JPH0138773B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (R ₁ is hydrogen or an organic residue having 1 to 18 carbon atoms.) Or general formula (R ₂ and R ₃ are each hydrogen or carbon number 1
~18 organic residues. This invention relates to a method for producing glutaraldehyde by thermally decomposing a cyclopentyl peroxide compound (R ₂ and R ₃ may be connected to form a ring). 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 oxygen fixation agents. Glutaraldehyde is currently mainly produced from acrolein 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, it is hoped that a method for producing glutaraldehyde using cyclopentene or a cyclopentene derivative, which can be obtained industrially at relatively low cost, as a raw material will be developed. The method for producing glutaraldehyde by oxidizing cyclopentene or cyclopentene derivatives generally involves synthesizing 1,2-cyclopentanediol from cyclopentene, and oxidizing this 1,2-cyclopentanediol with an oxidizing agent such as lead tetraacetate or periodic acid. A method of oxidizing is known. Although this method has good selectivity, it has the disadvantage that lead tetraacetate and periodic acid are stoichiometrically consumed as an oxidizing agent rather than as a catalyst. In addition, a method is known in which cyclopentene is reacted with ozone to form ozonide, which is then reductively decomposed to obtain glutaraldehyde. However, this method has the disadvantage that it is not suitable for production on an industrial scale because ozonide, which has a high risk of explosion, is produced as a reaction intermediate. Recently, a method has been proposed in which cyclopentene or cyclopentene oxide is catalytically oxidized with hydrogen peroxide in the presence of a molybdenum compound (for example, Japanese Patent Publication No. 52-28606;
33526). However, this method also has some serious 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 aqueous hydrogen peroxide solutions cannot be used, and water-free hydrogen peroxide obtained by extraction with an organic solvent must be used. Even so, water is still generated when hydrogen peroxide reacts with cyclopentene or cyclopentene oxide, and this water must be continuously removed. 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 problem is that it is difficult to separate the molybdenum compound, which is a catalyst, from glutaraldehyde. It is known that molybdenum compounds are solubilized by reacting with hydrogen peroxide or organic hydroperoxides, and such solubilization also occurs when molybdenum compounds are supported on a carrier such as silica or alumina. Therefore, this method consumes a large amount of energy to recover the catalyst. The fourth and most serious problem is that the generated glutaraldehyde reacts further.
Glutaraldehyde is a very unstable substance, and if the reaction is continued without being separated from the reaction system even after it has been produced, the produced glutaraldehyde may be further oxidized and become a carboxylic acid, or it may become a carboxylic acid due to a condensation reaction. It will end up being 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, it is considered to be very difficult to industrialize the method for producing glutaraldehyde by oxidizing cyclopentene using hydrogen peroxide. In general, when manufacturing various chemical products, it is of course required that the process be simple and have a high yield, but when manufacturing glutaraldehyde, it is necessary to take into account its instability. There must be. Therefore, even if the yield is simply high,
Production methods in which the produced glutaraldehyde undergoes further reaction or energy is wasted in removing impurities are not considered industrially appropriate. 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 is based on the general formula (R ₁ is hydrogen or an organic residue having 1 to 18 carbon atoms.) Or general formula (R ₂ and R ₃ are each hydrogen or carbon number 1
~18 organic residues. R ₂ and R ₃ may be connected to form a ring. ) relates to a method for producing glutaraldehyde by thermally decomposing a cyclopentyl peroxide compound. A feature of the present invention is that glutaraldehyde can be produced in high yield by thermally decomposing a cyclopentyl peroxide compound that can be easily synthesized industrially from cyclopentene or cyclopentene oxide, and 1,2-cyclopentanediol and other by-products can be produced. Almost no living things occur. Furthermore, since this method is a method for producing glutaraldehyde by thermal decomposition, the produced glutaraldehyde is not brought into contact with an acid, an alkali, or a metal catalyst, so that deterioration of the glutaraldehyde can be prevented. Therefore, the produced glutaraldehyde is not consumed by being polymerized by condensation reaction or further oxidized to become carboxylic acid. Therefore, the glutaraldehyde produced by this method has very high purity and is easy to purify.
