MXPA98001801A - Compoxes of metal containing peroxum, and amino axide, fosfine oxide, arsin oxide, piridine n-oxide or pyridine ligadures, as epoxidal catalysts - Google Patents

Abstract

The olefins can be epoxidized using the catalysts I: (See Formula) where M is a metal of the transition group 4§a 7§of the Periodic Table of the Elements, L1 is an amine oxide, phosphine oxide, oxide areine, pyridine N-oxide or pyridine, of the formulas II, III, VII or VII, L2 is a customary auxiliary ligature or a subsequent ligature L1, or a free coordination site, X is oxo oxygen or an imido ligature , m is 1 or 2, and n is 1, 2

Description

METAL COMPLEXES THAT CONTAIN PEROX, AND HAVE OXIDE OF AMINE, FOSF1NA OXIDE, ARS1NA OXIDE, PYRIDINE N-OXIDE OR PYRIDINE LIGADURES. AS CATALYSTS OF EPOXIDATION The present invention relates to novel catalysts in the form of peroxo-containing metal complexes, which have amine oxide, phosphine oxide, arsine oxide, pyridine N-oxide or pyridine ligatures, these catalysts are suitable for oxidation of olefins, which use aqueous hydrogen peroxide. Also, the invention relates to a process for preparing these catalysts and to a corresponding epoxidation process. The epoxidation of olefins using hydrogen peroxide (H2O2) is only successful in the presence of activators or organic or inorganic catalysts. The transfer of the oxide atom from the H202 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 need for an activator or catalyst is more than compensated by the ecological potential of hydrogen peroxide. In contrast to other oxidates, oxidation using H20 gives only water as a by-product. A further advantage is the high active oxygen content of the hydrogen peroxide, which, at 47%, is well above the other customary oxidates (except for 02). • Hydrogen peroxide has been used up to now mainly in the industry, as a non-selective oxidizing agent, for example for bleaching of paper, textiles and cellulose or in the treatment of waste water. A significant proportion of the compounds in the world production of H 02 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-oxide, which is mainly attributed to the lack of suitable activators or selective 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 an aqueous medium, and also to the disadvantages of percarboxylic acids, which lead to yield losses. Transition metal complexes containing peroxo, such as MO (02) 2L2 (M = Mo or, L = H20, DMF (dimethylformamide) or HMPA (hexa ethyl phosphoramide)), which can be easily prepared from H202 and Corresponding metal oxide, M03, are also capable of epoxidizing olefins, which corresponds to a stoichiometric activation of H 02- Compounds of this specific type have the advantage of being readily available. For catalytic activation in the epoxidation of olefins using H202, for example, the catalysts derived from the peroxo-containing transition metal complexes mentioned above are employed, MO (02) 2L. Thus, US Pat. No. 3,953,362 (1) describes molybdenum complexes which can be obtained from M0O3, H202 and tertiary amines whose three organic radicals are each C ^ -C ^ o or C6-C10 ° C alkyl aryl groups. s N-oxides of such tertiary amines, as catalysts for epoxidations using H2O2. EP-A-215 514 (2) relates to an oxidation process for converting olefins to aldehydes or ketones, by means of oxodiperoxo-molybdenum or tungsten complexes, which have phosphorusamides and, among other things, also ligatures of amine oxide or phosphine oxide. 