CZ305316B6 - Immobilized catalytic system for oxidation of pyridine and derivatives thereof to pyridine-1-oxides by hydrogen peroxide and process for preparing thereof - Google Patents

Abstract

In the present invention, there is provided a catalytic system and use thereof for oxidation of pyridine and methyl-derivatives thereof to corresponding pyridine-1-oxides by hydrogen peroxide, containing an active catalyzing component being represented by mixed heterooxo polyanions of the general formula [(P)ia(Si)ib(B)ic(W)ip(Mo)iq(V)irOi40]ex-, wherein phosphorus is in the oxidation state +5, silicon is in the oxidation state +4, boron is in the oxidation state +3, indices a, b, c are numbers in the range of 0 to 1, wherein the sum of a+b+c=1, tungsten is in the oxidation state +6, molybdenum is in the oxidation state +6, vanadium is in the oxidation state +5, the indices p, q, r are numbers in the range of 0 through 12, wherein the sum p+r+q=12, a x=80-5a-4b-3c-6p-6q-5r, and the mixtures of these hetero polyanions, wherein the active catalyzing component is ion-immobilized on an organic anion-exchange resin. The organic anion-exchange resin is preferably represented by copolymer of divinylbenzene, being preferably selected from the group consisting of a crosslinked methyl styrene-divinylbenzene, crosslinked copolymer acrylate-divinylbenzene, and crosslinked copolymer methacrylate-divinylbenzene. The active catalytic component is immobilized through the mediation of protonized or quaternized oligoamines -[NRCHi2CHi2(CHi2)im]inNRi3e+, wherein m = 0 to 2, n = 1 to 5, and the substituent R is selected from the group consisting of hydrogen and alkyl containing 1 to 4 carbon atoms, and/or through the mediation of quaternary ammonium groups -(NR´i3)e+, wherein R´ is selected from the group consisting of alkyl containing 1 to 4 carbon atoms and 2-hydroxyethyl, bound to the organic anion-exchange resin through the mediation of methylene-CHi2- or carbonyl -(C=O)- functional group. The invention also relates to a process for preparing the above-described catalytic system.

Description

Technical field

The invention relates to an immobilized catalyst system for the oxidation of pyridine and its methyl derivatives to the corresponding pyridine-1-oxides with hydrogen peroxide in aqueous solution.

BACKGROUND OF THE INVENTION

For the synthesis of pyridine-N-oxide and its methyl derivatives (PNO), the corresponding pyridine is used as starting material. Oxidation of tertiary nitrogen in tertiary amines generally can be accomplished in a number of ways. The oxidizing agent most commonly used is hydrogen peroxide, peracid, atmospheric oxygen or compounds containing a chlorine or bromine atom in the oxidation state of +1. Oxidations are also often carried out catalytically using various oxidation activating catalysts.

The advantage of using 30% H ₂ O ₂ as an oxidizing agent is its low cost and easy availability. It also only provides water as a by-product. Its disadvantage is that it is a very weak oxidant.

In 1926 PNO was prepared by the effect of peroxobenzoic acid on pyridine. The disadvantage of this process is the purification and isolation of the product via the picrate. Later, this process was improved by using monoperoxophthalic acid as the oxidizing agent. PNO precipitates here in the form of phthalate (Meisenheimer J .: Chem. Ber. 1926, 62, 1848; Boehme H .: Chem. Ber. 1937, 70, 379.).

The best known method for the preparation of PNO was published in 1953 by E. Ochiai (Ochiai E .: J. Org. Chem. 1953, 18, 548.). To a solution of pyridine in glacial acetic acid was first added 1.16 eq. 35% H ₂ O ₂ , after heating at 70 to 80 ° C for three hours, 0.84 eq. 35% H ₂ O ₂ and the reaction mixture was heated at the same temperature for an additional 9 hours. The resulting PNO acetate is then basified with anhydrous Na ₂ CO ₃ and extracted into chloroform. After suctioning off the precipitated salts and evaporating the solvent, 96% of the product was obtained. The author only reports the boiling point of the product (138-140 ° C / 15 mm Hg).

Another method directly uses 40% peroxoacetic acid as an oxidizing agent (Org. Syntheses 1953, Vol. 33, 79; 1963, Coll. Vol. 4, 828.). The mixture is heated to 85 ° C for only 50 to 60 minutes and the product is then converted to pyridine-1-oxide hydrochloride by bubbling the reaction mixture with hydrogen chloride gas (yield: 76-83%, mp: 179.5-181 ° C).

PNO acetate was also decomposed into low pressure PNO (1 mm Hg (133 Pa) or less) using a solid distillate separator (Org. Syntheses 1955, Coll. Vol. 3, 133.). Yield: 76-83%, mp .: 65-66 ° C.

A similar method has been used recently (especially for the synthesis of 3,5-disubstituted PNOs). However, peroxoacetic acid was added to pyridine at 0 ° C under Ar-atmosphere and after 2 hours at 85 ° C, the reaction mixture was neutralized with 4M NaOH and extracted into chloroform. The yield of PNO was 85% (Diemer V, Chaumeil H, Defoin A, Fort A, Boeglin A, Carre Ch .: Eur. J. Org. Chem. 2008, 10, 1767-1776).

Trifluoroacetic acid (TFA) in admixture with H ₂ O ₂ provides trifluoroacetic acid, which is a very potent oxidizing agent. This acid was prepared by dropwise addition of 30% H ₂ O ₂ to TFA at 0 ° C. The product is decarboxylated to fluoroform. The rate of decomposition is slow compared to substrate oxidation and therefore does not interfere with the reaction. The reaction with pyridine was rapid and exothermic. After 1 hour of stirring at room temperature, 100% PNO was obtained. The structure of the PNO is very resistant to further attack, and even after several hours of heating there is no further oxidation (Liotta R., Hoff WS: J. Org. Chem. 1980, 45, 2887.).

High yield (92% PNO) was also achieved using m-chloroperoxybenzoic acid (mCPBA) and Phase-Vanishing (perfluorohexane, dichloromethane and 1,2-dibromoethane as solvent) at 0 ° C or lower. The reaction was allowed to proceed for 2 days (Jana N.K., Verkade J.G .: Org. Lett. 2003, 5, 21, 3787).

P-Tolueneperoxosulfonic acid, which was generated in situ by reacting p-toluenesulfonylimidazole with 33% H 2 O 2 in the presence of aqueous NaOH (IN), was also used for pyridine oxidation. After stirring at room temperature for 1.5 hours, 60% PNO was obtained (Kluge R., Schulz M., Liebsch S .: Tetrahedron 1996, 52, 16, 5773.).

