JP4035611B2 - Process for producing cyclooctene oxide - Google Patents

Description

  The present invention relates to a method for producing cyclooctene oxide. More specifically, the present invention is useful as a synthetic intermediate for organic industrial products and pharmaceutical products under mild reaction conditions by using a transition metal skeleton-substituted zeolite catalyst. The present invention relates to a method for producing cyclooctene oxide with high selectivity. In the technical field of organic synthesis for synthesizing various industrially important epoxide compounds from olefins, the present invention relates to peroxides having a risk of explosion, such as hydrogen peroxide, peracetic acid, t-butyl hydroperoxide. It is possible to produce cyclooctene oxide from cyclooctene with high reaction conversion rate and reaction selectivity under mild reaction conditions using only molecular oxygen-containing gas and transition metal skeleton substitution type zeolite catalyst. The present invention provides a novel organic synthesis method.

Conventionally, as a method of industrially synthesizing various epoxide compounds from chain and cyclic olefins, a method of performing a dehydrochlorination reaction through the action of a strong alkali via a chlorohydrin intermediate is generally used. ing. However, this method has a problem that a large amount of inorganic salts is by-produced. Moreover, as a specific method for synthesizing cyclooctene oxide, a method of reacting hydrogen peroxide in the presence of potassium carbonate using an acetonitrile solvent in which cyclooctene is dissolved is known (Non-patent Document 1). Alternatively, there is also known a method of obtaining a target epoxide by reacting hydrogen peroxide or t-butyl hydroperoxide with cyclooctene in the presence of an iron (III) porphyrin complex catalyst (Non-patent Document 2). Furthermore, recently, a heteropolyacid (γ-SiW ₁₀ [Fe ³⁺ (OH ₂ )] ₂ O ₃₈ ^-6 ) in which a part of the tungsten skeleton in silicotungstic acid is substituted with iron (III) is used as a catalyst. There has been reported a method for obtaining cyclooctene oxide with high selectivity in a mixed solvent of 1,2-dichloroethane and acetonitrile in the presence of atmospheric oxygen (Non-patent Document 3).

  However, in the above-described method, (1) hydrogen peroxide, organic hydroperoxide, and peroxycarboxylic acids that are relatively expensive and have a danger of explosion are difficult to handle, and (2) mass synthesis is difficult. The use of a complex organometallic complex catalyst, the use of a large amount of a chlorine-based or nitrogen-containing organic solvent that requires countermeasures against environmental pollution, or (3) the repeated use of the catalyst is difficult. In this technical field, as an industrial synthesis method of cyclooctene oxide, it has been desired to develop a novel production method that solves these problems.

  As a method for solving the above problems, a method of obtaining cyclooctene oxide from cyclooctene using a zeolite-based solid catalyst in which cobalt oxide having a nanostructure is formed in MCM-41 type zeolite and molecular oxygen gas is proposed. (Non-Patent Documents 4 to 5). However, in this method, it is essential to add a large amount of isobutyraldehyde to the oxidation reaction solution, and the true catalytically active species is a solid catalyst and a perisobutyric acid radical in which isobutyraldehyde is oxidized by molecular oxygen gas. ing. Therefore, this method is a modification of the Mukaiyama reaction, and it is necessary to separate isobutyric acid and unreacted isobutyraldehyde generated at the end of the reaction.

  In addition, various chain olefins and 6-membered cyclic olefins are oxygen-oxidized using a zeolite catalyst and molecular oxygen gas that has undergone skeleton substitution using various transition metals such as manganese or cobalt, to selectively obtain epoxy compounds. A method has also been proposed (Non-Patent Document 6). However, this method is also a modification of the Mukaiyama reaction described above, and it is essential to add a large amount of benzaldehyde to the oxidation reaction solution, and it is necessary to separate benzoic acid and unreacted benzaldehyde produced at the end of the reaction. There is no change.

J. W. Knight et al., Organic Synthesis, CV 7, vol. 126 Traylor et al., J. Am. Chem. Soc., 1993, 115, 2775 N. Mizuno et al., Angew. Chem. Int. Ed., 2001, 40, 3639 V. Kesavan et al., J. Indian Inst Sci, 2002, 82, 113 T. Mukaiyama et al., Chem. Lett., 1991, 1 page J. M. Thomas et al., Chem. Commun., 1999, 829.