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 complexes of vanadium, niobium or tantalum of the formula Mo (0) L2 which have phosphoramide and also amine oxide or phosphine oxide ligatures, as epoxide 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, diethylphenylphosphine oxide and trimorpholinephosphine oxide. However, the disadvantages of the complexes described in documents (1) to (3) are the comparatively low activities, epoxide selectivities and olefin conversions in the case of olefin epoxidations with the use of aqueous H202. It is an object of the present invention to provide metal complex catalysts, in particular for olefin epoxidations, which use aqueous H2O2, which are simple and inexpensive to prepare and also have a high effectiveness and efficiency. We have found that this object is achieved by the catalysts of the general formula I: (L2) n- M (Oa) m (I) l in which: M is a metal of transition groups 42 to 72 of the Periodic Table of the Elements; L1 is an amine oxide ligation of the formula II, a ligation of phosphine oxide or of arsine oxide of the formula III, a ligation of pyridine N-oxide of the formula VII or a pyridine ligation of the formula VIII: (II) (III) (VII) (VIII) wherein R 1 to R 3 are C 1 -C 3 alkyl, C 7 -C 30 aralkyl or C 6 -C 30 aryl radicals, same or different, which may additionally contain ether oxygen atoms, groups carbonyl, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups unsubstituted or substituted with C 1 -C 4 alkyl as functional groups , wherein at least one of the radials R1 to R3 must have at least 11 carbon atoms and the two other radicals can be linked to form a ring, and R4 to R6 are C4-C30 alkyl, C7-C30 aralkyl or aryl radicals Equal or different carbon atoms, which may additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic ester groups, sulfo groups, phosphonic acid groups, groups nitro, atoms of halogen and / or amino groups unsubstituted or substituted by C 1 -C 4 alkyl, as functional groups, and R 11 to R 13 are, independently of each other, hydrogens or C1-C alkyl radicals, or C7-C30 aralkyl or C6-C30 aryl, alkoxy groups C7-C30, C7-C30 aralkoxy groups, C6-C30 aryloxy groups, or dihydrocarbylamino groups the same or different, having C1-C30 alkyl radicals, C7-C30 aryl Cg-C3o aralkyl, same or different, such as hydrocarbyl radicals, which may additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxy ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or unsubstituted amino groups or substituted with C 1 -C 4 alkyl, as functional groups, where at least one of the radicals E 11 or R 15 must be hydrogen, the sum of carbon atoms in the radicals R 11 to R 15 must be at least 8 and the radials R 11 to R15 may be linked in pairs to form rings; L2 is an auxiliary ligature, selected from the group consisting of oxo, halides, pseudohalides, carboxylates, phenoxides, alkoxides, enolates, ketones, ethers, amines, amides, urea, urea and water derivatives or a subsequent L1 ligature or a free coordination. X is an oxo oxygen or an imido bond, unsubstituted or substituted with C1-C4 alkyl; Z is phosphorus or arsenic; m is 1 or 2 and n is 1, 2 or 3. The catalysts I of the present invention differ from those known from the prior art in that they have longer or more bulky chain radicals in the L1 bonds which is the case in the amine oxide or phosphine oxide systems, previously described for this purpose. In the case of the amine oxide ligatures II, at least one of the three radicals R1 to R3 must contain at least 11, preferably at least 12, in particular at least 14, carbon atoms. This radical is preferably an alkyl group, linear or branched. In the case of ligatures III of phosphine oxide or arsine oxide, the lower limit for the size of the linear or branched alkyl radicals, R4 to R6 is 4, preferably is 6, in particular