In addition, the cyclopentyl peroxide compound used in this method is much safer than ozonide, which is produced by the reaction of cyclopentene and ozone, and has less risk of explosion, so it is a raw material that can be used industrially. When producing glutaraldehyde using cyclopentene or cyclopentene oxide as a raw material, it is necessary to synthesize a cyclopentyl peroxide compound in advance before carrying out the method of the present invention. Therefore, when cyclopentene or cyclopentene oxide is used as a raw material, the process to reach glutaraldehyde appears to be complicated at first glance. However, both the synthesis and decomposition of cyclopentyl peroxide compounds are easy to carry out, and the product obtained in each step has a high yield and is easy to purify, so the method for producing glutaraldehyde using this method can be fully implemented industrially. Moreover, the synthesis and decomposition of the cyclopentyl peroxide compound can be performed continuously, and the actual process becomes a simplified manufacturing method. Furthermore, compared to the conventionally known oxidation method of cyclopentene or cyclopentene oxide, the method for producing glutaraldehyde using this method is easier to purify and has a higher purity because it can go through a relatively stable intermediate called cyclopentyl peroxide compound. It is characterized by the ability to produce glutaraldehyde with a high level of glutaraldehyde. Furthermore, in the method of the present invention, even if cyclopentanediol is produced as a by-product, it can be converted into a cyclopentyl peroxide compound by reacting it with hydrogen peroxide or an organic hydroperoxide as shown below. . Therefore, even if cyclopentanediol is produced as a by-product, it can also be used as a raw material, so the yield of glutaraldehyde is very high, almost 100%. In the present invention, a cyclopentyl peroxide compound represented by the following general formula is used. Here, R ₁ is hydrogen or an organic residue having 1 to 18 carbon atoms. Typical organic residues include alkyl groups, cycloalkyl groups, aryl groups, acyl groups, etc., and organic residues containing halogen, hydroxyl groups, formyl groups, hydroperoxy groups, peroxyalkyl groups, etc. can also be used. This cyclopentyl peroxide compound can be synthesized in high yield by reacting cyclopentene oxide with hydrogen peroxide or an organic hydroperoxide in the presence of an acid such as sulfuric acid, hydrochloric acid, or a cation exchange resin. Also, this cyclopentyl peroxide compound has the general formula (X is OSO ₃ R′, OSO ₂ H, OSO ₂ R′, OCOR′,
Cl, Br, I, ClO ₄ , OH or OR'. However, R' is an alkyl group, a cycloalkyl group, or an aryl group having 1 to 16 carbon atoms. ), it can also be synthesized by reacting a β-hydroxycyclopentane derivative with hydrogen peroxide or an organic hydroperoxide. The present invention also uses a cyclopentyl peroxide compound represented by the following general formula. Here, R ₂ and R ₃ are each hydrogen or an organic residue having 1 to 18 carbon atoms. Typical examples of this organic residue are alkyl groups, cycloalkyl groups, aryl groups, etc., and organic residues containing halogen, hydroxyl group, formyl group, hydroperoxy group, peroxyalkyl group, cyclic peroxyketal, etc. bases can also be used. R ₂ and R ₃ may be connected to form a ring. This cyclopentyl peroxide compound can be synthesized by reacting β-hydroxycyclopentyl hydroperoxide, which can be synthesized by the method described above, with a ketone or aldehyde in the presence of an acid such as sulfuric acid, hydrochloric acid, or an anion exchange resin. Specific examples of these cyclopentyl peroxide compounds are:

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It is a compound such as. In this reaction, there is no problem in decomposing the above-mentioned cyclopentyl peroxide compounds as a mixture of one or more. In carrying out the present invention, the cyclopentyl peroxide compound may be thermally decomposed as it is without being diluted with a solvent, or may be diluted with a solvent and then decomposed. Alternatively, cyclopentyl peroxide may be vaporized and then thermally decomposed. When carrying out thermal decomposition, it is preferable to carry out little by little in any of the above cases to prevent the risk of heat generation and runaway. When decomposing cyclopentyl peroxide by diluting it with a solvent, any solvent can be used other than the solvent that reacts with the raw material cyclopentyl peroxide and the product glutaraldehyde. Examples of such solvents include hydrocarbons having 1 to 40 carbon atoms, esters and amides of carboxylic acids, phosphoric acids, phosphonic acids, and sulfonic acids, as well as ketones, alcohols, and ethers. Water can also be used. Specific examples of these solvents include hexane, nonane, dodecane,
Toluene, xylene, ethylbenzene, naphthalene, ethyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate,
Cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dimethyl formamide, dimethyl acetamide, triethyl phosphate, trihexyl phosphate,
Trioctyl phosphate, dimethyl methanephosphonate, acetone, methyl ethyl ketone, dibutyl ketone, acetophenone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, dodecyl alcohol, diethyl ether, dibutyl ether, diisoamyl ether ,
Contains anisole, water, etc. In carrying out this reaction, the decomposition temperature for thermally decomposing the cyclopentyl peroxide compound is 60
Preferably, the reaction is carried out in a temperature range of 0.degree. C. to 300.degree. C., particularly 70.degree. C. to 250.degree. If the decomposition temperature is too high, polymerization of glutaraldehyde will occur, which is undesirable, and if the decomposition temperature is too low, the reaction time will be too long, making it economically unsuitable. In carrying out this reaction, the reaction time varies depending on the concentration or decomposition temperature, but the decomposition usually ends in a short time.