  Under such circumstances, the present inventors, in view of the above prior art, easily absorb cyclooctene as a starting material and cyclooctene oxide as a reaction product in order to solve the above-described problems. Development of a zeolitic solid catalyst that has a detachable pore structure and only undergoes an epoxidation reaction without generating by-product cyclooctene peroxide, which has the risk of explosion when in contact with molecular oxygen gas. Used a transition metal skeleton substitution type zeolite catalyst obtained by skeletal substitution of a part of the elements forming the zeolite skeleton with a transition metal as a result of diligent examination of mild reaction conditions that enable highly selective reaction. As a result, it has been found that the above-described problems can be solved and the intended purpose can be achieved, and the present invention has been completed based on this finding.

  That is, the present invention is characterized in that only a transition metal skeleton substitution type zeolite catalyst and molecular oxygen gas are used, and cyclooctene is oxygen-oxidized under mild reaction conditions without adding other third substances. An object of the present invention is to provide a highly selective production method of cyclooctene oxide.

  The present invention also provides an industrial production method for synthesizing cyclooctene oxide in a simple and inexpensive manner, overcoming the drawbacks of the conventional synthesis methods described above, that is, cyclooctene oxide, which is a target product from cyclooctene. It is an object of the present invention to provide a method for selectively synthesizing cyclooctene oxide without adding a third substance other than molecular oxygen gas and a transition metal skeleton substitution zeolite catalyst. Is.

  Furthermore, the present invention obtains the desired product under mild reaction conditions of low temperature and constant pressure using extremely simple equipment and operation without accumulating cyclooctene hydroperoxide having a danger of explosion in the reaction system. In addition, by allowing repeated use of the catalyst and reaction under solvent-free conditions, post-treatment such as industrial industrial waste and industrial waste liquid becomes unnecessary, and it is extremely low cost and extremely industrially useful. An object of the present invention is to provide a method for producing cyclooctene oxide.

The present invention for solving the above-described problems comprises the following technical means.
(1) A method for producing cyclooctene oxide by oxidizing cyclooctene using a molecular oxygen-containing gas, and 1) a transition metal skeleton substitution type zeolite catalyst in which a part of the skeleton structure is substituted with a transition metal. In addition, only the molecular oxygen gas is used, and the cyclooctene is oxidized with oxygen without adding any other third substance. 2) The transition metal skeleton-substituted zeolite catalyst, cyclooctene and the molecular oxygen gas are liquid phase or gas. contacting the phase, 3) as the transition metal framework substituted Zeiraito catalysts, the use of a MFI type zeolite catalysts, the manufacturing method of cyclooctene oxide, wherein.
(2) MFI MFI-based zeolite catalysts, which are represented by a general formula _Na n _(H 2 _{O) 16 [Al n Si 96-n O 192]} (integer wherein, n is 0 ≦ n <27) The process for producing cyclooctene oxide according to (1) above, which is a transition metal skeleton-substituted zeolite having a structure corresponding to a zeolite and part of the skeleton structure substituted with another transition metal.
(3) a transition metal to perform skeleton substitution, is cobalt, the content for the zeolite catalyst is Ru 0.1 to 5 wt% der method of cyclooctene oxide according to (1).
(4) a transition metal to perform skeleton substitutions, cobalt, iron, manganese, nickel, vanadium, molybdenum, chromium, niobium, Ru der least one selected from tantalum, of cyclooctene oxide according to (1) Production method.
(5) charge of the transition metal used in order to perform the skeleton substitutions, Ru 0.2 to 20 wt% der respect zeolite as the starting material, method for producing cyclooctene oxide according to (1).
(6) Transition metal skeleton substitution type obtained by firing transition metal skeleton substitution type zeolite in a temperature condition of 200 to 700 ° C. in an oxygen atmosphere and activating the transition metal introduced into the zeolite skeleton to a higher oxidation electronic state. The method for producing cyclooctene oxide according to (1), wherein a zeolite catalyst is used.
(7) The process for producing cyclooctene oxide according to (1) above, wherein the transition metal skeleton substitution type zeolite catalyst, cyclooctene and molecular oxygen gas are contacted by a liquid phase reaction at a temperature of 10 to 150 ° C.
(8) The method for producing cyclooctene oxide according to (1) above, wherein the amount of the transition metal skeleton substitution type zeolite catalyst used is 0.1 to 50% by weight with respect to cyclooctene as a reaction substrate.