is 8, carbon, the lower limit for the size of the aralkyl radicals, R4 to R6 is 7, preferably 9, particularly 12, carbon atoms, and the lower limit for the size of the aryl radicals, R4 to R6 is 10, preferably 12, in particular 14, carbon atoms. For the ligations of the pyridine N-oxide and of pyridine, VII or VIII, the sum of the carbon atoms in the substituents of the ring must be at least 8, preferably at least 9.; in particular, one of the radicals R11 to R1 ^ is a linear or branched long chain alkyl radical having at least 8, especially at least 9, carbon atoms. Suitable transition metals for the catalyst complexes of the present invention are, in particular, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese and rhenium. Particular preference is given to molybdenum and tungsten. Typical examples of N-oxide amine ligatures II are: dimethyl-n-undecylamine oxide, dimethyl-n-dodecylamine oxide, dimethyl-n-hexadecylamine oxide, dimethyl-n-octadecylamine oxide, dimethyl-n oxide -icosylamine, methyldi (n-dodecyl) amine oxide, methyldi (n-octadecyl) amine oxide, tri (n-dodecyl) amine oxide, tri (n-octadecyl) amine oxide, benzyldi oxide (n-dodecyl) ) amine, diphenyl-n-octadecylamine oxide, N-undecylmorpholine oxide, N-dodecylpiperidine oxide, dimethyl- (6-phenylhexyl) amine oxide, dimethylbisphenylamine oxide and methyl-n-dodecyl- (6-phenylhexyl) oxide ) amine. Typical examples of ligatures III of phosphine oxide and arsine oxide are: tri-n-butylphosphine oxide and tri-n-butylarsine oxide, tri-tert.-butylphosphine oxide and tri-tert-butylarsine oxide, tri-n-hexylphosphine and tri-n-hexylarserin oxide, tri-n-octylphosphine oxide and tri-n-octylarsine oxide, tri (2-ethylhexyl) phosphine oxide and tri (2-ethylhexyl) arsine oxide, tri-n-dodecylphosphine oxide and tri-n-dodecylarsine oxide, tri-n-octadecylphosphine oxide and tri-n-octadecylarsine oxide, di-n-butyl-n-octylphosphine oxide and di-n-oxide butyl-n-octylarsine, n-butyldi-n-octylphosphine oxide and n-butyldi-n-octylarsine oxide, tribenzylphosphine oxide and tribencilarsin oxide, benzyldi-n-octylphosphine oxide and benzyldi-n-octylarsine oxide, Naphthyldi-n-octylphosphine oxide and Naphthyldi-n-octylarsine oxide and di-n-butylnaphthylphosphine oxide and di-n-butylnaphthylarsine oxide. Typical examples of ligatures VII and VIII of pyridine N-oxide and pyridine are: 4- (l-octyl) pyridine and its corresponding N-oxide, 4- [l- (2-ethylhexyl) [pyridine and its N-oxide] corresponding, 4- (1-nonyl) pyridine and its corresponding N-oxide, 4- (5-nonyl) pyridine and its corresponding N-oxide, 4- (1-decyl) pyridine and its corresponding N-oxide, 4- ( 1-dodecyl) pyridine and its corresponding N-oxide, 4- (n-octoxy) pyridine and its corresponding N-oxide, 4- (2-ethylhexoxy) pyridine and its corresponding N-oxide, 4- (n-nonoxy) pyridine and its corresponding N-oxide, 4- (di-n-octylamino) pyridine and its corresponding N-oxide, and 4- (di-2-ethylhexylamino) pyridine and its corresponding N-oxide. If the radicals R1 to R6 and R11 to R15 contain additional ether oxygen atoms, then these radicals are derived, in particular, from the corresponding ethylene oxide, propylene oxide, butylene oxide or the reaction products of tetrahydrofuran. The alkoxy substituents and the carboxylic ester substituents in R1 to R6 and R11 to R15 preferably have C1-C4 alkyl radicals, in particular methyl or ethyl. Halogen atoms in R1 to R6 and R11 to R15 are, in particular, chlorine or bromine. The number of the functional groups listed R1 to R6 and R11 to R15, if any is present, is usually from 1 to 3, in the case of ether oxygen atoms it is from 1 to 14, depending on the chain length.