Benzonitrile provides peroxocarboximide acid by reaction with 50% H ₂ O ₂ at pH 8. This acid oxidizes pyridine to PNO in 3 hours at room temperature in 79% yield. As a by-product, benzamide is formed which is relatively easy to separate from PNO. In the absence of a substrate (pyridine), peroxocarboximide acid reacts with H ₂ O ₂ to form benzamide and oxygen. The oxidation of pyridine was performed in methanol (Payne GB, Deming PH, Williams PH: J. Org. Chem. 1961, 26, 369).

A much better yield was achieved with the H ₂ O ₂ -acetonitrile system. This oxidation is rapid due to the formation of the active intermediates, which is peroxoacetimidic acid. The reaction was carried out in aqueous medium using 30% H ₂ O ₂ . Pyridine mixed with acetonitrile and water was heated to 75 ° C and then H ₂ O ₂ was added dropwise. After processing, 80-90% of PNO was obtained (Laus G .: J. Chem. Soc. Perk. Trans 2 2001, 6, 864-868).

Nafion-H® is a perfluorinated resinsulfonic acid which has also been used as a catalyst for the oxidation of pyridine in the presence of 30% H ₂ O ₂ as an oxidant. This catalyst is a very strong acid (H0 = -11 to -13) and is very thermally and chemically stable. The oxidation was carried out at reflux in 1,2-dichloroethane and pyridine yielded 85% PNO in 4.5 hours. Here again, oxidation proceeded faster and with higher yields for pyridines with electron-substituent substituents. The envisaged mechanism involves oxidation of the sulfo group of the catalyst with H ₂ O ₂ to form peroxosulfonic acid, followed by migration of oxygen to the organic substrate (Jain SL, Sain B .: Appl. Catalysis A: General 2006, 301,259-264.).

For pyridine oxidation, acetic acid (or OXONE) was adsorbed onto silica gel or alumina. OXONE is potassium monoperoxosulphate 2KHSO ₅ .KHSO ₄ .K ₂ SO ₄ , the active ingredient of which is potassium peroxomonosulphate (K.HSO5, potassium salt of Caroic acids). The reaction was carried out in benzene at 80 ° C and after 5 hours a percentage of PNO between 61 and 89% was obtained, better results were obtained for OXONE than peroxoacetic acid as oxidant. The differences in the behavior of the two different oxidants (acetic acid and OXONE) are dependent on the conditions of their respective mechanisms of action during oxidation (Fields JD, Kropp PJ: J. Org. Chem. 2000, 65, 5937-5941.).

Methods of oxidizing pyridines with hydrogen peroxide with the participation of metals in PNO are widely described in the literature. From metals, both p-elements (Mg, Al, Si, etc.) and d-elements (V, W, Ti, Mn, etc.) are used. The advantage of using metals as catalysts is an increase in the oxidation capacity of hydrogen peroxide. Heterogeneous catalysis has several other advantages, such as easy catalyst regeneration and recycling, safe handling, high atomic economy, increased stability and long catalyst life.

Magnesium monoperoxophthalate (MMPP) was used to oxidize pyridine to PNO. It is a stable, water-soluble peroxophthalic acid derivative used as an oxidizing agent for various organic molecules. Oxidations are carried out at room temperature in aqueous solutions at neutral pH (using Na ₂ DPO ₄ / KD ₂ PO ₄ buffer, pH = 6.5). The experiments were conducted in a NMR-cuvette using deuterated water (D ₂ O). In the case of pyridine, the product was reached as early as 30 minutes and the PNO yield was 99% (Zheng T.-C., Richardson DE: Tetrahedron Lett. 1995, 36, 6, 837.).

Further, Mn (TDCPP) Cl complex (TDCPP = 2,6-dichlorophenylporphyrin) was used which, when mixed with a 3% acetonitrile solution of H ₂ O ₂ , stirred overnight at room temperature, gave PNO in 87% yield. Dichloromethane: acetonitrile (1: 1) was used as solvent (Battioni P., Mansky D .: EP 0705824 A1, 1996.).

Various vanadium complexes are often used for oxidation. Oxidation has been described using [V (O) (C1) (PBHA) ₂ ] (PBHA = N-phenylbenzohydroxamate) as a catalyst, 30% H ₂ O ₂ as an oxidant and acetonitrile as a solvent. After five hours of reflux, PNO was obtained in 96% yield (Tapan KS, Chowdhury K., Mukherjee M., Dulal CB, Bhattacharyya R., J. Mol. Cat. A: Chemical 2004, 219, 241).

Vanadium may also form a complex with the silica in a stoichiometric formula Si4 _{X X X} 4 O6. This complex is formed by stirring a 1: 1 (w / w) mixture of silica gel and vanadyl acetylacetonate (VO (acac) ₂ ) in dichloromethane at room temperature for 24 hours. This catalyst was used to oxidize various tertiary amines in the presence of 30% H ₂ O ₂ using acetonitrile as a solvent at 80 ° C. The oxidation of pyridine to PNO took place in 10 hours with a yield of 79%. The advantage of this catalyst is that it does not decrease its activity when used repeatedly (Rout L., Punniyamurthy T .: Adv. Synth. Catal. 2005, 347, 1958).

Titanium (Ti) can also form complexes with silica gel. For the oxidation of tertiary amines, the catalyst TS-1 is most used. It is a complex of SiO ₂ / TiO ₂ (Si / Ti ~ 33) and belongs to molecular sieves. This catalyst also has an initial activity even after repeated use. In the first case, only the catalyst, 30% H ₂ O ₂ and pyridine were used. Oxidation was performed by two methods.

In Method A, the reactants were premixed and then added to the catalyst to achieve a 95.3% PNO yield. In Method B, pyridine was first mixed with the catalyst for 5 minutes before the oxidizer was added. In this case, the yield increased somewhat (96%). Both methods were run at 60 ° C for 24 h (Robinson DJ, McMom P., Bethell D., Bulman-Page PC, Sly C., King F., Hancock FE, Hutchings GJ: Catal. Lett. 2001, 72, 3- 4, 233.).

In the next article, the question of whether the oxidation of pyridine with the TS-1/30% H ₂ O _{2 system} is better in water or in methanol was addressed. In the case of pyridine, oxidation proceeded much better in water and also faster (92.9%; 2.5 hours) compared to methanol (91.9%; 16 hours) (Prasat MR, Kamalakar G., Madhavi G., Bullets SJ, Raghavan KV: J. Mol. Cat. A: Chemical 2002, 186, 109.).