Next, the present invention will be described in more detail.
Zeolite catalysts used in the present invention, one general formula _Na n _(H 2 _{O) 16 [Al n Si 96-n O 192]} (wherein, n is 0 ≦ n <27 integer) MFI type represented by This is a transition metal skeleton substitution type zeolite having a structure corresponding to zeolite and having a part of the skeleton structure substituted with another transition metal. This transition metal skeleton-substituted zeolite can be produced by a known method (Verified Synthesis of Zeolitic Materials 2nd Revised Edition, Edited by H. Robinson, Synthesis Competition 1) .

  The type of transition metal used for skeletal substitution is not particularly limited as long as it is a transition metal belonging to Group 3 to Group 14 in the Periodic Table of Elements. Preferably, cobalt, iron, manganese, Desirable is a transition metal such as nickel, vanadium, molybdenum, chromium, niobium, tantalum, etc., which easily changes its oxidation number by oxidation or reduction reaction and can take a higher oxidation electronic state, and particularly preferably cobalt is used. .

  The amount of transition metal used for skeletal substitution is 0.2 to 20% by weight based on the starting zeolite. By adjusting the charging amount, the cobalt content in the catalyst raw material finally obtained can be arbitrarily adjusted between 0.1 to 10% by weight. However, when the charge amount is large, in addition to the skeleton-substituted transition metal, transition metal oxides are formed on the surface of the pores as well as in the pores, and inhibit the selective epoxidation reaction. Preferably, 0.1 to 5% by weight is used.

  The resulting transition metal skeleton-substituted zeolite is calcined under high temperature conditions to burn and remove the organic compound used as the template compound, and the transition metal introduced into the zeolite skeleton is activated to a higher oxidation electronic state. It is necessary to make it. By performing this calcination treatment, the transition metal skeleton-substituted zeolite is induced into an active catalyst in which only the epoxidation reaction can mainly occur when it comes into contact with molecular oxygen gas. The firing temperature is 200 to 700 ° C., preferably 500 to 600 ° C. in an oxygen atmosphere.

  The transition metal skeleton substitution type zeolite catalyst thus obtained can be used in the form of powder or kneaded with a third substance and granulated. It is also possible to form a thin film on another carrier and use it as a catalyst. The amount of the catalyst used is 0.1 to 50% by weight, preferably 2 to 20% by weight, based on cyclooctene as the reaction substrate.

  The molecular oxygen-containing gas used as the oxidant is pure oxygen, normal air, industrial exhaust gas, or a mixture of pure oxygen and other inert gases such as helium, nitrogen, argon, carbon dioxide in any proportion. Although used, pure oxygen is preferable in order to shorten the reaction time. The reaction pressure is suitably in the range of 0.1 to 50 atmospheres, but preferably 0.5 to 10 atmospheres in order to suppress the progress of excessive oxygen oxidation reaction.

  The method for bringing the transition metal skeleton substitution zeolite catalyst into contact with cyclooctene and molecular oxygen gas is not particularly limited, and any of liquid phase and gas phase methods can be used. Preferably, a liquid phase reaction is used from the viewpoint of suppressing polymerization of cyclooctene under high temperature conditions. The reaction temperature in the liquid phase reaction is usually 10 to 150 ° C., preferably 50 to 100 ° C.

  The reaction of the present invention is caused by radical species that are active oxygen complexes obtained by reacting molecular oxygen gas with a skeleton-substituted transition metal. Therefore, the solvent used in the reaction of the present invention is not particularly limited as long as it does not generate peroxide under the reaction conditions of the present invention, does not deteriorate due to oxygen oxidation reaction, and does not contain a radical trapping agent. For example, benzene, toluene, n-hexane, n-octane and the like are used. However, in the method of the present invention, since the reaction is promoted more favorably under the solvent-free condition, the solvent-free condition is preferably used.

  Although reaction time changes also with the addition amount of a catalyst, the range of 1 to 120 hours is suitable normally. By performing the reaction continuously for a long time, the reaction conversion rate gradually increases, but even in that case, the oxygen oxidation reaction after the end of the epoxidation reaction further proceeds, and the reaction selection of the desired epoxy compound There is no decline in sex.

  The reaction mixture obtained by the above method can isolate the target cyclooctene oxide by filtering the transition metal skeleton substitution zeolite catalyst and distilling it. The zeolite catalyst separated by filtration and the recovered cyclooctene can be reused as they are. In addition, when the catalytic activity decreases due to long-term use, regeneration is possible by treating in an oxygen atmosphere at a temperature range of 500 to 600 ° C.