The auxiliary ligatures L2 are those that are customarily used and with which those skilled in the art, therefore, are familiar. Preferred catalysts of the present invention are those of the general formula IA or Ib: < Ia > (Ib) where L2 is water and the variables M, L1 and n are as defined above. In the case of M = chloro, molybdenum or tungsten, the number n of the ligatures L2 is preferably 1. A preferred embodiment comprises the catalysts of the present invention I or Ia or Ib, in which L1 is a ligation II of oxide of amine, which carries C ^ -C20 alkyl groups as the radicals R1 to R3, where at least one of these radicals R1 to R3 has to be a C12-C20 alkyl group and the other two radicals can be linked to form a saturated ring of 5 or 6 members, which may also contain heteroatoms, selected from the group consisting of oxygen and nitrogen.

A further preferred embodiment comprises the catalysts of the present invention 1 or la or Ib, in which L1 is a ligation III of a phosphine oxide or of an arsine oxide, which carries C4-C2 alkyl groups? as the radicals R4 to R6. The catalyst complexes I of the present invention are advantageously prepared from other complexes of metal M and hydrogen peroxide. Complexes I are usually obtained by replacing ligatures L, in the complexes of the transition metal, which contain the peroxo, mentioned above, MX (0)? N (L2) n + 1, where M, X, m and n have the above definitions and L is, in particular, H20, DMF or HMPA, by amine oxides II or phosphine oxides III. These precursor complexes, by themselves, can usually be prepared in a very simple manner from cheap starting materials (metal oxides, H202 and ligatures or ligating precursors). Advantageously, the catalysts I are prepared in situ or by dissolving the metal oxides in an excess of the aqueous H202 or easily available precursors, such as M02C12 (DME) (DME = dimethoxyethane), and the activation by adding the necessary amount of the amine II, phosphine or arsine III oxide, pyridine N-oxide VII or pyridine VIII. Instead of the amine N-oxides or the phosphine or arsine oxides, it is also possible to directly add the corresponding amines or phosphines or arsines, since they are oxidized in itself by the H202 to give the amine N-oxides or desired phosphine oxides. The catalysts can be generated in situ or can also be prepared separately, isolated and characterized. Other suitable precursors for the catalyst complexes I of the present invention are complexes of the formula VI: M = O (VI) Y- "/ \ L2> n Ll where Y is halide, for example chloro p pseudohalide, for example thiocyanate, and the variables M, X, L1, L2 and n are as defined above. Complexes VI are easily converted to complexes I in the presence of H202. The catalysts of the present invention are very suitable for the catalytic activation of the oxidation reactions, in particular for the epoxidation of olefins, especially using the aqueous hydrogen peroxide as the epoxidizing agent.

Therefore, the present invention also provides a process for preparing epoxides of the general formula IV: Rβ R9 R7- C - C- Ri ° (IV) \ / where R7 to R10 are the same or different and represent hydrogen or an unsubstituted or substituted alkyl, alkenyl, heteroalkyl cycloalkyl, aryl or heteroaryl radical, wherein the R7 to R10 radicals may also be linked to form rings, or substituents based on the elements of the major groups 42 to 72 of the Periodic Table of the Elements, of olefins of the general formula V: R8 R9 R7 ^ Rio with the use of aqueous hydrogen peroxide, in which the epoxidation of the olefins V is carried out in the presence of the catalysts I of the present invention.