For example, if the reaction time is 5 hours, the reaction will proceed sufficiently. This reaction can be carried out either batchwise or continuously. Furthermore, since this reaction generates heat due to decomposition of the cyclopentyl peroxide compound, it is preferable to decompose it little by little while removing heat. The present reaction will be explained below with reference to examples, but the present reaction is not limited thereto. Example 1 A dimethyl phthalate solution of β-hydroxycyclopentyl hydroperoxide as a raw material was prepared by the following method. Equipped with stirrer, reflux condenser and dropping funnel
After putting 3 g of Amberlyst 15 (strongly acidic cation exchange resin, manufactured by Rohm & Haas) and 20 g of dimethyl phthalate into a 200 c.c. glass reaction vessel, the temperature was raised to 30°C and the mixture was poured through a dropping funnel while stirring. A solution consisting of 16.8 g of cyclopentene oxide, 7.5 g of anhydrous hydrogen peroxide and 30 g of dimethyl phthalate was added over a period of 1 hour. After stirring at 30° C. for 3 hours, the catalyst was separated to obtain a dimethyl phthalate solution of β-hydroxycyclopentyl hydroperoxide. Furthermore, from H and C-NMR and iodometry, β
The amount of -hydroxycyclopentyl hydroperoxide produced was 22 g. Using the dimethyl phthalate solution of β-hydroxycyclopentyl hydroperoxide thus obtained, a decomposition reaction was carried out as described below. Equipped with stirrer, reflux condenser and dropping funnel
200 c.c. dimethyl phthalate 20 in a glass reaction vessel
After the mixture was heated to 150° C., 70 g of a dimethyl phthalate solution containing 20.7 g of β-hydroxycyclopentyl hydroperoxide was added from the dropping funnel over 2 hours while stirring. After heating and stirring for 1 hour after the completion of the dropwise addition, 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 26wt%. It was confirmed by iodometry that no peroxide remained in the reaction solution. Furthermore, glutaraldehyde was extracted from the reaction solution with water, and the yield was determined to be 15.1 g. Example 2 A raw material β-hydroxycyclopentyl-t-butyl peroxide was prepared by the following method by reacting cyclopentene oxide with t-butyl hydroperoxide. Equipped with stirrer, reflux condenser and dropping funnel
1515 g of Amberlyst in a 500 c.c. glass reaction vessel
After adding 100 g of benzene, the temperature was raised to 40°C, and while stirring, 85 g of cyclopentene oxide and 105 g of t-butyl hydroperoxide were added through the dropping funnel.
and 220 g of benzene were added over 30 minutes. After stirring at 40°C for 5 hours, the catalyst was separated and the reaction was distilled under reduced pressure. β-hydroxycyclopentyl-t-butyl peroxide was obtained.
115g was obtained. This β-hydroxycyclopentyl-t-butyl peroxide was decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
200 c.c. Diethyl phthalate paste in a glass reaction vessel.