  The transition metal skeleton-substituted zeolite used in the method of the present invention expresses a catalytically active species that promotes only the epoxidation reaction by adsorbing molecular oxygen gas in its pores. In the oxygen oxidation reaction of cycloolefins using a usual zeolite-based solid catalyst containing a transition metal, it is known that an explosive cycloolefin peroxy radical is generated as a reaction precursor. It is also known that enols and enones such as 2-cyclohexen-1-ol and 2-cyclohexen-1-one are by-produced through this peroxy radical, for example, in the case of cyclohexene. Yes.

  However, according to the method of the present invention, the cyclooctene peroxy radical generated as a reaction precursor undergoes a rapid transfer reaction in the pores of the skeleton-substituted zeolite catalyst and changes to the target cyclooctene oxide. Therefore, almost no enols or enones and peroxy radicals as by-products described above are confirmed, and only the epoxidation reaction proceeds preferentially, and high reaction selectivity is obtained.

  Moreover, the transition metal skeleton substitution type zeolite catalyst used in the method of the present invention has high lipophilicity, high specific surface area, and optimum pore diameter for reaction. For this reason, the target epoxidation reaction proceeds smoothly even under solvent-free conditions. In addition, the expression of catalytically active species for the epoxidation reaction is possible under low temperature and constant pressure conditions, and has the advantage that the catalyst can be used repeatedly.

  According to the present invention, (1) cyclooctene oxide can be produced with high selectivity under mild reaction conditions, and (2) the risk of explosion of hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, etc. Cyclooctene oxide can be produced from cyclooctene with high reaction conversion rate and reaction selectivity without using a peroxide having (3) Only the epoxidation reaction proceeds preferentially, and high reaction selectivity An effect is obtained that cyclooctene oxide is obtained.

EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.
Production Example 1
In this production example, a Co-MFI catalyst was synthesized by the following method. After dissolution of the solid sodium hydroxide 1.2g of distilled water 150 g, while stirring the colloidal silica solution (manufactured by Catalysts & Chemicals Industries (Ltd.) CATALOID SI-30, SiO2 30 %, Na 2 O 0.38%) 60. 0 g was added. Next, a solution in which 1.5 g of cobalt chloride hexahydrate is dissolved in 25 g of distilled water is added, and further, 7.99 g of tetrapropylammonium bromide is added as an organic structure-directing agent to make a slurry for hydrothermal synthesis. It was. The pH (11.9) of the resulting slurry was further adjusted to pH 13.4 by adding tetraethylammonium hydroxide, and reacted at 170 ° C. for 4 days in an autoclave having a Teflon (registered trademark) inner cylinder. The filter was washed. The obtained Na-type Co-MFI was further treated with 0.1N hydrochloric acid overnight, and calcined at 550 ° C. for 22 hours to remove organic substances, thereby obtaining a reaction catalyst.

  It was confirmed by an X-ray diffraction pattern and an electron microscope that there was no generation of Co-MFI and no precipitation of metal oxide after firing. The Co content in Co-MFI was confirmed by analysis of a Cs ion exchange sample and a proton type sample after acid treatment. The Co content of the proton type sample was 1.07 wt%.

Production Example 2 (Reference Example)
In this production example, a Co-ALPO-5 catalyst was synthesized by the following method. 11.55 g of orthophosphoric acid (manufactured by Nacalai Tax, reagent grade) was added to 31.3 g of ion-exchanged water, and the mixture was stirred until it was completely dissolved. This was cooled with ice water (0 ° C.), and 2.33 g of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, reagent special grade) was added and stirred until it was completely dissolved. Next, 6.25 g of pseudo boehmite (Catapal Alumina, SCC-30, 75% alumina) was added and stirred until completely dissolved. Further, 7.2 g of triethylamine (domestic chemistry, reagent special grade) was slowly added dropwise and stirred until completely dissolved. All operations during this time were performed while cooling with ice water (0 ° C.).

  The slurry solution thus obtained had a pH of 3.0. This slurry was transferred to an autoclave with a Teflon (registered trademark) inner cylinder and hydrothermally treated at 200 ° C. for 36 hours while rotating the autoclave. After hydrothermal treatment, the contents are taken out from the autoclave and separated into solid and liquid, and the solid is thoroughly washed with ion-exchanged water, dried at 100 ° C. for 20 hours, and calcined at 550 ° C. for 6 hours. It was. The Co content of this catalyst by ICP analysis was 2.9 wt%.