For the olefins that can be used, there is no restriction with respect to the type and number of substituents. Typical examples of olefins which can be epoxidized by the process of the present invention are ethylene, propene, 1-butene, 2-butene, isobutene, 1,3-butadiene, 1-pentene, 2-pentene, isoprene, cyclopentene, 1 -hexene, cyclohexene, Cs-C24 α-olefins, styrene, indene, norbornene, cyclopentadiene, dicyclopentadiene and also alkene oligomers having reactive double bonds, for example polypropylene and polyisobutene. Olefins V can also carry substituents based on elements of major groups 42 to 7 on the olefinic double bond. Examples are vinylsilicones, vinylamines, vinylphosphines, vinyl ethers, vinyl sulfides and halogenated alkenes, such as vinyl chloride, vinylidene chloride or trichlorethylene. In order to carry out the epoxidation, according to the present invention, it is usual to initially charge the catalyst I and add the necessary amount of the aqueous H202 and the olefin. If desired, dissolved in a suitable inert organic solvent. The concentration of the aqueous H202 varies from 2 to 70% by weight, in aprticular from 5 to 50% by weight. Suitable inert organic solvents are, for example, chloroform, dichloromethane, ethers, carboxylic or aromatic esters. This usually gives a two-phase reaction mixture. When water-miscible solvents are used, for example methanol, acetone, dimethoxyethane or dioxane, the reaction can also be carried out homogeneously. The reaction conditions of the epoxidation, according to the present invention, are very moderate, which is an advantage due to the high reactivity of the epoxides formed. Typically, the reaction is carried out at a temperature of from -20 to 160 ° C, in particular from 20 to 100 ° C, especially from 50 to 80 ° C, ie in a temperature range which is probably favorable for removing heat from the reaction. The increased pressure is necessary only in the case of highly volatile olefins, such as propene or butene; the reaction is carried out normally at atmospheric pressure. The use of ligatures I, III, VII or VIII, which have lipophilic substituents, in the form of long chain or bulky radials, generally gives active interface catalysts so that the epoxidation can also be advantageously carried out in a system of two phases, that is to say two liquid phases, that are not completely miscible with each other. This process has the advantage that, on the one hand, lipophilic, water-insoluble olefins can also be oxidized and, on the other hand, the epoxides formed remain in the organic phase and the formation of undesired by-products is thus suppressed. In addition, the separation of the product is made easier by the two aces procedure. In a preferred embodiment, the propene is epoxidized to the propylene oxide by the process of the present invention, in particular in a two-phase system. In a further preferred embodiment, 1,3-butadiene is epoxidized to vinyloxirane, by the process of the present invention, particularly in a two-phase system. Using the highly active catalysts I of the present invention, epoxides with high selectivities and with high conversion rates from olefins are obtained by means of aqueous hydrogen peroxide, in a simple and economical process, under mild and moderate conditions. Examples Example l; Preparation of the catalyst loading solutions a) Preparation of an aqueous filler solution of 6.00 g (41.7 mmol) of [Mo03] was suspended, with vigorous stirring, in 24.0 g (212 mmol) of a H20-2 solution at 30% by weight. The colorless suspension was stirred for 4 hours at 402 ° C, forming a pale yellow, clear solution, which was stored at 42 ° C. Content of [Mo (0) (02) (H20) 2]: 1.39 mmol / g. b) Preparation of an aqueous loading solution of [W (0) (O2IH2P-I2I 8.00 g (32.0 mmol) of [W03-H20] was suspended, with vigorous stirring, in 24.0 g (212 mmol) of a H20 solution at 30% by weight. The yellow suspension was stirred for 6 hours at 402 ° C, forming a cloudy, milky solution. After removing the insoluble residue (25 mg) by centrifugation, the clear, colorless solution was stored at 42c. Content of [W (O) (02) (H 0) 2]: 1.01 mmole / g.