Another metal used to oxidize pyridine to PNO was tungsten (W). The Nai ₂ complex [WZn 3 (H ₂ O) ₂ ] [(ZnW ₉ O 34) ₂ ] was used as a catalyst for aqueous two-phase oxidation of pyridine in the presence of 60% H ₂ O ₂ and was obtained at 75 ° C for 7 hours 96% PNO (FreedomRozner D., Witte P., Alsters PL, Neumann R., Adv. Synth. Catal. 2004, 346, 339-345.).

For tungsten I am also known type catalyst LDH-WO ₄ ^second It is Mg-Al layered double hydroxide (LDH). This catalyst was used to oxidize tertiary amines in the presence of 30% H 2 O 2 at room temperature. The yields of oxidation are about 94-97%. It has not been used to oxidize pyridines yet. The authors present a probable reaction mechanism of oxidation. This involves the formation of peroxo-tungstate by the interaction of WO4 ² 'with H2O ₂ . Peroxo-tungstate converts its electrophilic oxygen to an amine, forming an N-oxide while recovering the active catalyst (Choudary, M., Bharathi, B., Reddy, V., Kantam, ML, Raghavan, KV: Chem. Comm. 2001, 1736- 1737.).

Very good PNO yield (nearly 100%, 1 h) was achieved using the methyltrioxorhenium-H ₂ O ₂ (MTO) system (Murray RW, Iyanar K., Chen J., Wearing JT: Tetrahedron Lett. 1996, 37, 6, 805-808.). Catalytic systems containing rhenium have unique properties (high

Oxidation ability, universality and unproductive decomposition of H ₂ O ₂ ). The disadvantage of using MTO is its limited stability due to its easy decomposition in the aqueous environment and high cost.

For this reason, sodium percarbonate (Na ₂ CO ₃ + H ₂ O ₂ ) has been proposed as an oxidation system for the oxidation of pyridines MTO, which is very easy to prepare, easy to store and, above all, a safe alternative to hazardous anhydrous H ₂ O ₂ . Sodium percarbonate was used as a solid oxidant in the presence of MTO and, together with pyridine and acetic acid, the reaction was carried out in acetonitrile at 50 ° C under N ₂ atmosphere. After 2.5 hours, 90% PNO was obtained. Using trifluoroacetic acid yields were comparable, but inorganic acids (HCl, H ₂ SO ₄ ) did not provide oxidation (Jain SL, Joseph JK, Sain B .: Synlett 206, 16, 2661).

Another oxidizing agent used in PNO synthesis was oxygen in the presence of metals. Air oxygen as an oxidizing agent is very attractive (environmentally and economically).

Gold compounds (HAuC1 _4), platinum (K ₂ PtCl _4), and rhodium (RhCl ₃₎ were adsorbed onto carbon, aluminum oxide or titanium dioxide. The following catalysts were prepared: 1% Au / C, 1% Pt / C, 1% Rh / C, 0.5% Au to 0.5% Pt / C, 0.5% Au to 0.5% Rh / C, 1% Au / Al ₂ O ₃ , 1% Au / TiO ₂ . These catalysts were used to oxidize pyridine using atmospheric oxygen in aqueous solution under mild conditions. The oxidations were carried out in a glass reactor connected to an oxygen source (pO ₂ = 202 650 Pa). The pyridine oxidations were carried out in water at 90 ° C or in an alkaline aqueous solution (pH = 10.8). All the catalysts tested had a 100% conversion of pyridine to PNO during the 2-hour test (Pina CD, Falletta E., Rossi M .: Top. Catal. 2007, 44, 1-2, 325.).

The above methyltrioxorhenium (MTO) has also been used to oxidize pyridine under an oxygen atmosphere. After a 3.25 hour reflux of pyridine in acetonitrile, a yield of 90% PNO was obtained (Sharma, V. B., Jain, S.L., Sain, B .: Tetrahedron Lett. 2003, 44, 3235).

Oxidation of tertiary amines in the presence of RuCl ₃ .nH ₂ O catalyst was also carried out under mild laboratory conditions. The reactions were carried out in dichloroethane and the reaction mixture was bubbled with atmospheric oxygen. The pyridine was oxidized in 8 hours with a yield of 85%. It has been discovered that pyridines that contain electron-like substituents (eg, 4-picoline) react more rapidly and provide higher yields. Pyridines with electron-acceptor groups (4-cyanopyridine), on the other hand, reacted much more slowly and in lower yields. Here too, the rate of oxidation of 4-picoline in various solvents was observed. Dichloroethane turned out to be the best (in 6 h - 98% conversion). Approximately 50% yield was obtained after 12 hours in methanol and ethanol. In acetone the reaction did not run at all, even after 20 hours. For 4-picoline, another ruthenium catalyst has also been tested: dichlorotris (triphenylphosphine) ruthenium (2+) and has proven to be even more effective. After 5 hours 100% conversion was achieved. Although the mechanism of action of the Ru-catalyst is not entirely clear, the authors assume that it involves the formation of the oxo-ruthenium compound (by the action of O ₂ on Ru). This is followed by the transfer of oxygen to tertiary nitrogen, which leads to the desired PNO (Jain SL, Sain B .: Chem. Commun. 2002, 1040.). A disadvantage of the embodiment is the high cost of the ruthenium catalyst and the use of environmentally toxic dichloromethane.

Another described aerobic oxidation of pyridine is the use of a cobalt-containing catalyst. This complex contains Schiff's base as ligands. It binds very well with molecular oxygen and therefore has a high efficiency in oxidation reactions. The oxidation was carried out in dichloroethane at room temperature in the presence of a 5-Å molecular sieve (a molecular sieve with a void size of ⁵ x ^{10 -10} m, removing moisture from the reaction mixture) and a Co-catalyst. About 80% of PNO was obtained after 8 hours. Again, the pyridines with electron-donor substituents reacted more lychly than those with electronceptoms (Jain SL, Sain B .: Angew. Chem. Int. Ed. 2003, 42, 11, 1265.).

