JPS6346732B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the reaction of cyclopentene with alkylidene peroxide in the presence of a catalyst consisting of a mixture of at least one compound of elements of groups b, b, b, b of periods 4, 5 and 6 of the periodic table. The present invention relates to a method for producing glutaraldehyde. Glutaraldehyde is an important intermediate raw material for various chemical products, and is also used in applications such as leather tanning agents, hardening agents for microcapsules, disinfectants, crosslinking agents, and enzyme immobilization agents. Glutaraldehyde is currently mainly produced from allolein and vinyl ether.
It is produced by hydrolyzing 2-alkoxy-dihydropyran produced in the Diels-Alder reaction. However, this method has the disadvantage that the process is long and the raw materials are expensive and difficult to obtain.
In addition, a method of oxidizing 1,5-pentanediol is also known, but this method also has the disadvantages that the raw materials are expensive and the purity of the obtained glutaraldehyde is very poor. Therefore, glutaraldehyde is extremely expensive compared to other chemical products, and it is hoped that a method for producing glutaraldehyde of high purity using inexpensive raw materials that can be easily synthesized chemically will be developed. ing. From such an industrial standpoint, the development of a method for producing glutaraldehyde using cyclopentene, which is industrially available at relatively low cost, as a raw material is expected. The general method for producing glutaraldehyde by oxidizing cyclopentene is to synthesize 1,2-cyclopentanediol from cyclopentene, and oxidize this 1,2-cyclopentanediol with an oxidizing agent such as lead tetraacetate or periodic acid. method is known. Also known is a method in which cyclopentene is reacted with ozone to form ozonide, which is then reductively decomposed to obtain glutaraldehyde. The former method has good reaction selectivity, but as an intermediate raw material,
The disadvantages are that it is necessary to produce 1,2-cyclopentanediol and that lead tetraacetate and periodic acid used as oxidizing agents are stoichiometrically consumed as oxidizing agents rather than as catalysts. The latter method has the disadvantage that it is not suitable for production on an industrial scale because it produces ozonide, which has a risk of explosion, as a reaction intermediate. Conventionally, a method has been proposed in which cyclopentene is oxidized with hydrogen peroxide in the presence of a molybdenum compound and a boron compound (for example, Japanese Patent Publication No. 52-28606
issue). However, this method has some drawbacks. Firstly, the reaction must be carried out in a non-aqueous system since the reaction stops due to the presence of water. That is, commercially available low-concentration hydrogen peroxide solutions cannot be used, and water-free hydrogen peroxide obtained by extraction with an organic solvent must be used. Even if you do that, water will still be generated when hydrogen peroxide reacts with cyclopentene, so
This water must be removed continuously. The second problem is that a large amount of 1,2-cyclopentanediol is produced as a by-product. This diol is a substance that is very difficult to separate from glutaraldehyde and must be suppressed as a by-product as much as possible since it reduces the purity of the glutaraldehyde product. The third drawback is that the glutaraldehyde produced by the reaction is further oxidized to carboxylic acid, and the glutaraldehyde produced is wasted. For the reasons mentioned above, it is clear that it is difficult to produce highly pure glutaraldehyde using this method, and it is also difficult to