Example 2 Preparation of the catalysts [M (O) (2 2) 2L11 a) Preparation of fMo (O) (02) 2 ^ (n-Oct) 3) 4 ml of tetrahydrofuran (THF) were first added to 1.86 g ( 2.58 mmoles) of a loading solution of Mo (Example la). While stirring, 500 mg (1.29 mmol) of tri-n-octylphosphine oxide [0P (n-0ct) 3] was added to 252c. After vigorous stirring for 2 hours, the yellow solution was evaporated under reduced pressure to about 3 ml, with a separation of a yellow oil. The reaction mixture was extracted with CH2C12 3 times, 5 ml each time). The combined extracts were completely evaporated under reduced pressure. The waxy, pale yellow residue was washed with water (2 times, 2 ml each) and dried for 6 hours at 252C / 10"5 mbar Yield: 675 mg (93%) of pale yellow wax DTA: 81 C (exothermic decomposition) CHN analysis: c24H51P06Mo (562.6) Calculated C 51.24, H 9.14 Found C 51.68 H 9.45 b) Preparation of [W (0) (02) { OP (n-Oct) 3.}.] 12 ml of THF were first added to 6.00 g (6.06 mmol) of the loading solution (Example Ib) While stirring, 1.50 g (3.87 mmol) of [0 P (n-0ct) 3] were added to the solution 25 c) After vigorous stirring for 4 hours, the colorless solution was evaporated under reduced pressure to about 5 ml, with a separation of a colorless oil, the reaction mixture was extracted with C12CH (3 times, 10 ml each time) The combined extracts were completely evaporated under reduced pressure.The colorless oily residue was washed with water (3 times, 1 ml each time) and dried for 6 hours at 252C / 10-5 mbar. Note: 240 g (95%) of a colorless oil DTA: 982C (exothermic decomposition) CHN analysis: c24H5iP06 (650.0) Calculated C 44.35, H 7.91 Found C 45.14 H 8.53 .. c) Preparation of fMo (O) (02) 2 -f ONMe2 f n-C18H3 7) 1 6.00 g (5.74 mmol) of the dimethyl-n-octyldecylamine oxide [0NMe2 (n-C18H37)] (30 wt.% In water) were added at 252C while stirring, at 5.00 g (6.95 mmoles) of the loading solution of Mo (Example la), with a pale yellow precipitate being formed spontaneously. After vigorous stirring for 2 hours, the precipitate was filtered off, washed with water (3 times, 50 ml each) and dried under reduced pressure for 6 hours at 252C / 10-5 mbar. Yield: 2.00 g (71%) of an amorphous, pale yellow solid, DTA: 782C (exothermic decomposition) CHN Analysis: C2oH43MoN06 (489.5) Calculated C 49.07 H 8.85 N 2.86 Found C 49.07 H 8.88 N 2.82 d) Preparation of GMO (O) (02) 2-l "0N (dodec) 3>] 1.20 g (2.23 mmoles) of the tri-n-dodecylamine oxide [0N (dodec) 3] dissolved in 5 ml of CH2C12 were added at 252C, while stirring, at 2.00 g (2.87 mmol) of a loading solution of Mo (Example la.) After vigorous stirring for 5 hours at 252C, the organic phase was separated, washed with water (3 times , 5 ml each) and evaporated completely under reduced pressure The yellow amorphous residue was dried for 6 hours at 252C / 10-5 mbar Yield: 2.81 g (95%) of an amorphous solid, colored pale yellow, DTA: 752C (exothermic decomposition) CHN analysis: C36H75MoN06 (713.9): Calculated C 60.57 H 10.59 N1.96 Found C 60.62 H 10.72 N 1.95 d) Preparation of fW (O) (Oo) 2-fON (dodec) 3] 1.30 g (2.42 mmoles) of [ON (dodec) 3], dissolved in 5 ml of CH2Cl2, were added, at 252c, while stirring, to 3.00 g (3.03 mmol) of the solution of charge W (Example Ib). After vigorous stirring for 5 hours at 25 ° C, the organic phase was separated, washed with water (3 times, 5 ml each) and completely evaporated under reduced pressure. The colorless sticky residue was dried for 6 hours at 252C / 10-5 mbar. Yield: 1.84 g (95%) of a colorless sticky wax DTA: 68 c (exothermic decomposition) CHN analysis: C36H75WN06 (801.8): Calculated C 53.93 H 9.43 N 1.75 Found: C 53.88 H 9.29 N 1.67.

EXAMPLE 3 Catalytic oxidation of cyclooctene and 1-octene by 30% by weight H 2? 2, using catalysts of the type MO (02) 2L1 (H2 °) generated in situ. 36 mmoles of 30% by weight H202 and 9 mmoles of olefin were added to 25 s to an aliquot (0.36 mmoles? 4% molar) of the catalyst loading solution described in Example 1. The reaction solution was mixed subsequently. with 0.36 mmoles of the phosphine oxide or amine N-oxide ligature, dissolved in 4 ml of CHC13 and stirred for 24 hours at 60 ° C. The olefin conversion and the epoxide selectivity were determined by gas chromatography. The results of the experiments are summarized in Table 1. The same results are also obtained, in principle, by using analogous catalysts, prepared separately, described under Example 2 (in each case, using 0.36 mmole dissolved in 4 ml of CHC13).