In the next article, the study of O ₂ / RCHO / Fe ₂ O ₃ activity on pyridine oxidation was first published. The reaction was carried out with 3 eq. of aldehyde in 1,2Dichloroethane at 50 ° C (O ₂ was bubbled through the apparatus) and after 3 hours 89% PNO was obtained. The oxidation of pyridine has been shown to be

It strongly depends on the type of aldehyde (isovaleraldehyde was the most effective) and also on its amount. At 2 eq. of aldehyde, the yield decreased to 49% and at 1 eq. up to 29%. Furthermore, the activity of several transition metals has been studied, and Fe ₂ O ₃ and Cu (OH) ₂ , whose activity is much greater than that of cobalt salts (Wang F., Zhang H., Song G., Lu X. Synth. Commun., 1999, 29 (1), 11-).

In addition to the above reagents for oxidizing pyridines to PNO, another has been described.

Anhydrous 33% t-butyl hydroxyperoxide in toluene was used to oxidize pyridine with catalyst (MoO ₃ absorbed on alumina) at 110 ° C under N ₂ atmosphere. It has been found that aliphatic tertiary amines are more reactive and substituted anilines less reactive than pyridines. Again, pyridines with electron-substituent substituents proved to be the most reactive of all pyridines. The advantage of using this catalyst is again the retention of activity in multiple uses. Pyridine yielded 90% yield in 4.5 hours (Jain SL, Joseph JK, Sain B .: Catal. Let. 2007, 115, 1-2.8).

Urea adduct with H ₂ O ₂ was also used for PNO preparation. The oxidation was carried out in the solid phase at 85 ° C and 87% PNO was obtained after 45 minutes (Varma RS, Naicker KP: Org. Lett. 1999, 1, 2, 189-191).

A heterogeneous catalyst (perflurated ketone bound to silica gel) was also used to activate aqueous H ₂ O ₂ . This insoluble silicate was prepared by sol-gel polymerization of octafluoroacetophenone with silica gel. First, the ketone group is protected by the formation of an imine with n-butylamine. The protected ketone is then subjected to nucleophilic substitution with an aminosilane. Insoluble silicate was prepared by copolymerization with tetraethoxysilane by the sol-gel method. The final catalyst was observed after deprotection (with 30% H ₂ O ₂ ). 99% PNO was obtained after heating in acetonitrile (80 ° C, 24h) by treatment with 60% H ₂ O ₂ . Oxidation proceeds by the same mechanism as previously known for hexafluoroacetone. Reaction with H ₂ O ₂ produces the intermediate ahydroperoxoperfluor alcohol which is able to react with the nucleophilic substrate to form the oxo product. The disadvantage of using hexafluoroacetone is its high toxicity and instability (Neimann K., Neumann R .: Chem. Commun. 2001, 487).

In addition to hydrogen peroxide, dioxiranes can also be used as oxidizing agents.

In 1985 PNO was prepared in 93% yield by oxidation of pyridine with oxone in water, which was added dropwise to a solution of pyridine in acetone with phosphate buffer. The product was obtained in 2 hours with stirring at room temperature. When the reaction mixture was heated to 50 ° C for 16 hours, acetone peroxide was formed as a by-product and the PNO yield was only 63%. When the reaction was carried out in the absence of water, the PNO yield was 70-80% and other by-products (Murray R. W., Jeyaraman R., J. Org. Chem. 1985, 50, 2847.).

Later, in 1992 an article was published using another dioxiran. 1,2-dioxaspiro [2.5] octane was obtained by reaction of cyclohexanone with OXONE. The oxidation of pyridine with this dioxirane was carried out at -20 ° C and 100% PNO was obtained in 5 minutes (Murray R. W., Singh M., Jeyaraman R., J. Am. Chem. Soc. 1992, 114, 1346).

Dioxiran has also been used as an oxidizing agent in the form of a polymer. This synthesis is carried out in six steps. The starting material is 2% divinylbenzene crosslinked with polystyrene resin. This beaded polymer first undergoes Friedel-Crafts reaction with adipoyl chloride to form δ-ketopentanoic acid. It is reduced by Zn / Hg in HCl to hexanoic acid, which affords the acid chloride by reaction with thionyl chloride, which gives the malonic ester with ethoxymagnesium diethyl malonate, followed by hydrolysis to the ketone. This ketone is finally converted to the dioxirane group. Pyridine was oxidized with this resin in chloroform at 30 ° C (resin: pyridine = 2: 1) and 83% PNO was obtained after 35 hours (Shiney A., Rajan PK, Sreekumar K .: Polymer International 1996, 41, 377.) .

-5 CZ 305316 B6

N-halogen- N -metallosulfonainides are highly appreciated intermediates in various group transformations (sources of halogen cation or A-anion). Bromamine-T is a strong oxidant in both acidic and basic environments and has therefore been tested for the oxidation of pyridine and its derivatives. Reactions were carried out at 80 ° C in acetonitrile-water (1: 1) at alkaline pH (8.4) using a catalytic amount of RuCl ₃ . The substrate: bromamine-T ratio was 1: 1.2. Pyridine gave 75% PNO in 3 hours (Sharma VB, Jain SL, Sain B., Tetrahedron Lett. 2004, 45, 4281). Trichloroisocyanuric acid [1,3,5-trichloro-1,3,5triazine-2,4,6- (1 Η, 3H, 5H) -trione] was used as another oxidizing agent for PNO synthesis. Pyridine gave 81% PNO at 40 ° C in 2 hours. The reaction was carried out in the presence of a buffer (NaOAc / AcOH) as the reaction releases HCl gas which could react with the oxidant to form chlorine. In the absence of buffer, only about 50% yield was achieved. Acetonitrile: dichloromethane: water (1: 1: 0.05) was used as the reaction medium. Dichloromethane was used because of the low solubility of N-heterocycles in acetonitrile. Traces of added water serve to accelerate the reaction, under very anhydrous conditions the reaction is very difficult, but excessive amounts of water slow the reaction and reduce yields (Zhoní P., Guo S., Song C .: Synth. Commun. 2004, 34, 2, 247 .).

In the absence of a metal catalyst, pyridine was oxidized with a molecular oxygen / 2-methylpropanal system. Oxygen was introduced into a solution of 2-methylpropanol in 1,2-dichloroethane and, after cooling to 10 ° C, pyridine (aldehyde-amine amine ratio = 3.5: 1) was added. After 20 hours of stirring at room temperature, 76% PNO was obtained. Much greater yield (100%) was achieved in approximately the same reaction time with other aldehydes (isobutyraldehyde, n-butyraldehyde and cyclohexanecarbaldehyde) (Donore RS, Rao Τ V., Sharma K. K., Bhatia VK: Synth. Commun. 2001, 31.2, 167.).