improve the yield. Therefore, industrialization of a method using hydrogen peroxide is considered to be extremely difficult. Recognizing this situation, the inventors of the present invention have conducted intensive research into a method for producing glutaraldehyde, which is an important chemical raw material, at low cost and efficiently, and have completed the present invention. That is, the present invention provides cyclopentene and alkylidene peroxide in the presence of a catalyst containing at least one compound selected from compounds of elements of groups b, b, b, and b of periods 4, 5, and 6 of the periodic table. The present invention relates to a method for producing glutaraldehyde by reacting glutaraldehyde. The method of the present invention is characterized in that it is possible to easily produce glutaraldehyde with high yield and high purity from cyclopentene, which is industrially available at low cost. That is, in the method of the present invention, 1,
There are almost no 2-cyclopentanediol and other by-products, and once glutaraldehyde is produced, it is not further oxidized to carboxylic acid or consumed by condensation reactions, so The glutaraldehyde produced in the reaction is characterized by being extremely easy to purify. The catalysts used in the process of the present invention are b, b, and b of periods 2, 5, and 6 of the periodic table.
b, b and group elements i.e. Ti, Zr,
Hf, V, Nb, Cr, Mo, W, Mn, Re, Fe,
It is a mixture of at least one or more of Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt compounds. These compounds are used in the form of complexes of elements with zero valence, or inorganic or organic compounds with various valences. Inorganic compounds of these elements include oxides, mixed oxides, hydroxides, oxyacids, heteropolyacids,
Mention may be made of these salts and esters. These salts are derived from inorganic hydroacids, oxyacids and organic carboxylic or sulfonic acids having up to 40 carbon atoms. The elemental complex is mainly a complex called an organometallic complex, which usually has a valence of 0 to +6 and is coordinated by an organic group and/or an inorganic group. Examples of catalysts that can be used in the present invention are as follows. i.e. titanium, zirconium, hafnium, vanadium, niobium, chromium,
Molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum metal carbonyls, (V(CO) ₆ , Cr
(CO) ₆ Mo(CO) ₆ , W(CO) ₆ , Fe(CO) ₅ , Ni
(CO) ₄ , Ru ₃ (CO) ₁₂ , Os ₃ (CO) ₁₂ , etc.); oxides of these metals (MoO ₂ , Mo ₂ O ₅ , Mo ₂ O ₃ , MoO ₃ ,
_{WO2 , W2O5 , WO6} , _CrO2 , _Cr2O3 , _CrO3 ,
VO ₂ , V ₂ O ₅ , ZrO ₂ , TiO ₂ , HfO ₂ , NbO ₂ ,
Nb ₂ O ₃ , MnO ₂ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , CoO,
CO ₃ O ₄ , NiO, Rh ₂ O ₃ , OsO ₄ , Re ₂ O ₇ , etc.), inorganic acid salts such as oxychlorides, fluorides, chlorides, bromides, iodides, nitrates, sulfates, phosphates, etc. ,
Pyrophosphate, polyphosphate, borate, carbonate, formate, acetate, propionate, butyrate,
Isobutyrate, caproate, caprylate, laurate, laurate, naphthenate, stearate, oxalate, succinate, glutarate, adipate, benzoate, phthalate Organic acid salts such as benzenesulfonates, acetylacetonates, phthalocyanine complexes, molybdic acid, tungstic acid, vanadic acid, chromic acid, osmic acid and corresponding heteropolyacids, and alkali metal or alkaline earth of the above acids. Examples include metal salts and cyclopentadienyl compounds. There is no problem in using a mixture of one or more of the above compounds. Furthermore, according to known methods, alumina, silica,
It is also possible to use silica alumina, zeolite, etc., or in some cases supported on a carrier such as an organic polymer. The alkylidene peroxide used in the method of the present invention has a