Table 1 Examples 4 v 5 Epoxidation using L1 = tri (n-dodecyl) arsine oxide A glass autoclave was charged with 1-octene (500 mg, 4.45 mmole), M03 (0.17 mmole, 4.0 mole%, based on 1- octene, as a 0.5M solution in H202 at 30% by weight) and tri- (n-dodecyl) arsine oxide (0.17 mmoles dissolved in 3 ml of chloroform). Then H2O2 (17.8 mmol, as a 30% by weight aqueous solution) was added and the mixture was stirred at 60 ° octene epoxide was the only product tried. The octene oxide was supplied at various times of the reaction summarized in Table 2.

Table 2 Examples 6 and 7 Epoxidation using L1 = 4- (S-nonyl) pyridine A glass autoclave was charged with 1-octene (500 mg, 4.45 mmole), MO3 (0.17 mmole, 4.0 mole%, based on 1-octene , as a 0.5M solution in H202 at 30% by weight) and 4- (5-nonyl) -pyridine (0.17 mmoles dissolved in 3 ml of chloroform). Then H202 (17.8 mmol, as an aqueous solution at 30% by weight) was added and the mixture was stirred at 602C. Octene epoxide was the only product tried. The octene oxide supplies at various times of the reaction are summarized in Table 3.

Table 3 Examples 8 and 9 Epoxidation using L1 = 4- (5-nonyl) pyridine N-oxide A glass autoclave was charged with 1-octene (500 mg, 4.45 mmole), M03 (0.17 mmole, 4.0 mole%, based on 1-octene, as a 0.5M solution in 30% by weight H2O2) and 4- (5-nonyl) -pyridine N-oxide (0.17 mmoles dissolved in 3 ml of chloroform). Then H202 (17.8 mmol, as an aqueous solution at 30% by weight) was added and the mixture was stirred at 602C. Octene epoxide was the only product tried. The octene oxide was supplied at various times in the reaction summarized in Table 4. Table 4 Examples 10 v 11 Epoxidation using 1 = 4- (dioctylamino) pyridine A glass autoclave was charged with 1-octene (500 mg, 4.45 mmol), MO3 (0.17 mmol, 4.0 mol%, based on l-octene, as a 0.5M solution in H202 at 30% by weight) and 4- (dioctylamino) pyridine (0.17 mmoles dissolved in 3 ml of chloroform). Then H202 (17.8 mmol, as an aqueous solution at 30% by weight) was added and the mixture was stirred at 60 c. Octene epoxide was the only product tried. The octene oxide was supplied at various times of the reaction summarized in Table 5.

Table 5

Claims (11)