Methylosinus trichosporium and Methylococcus capsulatus are bacteria that use methane as a source of carbon and energy. They are commonly referred to as "methylotriols" (Anthony, C., The Biochemistry of Methylotrophs, Academic Press, 1982: 2-30). Recently, it has been discovered that these bacteria, or their enzyme extracts, are capable of oxidizing organic molecules. Oxidations are probably catalyzed by the enzyme methanmonooxygenase (MMO), which is contained in the cells of these bacteria. It has now been found that these bacteria can be adapted to utilize methanol as the sole carbon source for growth without suppressing the ability to produce the MMO enzyme. This method was used for oxidation of alkanes, alkenes and alcohols as well as pyridine. Reactions were carried out at pH 7-8 (adjusted with phosphate buffer) and 70-90% of the product was obtained after 12 hours at 30 ° C (Higgins I.J .: GB 2081306, 1982.).

A disadvantage of the prior art solutions is either the use of acid oxidizing agents or solvents in which the oxidation of pyridines to PNO takes place. This results in the formation of pyridine oxides in the form of salts, which need to be converted to the free bases, resulting in increased production costs and an increased environmental impact of such processes. Furthermore, application of expensive and toxic solvents, excipients, eventually catalysts and co-catalysts. Processes using inorganic carriers such as silica gel, alukina and clays have the disadvantage that they can mechanically damage the process equipment. Processes operating at high pressures and / or temperatures, or vice versa, lower than conventional temperatures are energy intensive and hence economically demanding.

It is an object of the present invention to overcome the disadvantages of the prior art and to provide an active, stable, simple and thus cost-effective system providing high PNO yields.

SUMMARY OF THE INVENTION

It is an object of the present invention to use a catalytic system comprising an active catalyst component of the general formula [(P) _a (Si) b (B) _c (W) _p (Mo) q (V) _r 0 ₄ o] ^x , wherein phosphorus is in an oxidation state +5, silicon is in oxidation state +4, boron is in oxidation state +3, indices a, b, c are numbers from interval 0 to 1, the sum of a + b + c = 1, tungsten is in oxidation state +6 , molybdenum is

-6GB 305316 B6 in oxidation state +6, vanadium in oxidation state +5, indexes p, q, r are numbers from interval 0 to 12, where sum of p + r + q = 12, ax = 80-5a-4b- 3c-6p-6q-5r, and mixtures of these heteropolyanions, wherein the active catalyst component is ionically immobilized on an organic anion exchange resin by protonated or quaternized oligoamines of the general formula - [NRCH ₂ CH ₂ . (CH ₂ ) _m ] n NR ₃ ⁺ , wherein m = 0 to 2, n = 1 to 5, and R is selected from the group consisting of hydrogen and C 1 to C ₄ alkyl, and / or via quaternary ammonium groups of the formula - ( NR ' ₃ ), wherein R' is selected from the group consisting of C 1 -C 4 alkyl and 2-hydroxyethyl, wherein the protonated or quaternized oligoamines and / or the quaternary ammonium groups are bonded to the organic anion exchanger via methylene -CH ₂ - or carbonyl - (C = O) functional groups for oxidizing pyridine and its methyl derivatives to the corresponding pyridine-1-oxides with hydrogen peroxide.

Preferably, the organic anion exchange resin is selected from the group consisting of a cross-linked methylstyrene-vinylbenzene gel or macroporous type copolymer, a gel or macroporous type acrylate polymer, and a gel or macroporous type methacrylate polymer.

In a preferred embodiment of the invention, the divinylbenzene content of the methylstyrenedivinylbenzene copolymer is in the range of 5 to 20% by weight.

The present invention further provides a process for the preparation of an immobilized catalytic system for oxidizing pyridine and its methyl derivatives to the corresponding pyridine-1-oxides with hydrogen peroxide, the process comprising, preferably at a temperature of 20 ° C to 30 ° C, an aqueous a solution of the active catalyst component in the form of a salt, preferably a salt selected from the group consisting of ammonium, sodium, potassium salts, is eluted through a column packed with an organic anion exchanger or stirred with the organic anion exchanger to saturate the anion exchanger with the active catalyst component; [NRCH ₂ CH ₂ (CH 2) _m ] n NR ₃ ⁺ , wherein m = 0 to 2, n = 1 to 5, and R is selected from the group consisting of hydrogen and C 1 to C 4 alkyl, and / or quaternary ammonium groups - ( NR '3) ⁺ , wherein R' is selected from the group consisting of C 1 to C 4 alkyl and 2-hydroxyethyl, bonded to the organic anion exchanger via methylene -CH ₂ - or carbonyl (C = O) functional groups. The aqueous solution of the active catalyst component of the heterooxopolyanion is prepared in situ from the oxo compounds of molybdenum and / or tungsten and / or vanadium by reacting them with the oxo compounds of boron and / or silicon and / or phosphorus (phosphorus in oxidation stage +5).

Preferably, the aqueous solution of the active catalyst component is used in a concentration ranging from 0.05 mol / liter to 0.5 mol / liter.

Preferably, the organic anion exchanger bearing the quaternized oligoamines and / or the quaternary ammonium group is used in chloride form, the organic anion exchanger bearing the protonated oligoamines in the free base form.

The present invention provides an immobilized catalyst system for the oxidation of pyridine and its methyl derivatives to the corresponding pyridine-1-oxides (PNO) with hydrogen peroxide and a process for its preparation. The actual catalyst is mixed heterooxopolyanions (ΗΌΡΑ) of the general formula [(P) _and (Si) b (B) _c (W) _p (Mo) _q (V) _r 0 ₄ o] ^x “, where the phosphorus is in the oxidation state +5 , the silicon is in the oxidation state +4, the boron is in the oxidation state +3, the indices a, b, c are numbers from 0 to 1, the sum of a + b + c = 1, the tungsten is in the oxidation state +6, molybdenum is in oxidation state +6, vanadium in oxidation state +5, indexes p, q, r are numbers from interval 0 to 12, where sum of p + r + q = 12, ax = 80-5a-4b-3c6p-6q -5r, and mixtures of these heteropolynions which are ionically immobilized on commercial industrial organic anion exchangers. Hydrogen peroxide is activated for oxidation by the formation of highly active peroxo- or hyperoxo- immobilized HOPA. Similar catalyst systems for the activation of oxidizing agent, hydrogen peroxide, for oxidation of pyridine and its methyl derivatives to PNO are not known in the literature. For the oxidation of other organic substrates such as secondary and tertiary amines, alkenes and others, Keggin-type HOPAs (Kozhevnikov IV: Chemical Reviews 1998, 98, 171) are used in homogeneous systems (Murahashi S.-I., Mitsumi H., Shiota T., TsudaT., Watanabe S., J. Org. Chem., 1990, 55, 1736; Sheng, N., Zajacek JG, J. Org. Chem., 1968, 33, 2, 588; , D'Aloisio R., J. Org. Chem., 1988, 53, 1553 .;