  Only 0.05 g of the 5Co-MFI-based zeolite catalyst obtained in Production Example 1 and 1.0 g of cyclooctene were added into a 100 ml pressure-resistant glass container equipped with an oxygen inlet at 1 atm, and oxygen gas was added under solvent-free conditions. While feeding, the mixture was stirred at 80 ° C. for 24 hours. After completion of the reaction, the reaction solution and the catalyst were separated by filtration. The obtained reaction solution was analyzed using gas chromatography, and the reaction conversion rate of cyclooctene and the reaction selectivity for cyclooctene oxide were determined. The results are shown in Table 1. Further, 1H-NMR was measured using a nuclear magnetic resonance apparatus, but no explosive cyclooctene hydroperoxide was confirmed.

Example 2 (reference example)
Synthesis and analysis of cyclooctene oxide were carried out in the same manner as in Example 1, using 0.05 g of the Co—AlPO-based zeolite catalyst obtained in Production Example 2 (Reference Example) . The results are shown in Table 1. In addition, in this catalyst, formation of cyclooctene hydroperoxide was not confirmed.

Example 3
Using the same method as in Production Example 2, a transition metal skeleton substitution type MFI-based zeolite catalyst was synthesized using iron, manganese, vanadium, and niobium. Using this catalyst, an oxygen oxidation reaction of cyclooctene was attempted in the same manner as in Example 1. The results are summarized in Table 1.

As described above in detail, the present invention relates to a method for producing cyclooctene oxide, and according to the present invention, there is little risk of explosion, and a mild reaction such as low temperature and constant pressure using an extremely simple apparatus and operation. Under the conditions, it is possible to provide a method for producing cyclooctene oxide, which is a useful industrial product intermediate, with high selectivity. In addition, the present invention can repeatedly use the catalyst, can be reacted in a solvent-free condition, does not require treatment of industrial industrial waste or industrial waste liquid, and has advantages such as extremely low cost, It is possible to provide a method for producing cyclooctene oxide having high industrial utility value.

Claims (8)

A method for producing cyclooctene oxide by oxidizing cyclooctene using a molecular oxygen-containing gas, 1) a transition metal skeleton-substituted zeolite catalyst in which a part of the skeleton structure is substituted with a transition metal, and a molecular Use only oxygen gas and oxidize cyclooctene with oxygen without adding any other third substance. 2) Contact transition metal skeleton-substituted zeolite catalyst with cyclooctene and molecular oxygen gas in liquid or gas phase. 3) A method for producing cyclooctene oxide , comprising using an MFI-based zeolite catalyst as the transition metal skeleton substitution type zeolite catalyst . MFI-based zeolite catalyst is one general formula _Na n _(H 2 _{O) 16 [Al n Si 96-n O 192]} (wherein, n is 0 ≦ n <27 integer) the MFI based zeolite represented by The method for producing cyclooctene oxide according to claim 1, which is a transition metal skeleton-substituted zeolite having a corresponding structure and a part of the skeleton structure substituted with another transition metal. Transition metal performing backbone substitution, it is cobalt, the content for the zeolite catalyst is Ru 0.1 to 5 wt% der method of cyclooctene oxide according to claim 1. Transition metal performing backbone substitution, cobalt, iron, manganese, nickel, vanadium, molybdenum, chromium, niobium, Ru der least one selected from tantalum, a manufacturing method of cyclooctene oxide according to claim 1. Charged amount of the transition metal used in order to perform the skeleton substitutions, Ru 0.2 to 20 wt% der respect zeolite as the starting material, cyclooctene oxide method according to claim 1.   A transition metal skeleton-substituted zeolite catalyst in which a transition metal skeleton-substituted zeolite is calcined in an oxygen atmosphere at a temperature of 200 to 700 ° C., and the transition metal introduced into the zeolite skeleton is activated to a higher oxidation electronic state. The manufacturing method of the cyclooctene oxide of Claim 1 used.   The method for producing cyclooctene oxide according to claim 1, wherein the transition metal skeleton substitution type zeolite catalyst, cyclooctene and molecular oxygen gas are contacted by a liquid phase reaction at a temperature of 10 to 150 ° C.   The manufacturing method of the cyclooctene oxide of Claim 1 whose usage-amount of a transition metal frame | skeleton substitution type | mold zeolite catalyst is 0.1 to 50 weight% with respect to the cyclooctene which is a reaction substrate.