1. A catalyst of general formula I: X II (2) n- M (02) m (I) Ll in which: M is a metal from 42 to 72 transition group of the Periodic Table of the Elements; L1 is an amine oxide ligation of formula II, a phosphine oxide or arsine oxide ligation of formula III, a pyridine N-oxide ligation of formula VII or a pyridine ligation of formula VIII : (II) (III) (VII) (VIII) wherein R 1 to R 3 are C 1 -C 30 alkyl, C 7 -C 30 aralkyl or C 1 -C 30 aryl radicals, same or different, which may additionally contain ether oxygen atoms, groups carbonyl, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or amino groups unsubstituted or substituted with C 1 -C 4 alkyl as functional groups , wherein at least one of the radials R1 to R3 must have at least 11 carbon atoms and the two other radicals can be linked to form a ring, and R4 to R6 are C4-C30 alkyl, C7-C30 aralkyl or aryl radicals C10-c30 'identical or different, which may additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxy ester groups, sulfo groups, phosphonic acid groups, nitro groups, atoms of halogen and / or amino groups unsubstituted or substituted by 4-ring alkyl as functional groups, and R 11 to R 13 are, independently of each other, hydrogens or alkyl radicals of 0,000, C 7 -C 30 aralkyl or C 5 -C 30 aryl, C 7 alkoxy groups -C30, C7-C30 aralkoxy groups, C6-C30 aryloxy groups, or dihydrocarbylamino groups the same or different, having C1-C30 alkyl radicals, C7-C30 aryl C5-C30 aralkyl, the same or different, as hydrocarbyl radicals, which they may additionally contain ether oxygen atoms, carbonyl groups, hydroxyl groups, alkoxy groups, carboxyl groups, cyano groups, carboxylic ester groups, sulfo groups, phosphonic acid groups, nitro groups, halogen atoms and / or unsubstituted amino groups or substitios with C -C4 alkyl, as functional groups, where at least one of the radicals E11 or R15 must be hydrogen, the sum of carbon atoms in the radicals R11 to R15 must be at least 8 and the radials R11 to R15 they can be linked in pairs to form rings; L2 is an auxiliary ligature, selected from the group consisting of oxo, halides, pseudohalides, carboxylates, phenoxides, alkoxides, enolates, ketones, ethers, amines, amides, urea, urea and water derivatives or a subsequent L1 ligature or a free coordination. X is an oxo oxygen or an imido bond, unsubstituted or substituted with C-C4 alkyl; Z is phosphorus or arsenic; m is 1 or 2 and n is 1, 2 or 3.

2. A catalyst I, as claimed in claim 1, wherein M is molybdenum or tungsten.

3. A catalyst of the general formula Ia or Ib, as claimed in claims 1 or 2, of the formulas: (the) (Ib) where L2 is water and the variables M, L1 and n have the above definitions.

4. A catalyst I, as claimed in any of claims 1 to 3, wherein L1 is an amine oxide ligation II, which carries C1-C20 alkyl groups as the radicals R1 to R3, wherein at least one of the radicals R1 to R3 must be a C? -C2o alkyl group and the other two radicals can be linked to form a saturated ring of 5 to 6 members, which may contain additional heteroatoms, selected from the group consisting of oxygen and nitrogen.

5. A catalyst I, as claimed in any of claims 1 to 3, wherein L1 is a ligature of phosphine oxide or arsine oxide, which carries C4 to C20 alkyl groups with the radicals R4 to R6.

6. A process for preparing a catalyst I, as claimed in any of claims 1 to 5, which comprises preparing the catalytically active complex of the general formula I from another complex of the metal M and the hydrogen peroxide.

7. Use of a catalyst I, as claimed in any of claims 1 to 5, for the epoxidation of olefins.

8. A process for preparing epoxides of the general formula IV: R8 R9 R7 C - c Rl ° (IV) \ / where R7 to R10 > they are the same or different and represent hydrogen or an unsubstituted or substituted alkyl, alkenyl, heteroalkyl cycloalkyl, aryl or heteroaryl radical, where these radials R7 to R10 may also be linked to form rings, or substituents based on the elements of the main groups 4 to 7 of the Periodic Table of the Elements, of olefins of the general formula V: Rß R9 .C = C (V) R7 'RO with the use of aqueous hydrogen peroxide, in which the epoxidation of the olefins V is carried out in the presence of a catalyst I, as claimed in any of claims 1 to 5.

9. A process for preparing the epoxides IV, as claimed in claim 8, in which the epoxidation of the olefins V is carried out using aqueous hydrogen peroxide, in two liquid phases, which are not completely miscible with each other.

10. A process for preparing propylene oxide from propene, as claimed in claims 8 or 9.

11. A process for preparing the vinyloxirane from 1,3-butadiene, as claimed in claims 8 or 9.