-7EN 305316 B6

Aoki, M., Ogawa, M., Hashimoto, T., Noyori, R., J. Org. Chem. 1996, 61, 8310.), optionally mobilized on inorganic carriers (e.g. Pizzio LR, Vazquez PG, Caceres CV, Blanco MN: Applied Catalysis A: General 256 (2003) 125 .; Liu H., Iglesia E .: Journal of Catalysis 223 (2004) 161.), or on a polyvinyl alcohol matrix or poly (4-vinylpyridine) (Nomiya K., Murasaki H., Miwa M.: Polyhedron 5 (1986) 1031).

Furthermore, it has been found that immobilized HOPAs are bound to commercial industrial organic anion exchangers by ionic interaction through protonated or quartemized oligoamine structural motifs - [NRCH ₂ CH ₂ (CH ₂ ) _m ] n NR ₃ ⁺ , where m = 0 to 2, n = 1 to 5, and R is hydrogen and / or C1-C4 alkyl, or quaternary ammonium groups - (NRjjj where R 'is C1-C4 alkyl or 2-hydroxyethyl, immobilized on an anion exchange resin, preferably a crosslinked methylstyrene-divinylbenzene gel or macroporous copolymer type or acrylate or methacrylate polymers, gel or macroporous type, via a methylene -CH ₂ - or carbonyl - (C = O) - functional group. the content of divinylbenzene crosslinker is methylstyrene-divinylbenzene copolymer from 5 to 20 wt% .

It has further been found that the catalyst system according to the invention can be prepared by washing an aqueous solution of the above HOPA in the form of a salt, preferably ammonium and / or sodium and / or potassium salt, through a column packed with an organic industrial anion exchange resin or anion exchange saturation. The concentration of HOPA in the anion exchange resin according to the invention varies between about 0.5 and 1 mol / liter of anion exchange resin, depending on the type of anion exchange resin used. After saturation, the catalyst system is ready for application.

Oxidation of pyridine and its methyl derivatives directly to the corresponding pyridine-1-oxides in the form of the free bases with said immobilized catalyst system can be carried out with 5 to 30% hydrogen peroxide in an aqueous non-acidic solution without the use of other organic solvents and other additives at temperatures in the range of 25 to 70 ° C and at atmospheric pressure for 6 to 12 h.

In the oxidation process, high selectivity of the reaction and high yields of 90-98% of the respective pyridine-1-oxides are achieved while significantly reducing the reaction time compared to other cheap systems using hydrogen peroxide as an oxidant. free bases by simply evaporating water, which is in fact the only waste. Advantages of the solution according to the invention are, for example, the fact that the immobilized catalyst can be easily separated from the reaction mixture and reused without losing its activity, further reducing economic costs, including environmental burden. The used anion exchangers are cheap synthetic resins used industrially for water treatment. Compared to HOPA, which are immobilized on inorganic supports such as silica gel, alumina, alumosilicates and the like, the organic polymeric anion exchangers used do not rub the surface of the reaction vessels.

The invention is illustrated by the following examples without limiting the scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Ammonium dodecamoyl phosphate (NH4) ₃ (PMoi ₂ 0 ₄ o) (18.80 g, 10 mmol) is dissolved in 150 ml of water at 30 ° C, acidified with 5% aqueous hydrogen chloride solution to pH 1-2 and 67 are added. g of a macroporous type polyacrylate polymer with 2 - [(2 - {[2- (dimethylamino) ethyl] - (methyl) amino} ethyl) (methyl) amino] ethyl functionality linked to the carbonyl of the polyacrylate polymer, in the free base form, o a minimum total capacity of 1.25 mol / liter and a bulk density of 670 g / liter. The suspension is stirred for 120 min at 25-30 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight.

-8EN 305316 B6

The concentration of molybdenum determined by flame atomic absorption spectrometry according to ČSN EN 27627 ^ 1 was about 0.59 mol Mo / liter of prepared catalyst, concentration of phosphorus by spectrophotometric method according to ČSN EN ISO 10714 was about 0.05 mol P / liter of prepared catalyst.

Example 2

Potassium tungstate K ₂ WO (16.30 g, 50 mmol), ammonium vanadate NH4VO3 (5.85 g, 50 mmol) and boric acid H3BO3 (0.56 g, 9) are dissolved in 150 ml of water at 60 ° C. The solution is cooled to 25 ° C and acidified with 5% aqueous hydrogen chloride to pH 1-2. 70 g of methylstyrene-divinylbenzene copolymer containing 20 g of methylstyrene-divinylbenzene are added. % Of DVB (divinylbenzene), having a tri (2-hydroxyethyl) ammonium function attached to the -CH ₂ -group, in chloride form, with a minimum total capacity of 1.15 mol / liter and a bulk density of 700 g / liter. The suspension is stirred for 50 min at 25 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight. The concentration of tungsten and vanadium determined polarographically on a mercury drop electrode in the presence of cinnamic acid (Spálenka M .: Handbook of Inorganic Polarographic Analysis, SNTL, Prague 1961, p. 294) was about 0.29 mol W / liter and about 0.25 mol V / liter of prepared catalyst. The boron concentration determined by titration to the complex of boric acid with mannitol according to ČSN ISO 6849 was about 0.05 mol / liter of prepared catalyst.

Example 3

Ammonium molybdate (NH ₄ ) ₂ MoO ₄ (9.80 g, 50 mmol), ammonium vanadate NH ₄ VO ₃ (5.85 g, 50 mmol) and sodium silicate are successively dissolved in 150 mL of water at 60 ° C. ₂ SiO ₃ (1.10 g, 9 mmol) and the solution was stirred at this temperature for 4 h. after the solution was cooled to 25 ° C and acidified with 5% aqueous HCl solution to pH 1 to 2 to this solution was 72 g of a gel type polymethacrylate polymer having a 3- (trimethylammonio) propyl functionality linked to the carbonyl of the polymethacrylate polymer, in chloride form, with a minimum total capacity of 1.25 mol / liter and a bulk density of 720 g / liter are added. The suspension is stirred for 40 min at 25 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight. The concentration of molybdenum was about 0.31 mol Mo / liter, vanadium about 0.30 mol V / liter and the silicon concentration (determined spectrophotometrically according to ISO 5997) was about 0.06 mol / liter of prepared catalyst.