[Formula] A compound having a bond, with the general formula (R ¹ to ^{R 4} represent hydrogen or an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, an aryl group, and/or a derivative thereof. ^{R 1} and R ² and/or R ³ and R ⁴ are alkylene chains. They may be connected to form a ring, and n is an integer of 1 to 10). Ketone peroxide and peroxyketal are generally known as these alkylidene peroxides. Ketone peroxide can be produced, for example, by reacting hydrogen peroxide with a ketone compound;
3361, 5824, 6461 (1959), it is known that it is a mixture of as many as 7 to 8 components as shown in the following general formula.

【formula】 【formula】

【formula】

[Formula] (Here, R ₁ and R ₂ represent hydrogen or an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, or an aryl group) In this reaction, the active oxygen of any peroxide can be effectively utilized. can. Peroxyketals can also be produced by reacting ketones with organic hydroperoxides.

[Formula] (where R ₁ and R ₂ represent hydrogen or an alkyl group having 1 to 16 carbon atoms, a cycloalkyl group, or an aryl group, and R ₃ and R ₄ have 1 to 16 carbon atoms.
(indicates an alkyl group, cycloalkyl group, or aryl group). Specific examples of these compounds include acetone peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, diisobutyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, acetylacetone peroxide, 2 , 2-bis(t-butylperoxy)butane, n-butyl-4,4-
Bis(t-butylperoxy)valerate, 1,
1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-
Examples include 3,3,5-trimethylcyclohexane. In the reaction, there is no problem in using one or more of the above alkylidene peroxides as a mixture. Also usable are mixed ketone peroxides prepared by reacting a mixture of ketone compounds with hydrogen peroxide, and mixed peroxyketals prepared by reacting a mixture of hydroperoxides with a ketone compound. Furthermore, it is also possible to use alkylidene peroxide prepared in the reaction system. Glutaraldehyde is produced by catalytic oxidation of cyclopentene by producing alkylidene peroxide from a ketone compound while supplying oxygen in the presence of a catalytic amount of peroxide or under light irradiation using the method described above. method is also possible. In the present invention, it is preferable to use the following solvents in order to uniformly mix cyclopentene and alkylidene peroxide, to sufficiently disperse or uniformly dissolve the catalyst, and to carry out the reaction under mild conditions. That is, carboxylic acids having 1 to 40 carbon atoms, phosphoric acids, phosphonic acids,
Sulfonic acids and their esters, amides,
Further examples include ethers. Specific examples of these include ethyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, cyclohexyl acetate, ethyl propionate, butyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dimethyl Terephthalate, diethyl terephthalate, dimethylformamide, dimethylacetamide, dimethyl sulfate, triethyl phosphate, tributyl phosphate, trihexyl phosphate, trioctyl phosphate, methanephosphonic acid dimethyl ester, dibutyl ether,
Examples include diisoamyl ether. In carrying out the present invention, the concentration of alkylidene peroxide in the reaction solution is preferably in the range of 1 to 50 weight percent, particularly in the range of 3 to 25 weight percent, in order to prevent heat generation and runaway risk due to rapid reaction. It is preferable that Further, in carrying out the method of the present invention, there is no particular restriction on the order in which the catalyst, alkylidene peroxide and cyclopentene are added to the reactor.
For example, cyclopentene may be added after adding a solution of alkylidene peroxide to the catalyst, or the catalyst may be added after mixing a solution of alkylidene peroxide and cyclopentene.
Furthermore, these essential components may be added at once or in portions. When oxidizing cyclopentene according to the method of the present invention, the amount of catalyst used can be varied over a wide range; however, if the amount of catalyst is small, the reaction rate will be slow; if the amount of catalyst is too large, the reaction will be fast but the catalyst cost will be high. In particular, from 10 ^-5 mol to 10 ^-1 per mol of olefin.
Moles are preferred, particularly amounts of 10 ⁻⁴ to 10 ⁻² mol are preferred. The amount of alkylidene peroxide used in the process can vary over a wide range. However, using an excessive amount of alkylidene peroxide is not only uneconomical, but also requires post-treatment such as recovery or inactivation of unreacted alkylidene peroxide. Therefore, alkylidene peroxide has an active oxygen content of 0.1 to 4.0 gram atoms, preferably 0.5 gram atoms to 1 mole of cyclopentene.
Preferably, a 2.0 gram atom amount is used. In carrying out the method of the present invention, it is not preferable to carry out the reaction at high temperatures in order to prevent consumption of alkylidene peroxide by autolysis and to prevent further oxidation of glutaraldehyde. On the other hand, when this method is carried out at low temperatures, the reaction rate is slow. The process is therefore preferably carried out in the temperature range from -40°C to 150°C, especially in the temperature range from -20°C to +100°C. Furthermore, although the reaction time for carrying out the present invention varies depending on the reaction temperature and the composition of the reaction system, the reaction usually completes in a short time. For example, reaction time is 5
The reaction will progress sufficiently if given enough time. This reaction can be carried out either batchwise or continuously. The method of the present invention not only enables the production of glutaraldehyde from cyclopentene in high yield at low cost, but also has the great feature of avoiding the dangers associated with oxidation reactions. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Example 1 (Note) Peroxide in the above formula shows the structure of a typical component of methyl ethyl ketone peroxide. After adding 0.35 g of MoO ₂ (C ₅ H ₇ O ₂ ) ₂ , 60 g of dimethyl phthalate and 13.6 g of cyclopentene to a 200 c.c. glass reaction vessel equipped with a stirrer and a reflux condenser, the temperature was raised to 31°C. While stirring, 32 g of a dimethyl phthalate solution of methyl ethyl ketone peroxide having an active oxygen concentration of 10.5 wt% was added. After heating and stirring for 1.5 hours, the reaction solution was analyzed by gas chromatography using a column whose liquid phase was FFAP (free fatty acid polyester), and it was found that glutaraldehyde was present in the reaction solution.
It contained 5.8wt%. Note that 1,2-cyclopentanediol and glutaric acid were not detected at all. In addition, after extracting glutaraldehyde from the reaction solution with water, the yield of glutaraldehyde was determined by reacting it with 2,4-dinitrophenylhydrazine.
It was found that g was generated. Furthermore, as a result of measuring the content of unreacted ketone peroxide in the reaction solution by iodometry, the decomposition rate of ketone peroxide was 61%. This means that the selectivity of glutaraldehyde to the reacted ketone peroxide is 95%. Examples 2 to 24 When cyclopentene was oxidized in the same manner as in Example 1, and the reaction solution was analyzed according to the method shown in Example 1, the results shown in Table 1 were obtained.

【table】

【table】

【table】

Claims (1)

[Claims] 1 Selected from compounds of elements selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. A method for producing glutaraldehyde, which comprises reacting cyclopentene and alkylidene peroxide in the presence of a catalyst containing at least one type of glutaraldehyde.