After adding 50g of β-hydroxycyclopentyl, the temperature was raised to 200℃ and β-hydroxycyclopentyl
95 g of t-butyl peroxide was slowly added over 1.5 hours. After heating and stirring for 2 hours, the mixture was cooled and extracted with water to obtain 45 g of glutaraldehyde. Example 3 β-Hydroxycyclopentyl peroxide was synthesized in the same manner as in Example 1, and then treated with methyl ethyl ketone to form a cyclopentyl peroxide compound, 4-ethyl-4-methyl-2,3,5
-trioxabicyclo[4,3,0]nonane was prepared as follows. After putting 2 g of concentrated sulfuric acid and 100 g of dodecane into a 500 c.c. glass reaction vessel equipped with a stirrer, a reflux condenser, and a dropping funnel, the temperature was raised to 40°C, and while stirring, cyclopentene oxide was added through the dropping funnel.
1 solution consisting of 84 g and 40 g of 90% hydrogen peroxide
Added over time. After stirring at 40°C for 3 hours, 144 g of methyl ethyl ketone was added and the temperature was raised to 60°C. After stirring while continuing to heat the mixture at 60°C for 1 hour, the reaction solution was immediately distilled under reduced pressure.
129 g of cyclopentyl peroxide compound was obtained. This cyclopentyl peroxide compound was decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
After putting 100g of water into a 300c.c. glass reaction container,
The temperature was raised to 90°C, and 78 g of a cyclopentyl peroxide compound was added from the dropping funnel over 1 hour while stirring. After heating and stirring at 90℃ for 5 hours, analysis by gas chromatography using an FFAP column revealed that glutaraldehyde was present in the decomposition solution.
It contained 19wt%. The remaining amount of peroxide in the decomposition solution was examined by iodometry, but no peroxide was detected. Further, when the decomposition liquid was distilled under reduced pressure, 30 g of glutaraldehyde was obtained. Example 4 The above β-hydroxycyclopentyl cumyl peroxide was prepared in the same manner as in Examples 1 and 2, and the peroxide was thermally decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
After putting 50 g of dodecane into a 200 c.c. glass reaction vessel, the temperature was raised to 160°C, and while stirring, 59 g of β-hydroxycyclopentylcumyl peroxide was added from a dropping funnel over 1 hour. After heating and stirring at 160℃ for 4 hours, the decomposition liquid was distilled under reduced pressure, and 20g of glutaraldehyde was found.
Obtained. Example 5 The above β-hydroxycyclopentylacetyl peroxide was prepared in the same manner as in Examples 1 and 2, and the peroxide was thermally decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
After putting 50 g of trioctyl phosphate into a 200 c.c. glass reaction vessel, the temperature was raised to 120°C, and a solution consisting of 39 g of β-hydroxycyclopentylacetyl peroxide and 20 g of trioctyl phosphate was poured into the dropping funnel for 1.5 hours while stirring. It was added over a period of time. After heating and stirring at 120℃ for 2 hours, the decomposition liquid was distilled under reduced pressure, and glutaraldehyde was found to be 19
g was obtained. Example 6 The above β-hydroxycyclopentyl peroxide was prepared in the same manner as in Examples 1 and 2, and the peroxide was thermally decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
After putting 30g of water into a 200c.c. glass reaction container,
The temperature was raised to 95° C., and a solution consisting of 31 g of β-hydroxycyclopentyl peroxide and 35 g of water was added from the dropping funnel over 1 hour while stirring. After heating and stirring at 95° C. for 4 hours, the decomposition liquid was distilled under reduced pressure to obtain 16 g of glutaraldehyde. Example 7 The above β-hydroxycyclopentyl 2',4' dichlorobenzoyl peroxide was prepared in the same manner as in Examples 1 and 2, and the peroxide was thermally decomposed as follows. Equipped with stirrer, reflux condenser and dropping funnel
After putting 50 g of n-butanol into a 200 c.c. glass reaction vessel, the temperature was raised to 130°C, and while stirring, β-hydroxycyclopentyl 2',4'-
Dichlorobenzyl peroxide 20.1g and n
- A solution consisting of 55 g of butanol was added over a period of 2 hours. After heating and stirring at 130℃ for 3 hours, the decomposition liquid was distilled under reduced pressure, and glutaraldehyde was found.
4.5g was obtained.

Claims (1)

[Claims] 1. General formula (R ₁ is hydrogen or an organic residue having 1 to 18 carbon atoms.) Or general formula (R ₂ and R ₃ are each hydrogen or carbon number 1
~18 organic residues. R ₂ and R ₃ may be connected to form a ring. ) A method for producing glutaraldehyde, which comprises thermally decomposing a cyclopentyl peroxide compound.