Example 4

Ammonium molybdate (NH 4) ₂ MoO ₄ (9.80 g, 50 mmol), potassium tungstate K ₂ WO ₄ (16.30 g, 50 mmol) and boric acid H 3 BO3 ( The solution was stirred at this temperature for 5 h. The solution was cooled to 25 ° C and acidified to pH 1-2 with 5% aqueous hydrogen chloride solution. 67 g of copolymer were added to the prepared solution. Acrylic acid-DVB containing 20% DVB, with 2 - [(2 - {[2 (dimethylamino) ethyl] (methyl) amino} ethyl) - (methyl) amino] ethyl functionality linked to -CH ₂ - methylstyrene copolymer group , in the form of the free base, with a minimum total capacity of 1.25 mol / liter and a bulk density of 670 g / liter. The suspension is stirred for 45 min at 25 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight. The concentration of molybdenum was about 0.34 mol Mo / liter, tungsten about 0.32 mol W / liter and the boron concentration was about 0.05 mol / liter of prepared catalyst.

-9EN 305316 B6

Example 5

Ammonium molybdate (NH ₄ ) ₂ MoO ₄ (6.47 g, 33 mmol), potassium tungstate K ₂ WO ₄ (10.76 g, 33 mmol) ammonium vanadate NH _{4 are} gradually dissolved in 150 mL of water at 60 ° C. VO ₃ (3.86 g, 33 mmol), sodium silicate Na ₂ SiO ₃ (0.57 g, 4.7 mmol) and boric acid H ₃ BO ₃ (0.29 g, 4.7 mmol), The solution was cooled to 25 ° C and acidified with 5% aqueous hydrogen chloride to pH 1-2. 70 g of a macroporous type polyacrylate polymer with 2 - [(2- {[2- (dimethylamino) ethyl] (methyl) amino} ethyl) - (methyl) amino] ethyl functionality linked to the carbonyl of the polyacrylate polymer, in free base form, with a minimum total capacity of 1.5 mol / liter and a bulk density of 700 g / liter. The suspension is stirred for 45 min at 25 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight. The concentration of molybdenum was about 0.36 mol Mo / liter, tungsten about 0.33 mol W / liter, vanadium 0.35 mol V / liter, silicon concentration about 0.026 mol Si / liter and boron concentration was about 0.029 mol B / liter of prepared of the catalyst.

Example 6

Ammonium molybdate (NH 4) ₂ MoO ₄ (6.47 g, 33 mmol), potassium tungstate K ₂ WO ₄ (10.76 g, 33 mmol) ammonium vanadate NH ₄ VO are gradually dissolved in 150 mL of water at 60 ° C. ₃ (3.86 g, 33 mmol), sodium silicate Na ₂ SiO ₃ (0.38 g, 3.1 mmol), boric acid H ₃ BO ₃ (0.19 g, 3.1 mmol) and ammonium dihydrogen phosphate NH _{The 4} H ₂ PO ₄ (0.36 g, 3.1 mmol) solution was stirred at this temperature for 5 h. The solution was then cooled to 25 ° C and acidified to pH 1-2 with 5% aqueous HCl. 69 g of methyl styrene-DVB copolymer containing 10% DVB, with 2 - [(2 - {[2- (dimethylamino) ethyl] (methyl) amino} ethyl) (methyl) amino] ethyl functionality linked to the - A CH ₂ - methylstyrene copolymer group, in free base form, with a minimum total capacity of 1.25 mol / liter and a bulk density of 690 g / liter. The suspension is stirred for 45 min at 25 ° C. Then the catalyst was decanted, washed three times with 80 ml of water and air dried to constant weight. The concentration of molybdenum was about 0.36 mol Mo / liter, tungsten about 0.33 mol W / liter, vanadium 0.35 mol V / liter, silicon concentration about 0.017 mol Si / liter, boron concentration was about 0.018 mol B / liter and of phosphorus about 0.017 mol P / liter of prepared catalyst.

Example 7

Dissolve (NH ₄ ) ₂ MoO ₄ (9.80 g, 50 mmol), ammonium vanadate NH ₄ VO ₃ (5.85 g, 50 mmol) and boric acid H ₃ BO in 150 mL water at 60 ° C. ₃ (0.56 g, 9 mmol) and the solution was stirred at this temperature for 4 h. The solution was cooled to 25 ° C and acidified to pH 1-2 with 5% aqueous hydrogen chloride solution. 5 cm in diameter containing 67 g of a macroporous type polyacrylate polymer with 2 - [(2 - {[2- (dimethylamino) ethyl] (methyl) amino} ethyl) (methyl) amino] ethyl functionality attached to the carbonyl group of the polyacrylate polymer, in free base form, with a minimum total capacity of 1.25 mol / liter and a bulk density of 670 g / liter, at a rate of 2ml / min, at 25 ° C. The catalyst was then spilled from the column, washed three times with 80 ml of water and air dried to constant weight. The molybdenum concentration was about 0.29 moles Mo / liter, vanadium 0.30 moles V / liter and the boron concentration was about 0.04 moles B / liter of prepared catalyst.

Example 8

Ammonium molybdate (NH 4 MoCl 4 (6.47 g, 33 mmol), potassium tungstate K ₂ WO ₄ (10.76 g, 33 mmol) ammonium vanadate NH ₄ VO _{3 are} dissolved in 150 ml water at 60 ° C successively. (3.86 g, 33 mmol), sodium silicate Na ₂ SiO ₃ (0.57 g, 4.7 mmol) and boric acid H ₃ BO ₃

- 30 ° C 305316 B6 (0.29 g, 4.7 mmol), the solution was stirred at this temperature for 5 h. The solution was then cooled to 25 ° C and acidified to pH 1-2 with 5% aqueous HCl. the solution is passed through a 5 cm diameter column containing 71 g of a macroporous type polyacrylate polymer copolymer with 2 - [(2 - {[2- (dimethylamino) ethyl] (methyl) amino} ethyl) (methyl) amino} ethyl functional group on a carbonyl of a polyacrylate polymer, in free base form, with a minimum total capacity of 1.5 mol / liter and a bulk density of 710 g / liter, at a rate of 2 ml / min. The suspension is stirred for 45 min at 25 ° C at 25 ° C. The catalyst was then spilled from the column, washed three times with 80 ml of water and air dried to constant weight. The concentration of molybdenum was about 0.33 mol Mo / liter, tungsten about 0.30 mol W / liter, vanadium 0.34 mol V / liter, silicon concentration about 0.024 mol Si / liter and boron concentration was about 0.028 mol B / liter of prepared of the catalyst.

