramide and also amine oxide or phosphine oxide ligands as epoxidation catalysts for olefins. Examples of amine oxides which are mentioned are trimethylamine N-oxide, N-methylmorpholine N-oxide, pyridine N-oxide, 2-, 3- or 4-picoline N-oxide, quinoline N-oxide and 2,2'-bipyridine N-oxide; examples of phosphine oxides which are mentioned are triphenylphosphine oxide, trimethylphosphine oxide, methyldiphenylphosphine oxide, die
REFERENCES:
patent: 3953362 (1976-04-01), Lines et al.
patent: 4104312 (1978-08-01), Angstadt et al.
patent: 4973718 (1990-11-01), Buchler et al.
patent: 5223631 (1993-06-01), Cheng et al.
M. Postel et al ; Structural and Stereodynamics . . . ; Inorganic Chimica Acta vol. 32 pp. 175-180, May 11, 1978.
Chem. Abstract 70:110163 RN-23303-41-5.
Chem. Abstract 84:173189.
Chem Abstract 83:137726.
Schulz Michael
Sundermeyer Jorg
Teles Joaquim Henrique
Wahl Gunter
BASF Aktiengesllschaft
Desai Rita
Rotman Alan L.
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