Example 9

Pyridine (79.0 g, 1 mol) was dissolved in 300 mL of methanol, the catalyst of Example 2 (25 g) was added, and 30% hydrogen peroxide (136.0 g, 1.2 mol). The reaction mixture was then refluxed for 8 h. The catalyst was then filtered off and stored for further use. 3 g of activated carbon were added to the filtrate, the suspension was filtered and the filtrate was vacuum fractionated. The major portion was collected at 100-105 ° C and torr (= 133 Pa). 90.2 g (94.7%) of pyridine-1-oxide, mp 65.5-66.0 ° C, literature (Org. Synth. 1963, Coll. Vol. 4, 828) 65-66 ° were obtained C. The content of the main component determined by gas chromatography, the internal standard 2,6-dimethylpyridine-1-oxide, was 99.5% relative. (from peak area).

Example 10

3-Methylpyridine (93.0 g, 1 mol) was dissolved in 300 mL of water, the catalyst of Example 4 (25 g) was added, and 30% hydrogen peroxide (136.0 g) was added dropwise at 50 ° C over 10 min. g, 1.2 mol). The reaction mixture was then heated at 70 ° C for 7 h. The catalyst was then filtered off and stored for further use. 3 g of activated carbon were added to the filtrate, the suspension was filtered and the filtrate was vacuum fractionated. The bulk was collected at 101-103 ° C / 0.7-0.8 torr (= 93-107 Pa). 99.9 g (90.9%) of 3-methylpyridine-1-oxide were obtained. Melting point 40.0-40.5 ° C, literature (http://www.tcieurope.eu/no/catalog/P0419.html) 37 ° C. The content of the main component determined by gas chromatography, the internal standard 2,6-dimethylpyridine-1-oxide, was 99.3% relative. (from peak area).

Industrial applicability

The invention can be used industrially in small-scale production of pyridine-1-oxide and its methyl derivatives. Pyridine-1-oxide and its methyl derivatives are widely used as starting intermediates in the manufacture of substituted pyridines with a wide range of applications in the pharmaceutical and phyto-effector chemical industries (particularly as pesticides, growth promoters, etc.). Pyridine-1-oxide and its methyl derivatives are also used in organic syntheses as activators and carriers of electrophilic structural motifs to nucleophilic substrates in the aforementioned industries. Pyridine and its methyl derivatives are part of the so-called pyridine fraction resulting from hard coal coking.

Claims (7)

PATENT CLAIMS Use of a catalytic system comprising an active catalyst component which is a mixed heterooxopolyanion of the general formula [(P) _a (Si) _b (B) _c (W) _p (Mo) _q (V) _r 0 ₄ o] ^x y wherein phosphorus is in oxidation state +5, silicon is in oxidation state +4, boron is in oxidation state +3, indices a, b, c are numbers from interval 0 to 1, where sum of a + b + c = 1, tungsten is in oxidation state +6, molybdenum is in oxidation state +6, vanadium is in oxidation state +5, indexes p, q, r are numbers from interval 0 to 12, where sum of p + r + q = 12, ax = 80-5a -4b-3c-6p-6q-5r, and mixtures of these heteropolyanions, wherein the active catalyst component is ionically immobilized on an anion exchange resin via protonated or quaternized oligoamines of the general formula - [NRCH 2 CH 2 (CH 2) m] n NR 3 ⁺ , where m = 0 to 2, n = 1 to 5, and R is selected from the group consisting of hydrogen and C 1 to C 4 alkyl, and / or via quaternary ammonium groups of the general formula of the formula - (NR ' ₃ ) ⁺ , wherein R' is selected from the group consisting of C 1 -C ₄ alkyl and 2-hydroxy ethyl, wherein the protonated or quaternized oligoamines and / or the quaternary ammonium groups are bonded to the organic anion exchange via methylene -CH ₂ - or carbonyl - (C = O) - functional groups for oxidizing pyridine and its methyl derivatives to the corresponding pyridine-1-oxides with hydrogen peroxide. Use according to claim 1, characterized in that the organic anion exchange resin is selected from the group consisting of a crosslinked methylstyrene-divinylbenzene copolymer of the gel or macroporous type, an acrylate polymer of the gel or macroporous type, and a methacrylate polymer of the gel or macroporous type. Use according to claim 2, characterized in that the content of divinylbenzene in the methylstyrenedivinylbenzene copolymer is in the range of 5 to 20% by weight. Process for the preparation of an immobilized catalytic system for oxidizing pyridine and its methyl derivatives to the corresponding pyridine-1-oxides with hydrogen peroxide according to any one of claims 1 to 3, characterized in that the aqueous solution of heterooxopolyanion is prepared in a network of molybdenum and / or tungsten oxo compounds. and / or vanadium by reaction with oxo compounds of boron and / or silicon and / or phosphorus, and subsequently the aqueous solution of the active catalyst component in the salt form is washed through a column packed with an organic anion exchanger or stirred with the organic anion exchanger to saturate the anion exchanger with the active catalyst component. carries protonated or quaternized oligoamines - [NRCH ₂ CH ₂ (CH ₂ ) _m ] _n NR 3 ⁺ , wherein m = 0 to 2, n = 1 to 5, and R is selected from hydrogen and C 1 to C 4 alkyl, and / or a quaternary ammonium group - (NR'3) ⁺ , wherein R 'is selected from the group consisting of C 1 -C 4 alkyl and 2-hydroxyethyl, bound to the organic anion exchange resin through a methylene -CH ₂ - or carbonyl- (C = O) - functional group. 5. The process of claim 4 wherein the salts of the active catalyst component are selected from the group consisting of ammonium, sodium, potassium salts. The process according to claim 4, characterized in that the aqueous solution of the active catalyst component is used in a concentration ranging from 0.05 mol / liter to 0.5 mol / liter. Method according to claim 4, characterized in that the organic anion exchange resin carrying the quaternized oligoamines and / or the quaternary ammonium group is used in chloride form, the organic anion exchange resin carrying the protonated oligoamines in the form of the free base.