JPH09249601A - Production of cycloalkanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound in a high yield by using an accelerator in a reaction system. SOLUTION: This method for producing a cycloalkanol is obtained by mixing an oil phase containing a cycloalkane and an aqueous phase and performing a hydration reaction in the presence of a solid acid catalyst (e.g. mordenite) preferably at 80-160 deg.C, under 0.2-2MPa pressure for 0.5-5hr. In the reaction system, an accelerator for dissolving the cycloalkane to the aqueous phase (e.g. alkyl sulfonic acid) and an accelerator for extracting the cycloalkanol into the oil phase (e.g. aromatic carboxylic acids) are made as coexisting. The coexisting amounts of each of the accelerators are preferably 0.1-10wt.% accelerator for dissolving the cycloalkane to the aqueous phase and 0.1-40wt.% accelerator for extracting the cycloalkanol into the oil phase based on the cycloalkane.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a cycloalkanol by hydrating a cycloalkene.

[0002]

2. Description of the Related Art There is known a method of using a strongly acidic ion exchange resin or a solid acid catalyst such as zeolite for the production of cycloalkanol by hydration of cycloalkene such as cyclohexene. The advantage of these methods is that the catalyst can be easily separated as compared with a homogeneous catalyst such as a mineral acid, but there is a problem that the yield is low. Therefore, for the purpose of improving the yield, organic solvents such as alcohols having 1 to 10 carbon atoms, halogenated hydrocarbons, ethers, acetone and methyl ethyl ketone (JP-A-58-194828) and phenols (JP-A-62-62). -120333 gazette, Unexamined-Japanese-Patent No. 62-
126141), fluoroalcohols (JP-A-64-13044), benzoic acids (JP-A 5-2).
No. 55162) is added to the hydration reaction system.

[0003]

However, the methods using the above-mentioned various additives still have problems such as insufficient yield and generation of by-products derived from organic solvents.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific addition which affects the solubility properties of cycloalkene or cycloalkanol in a hydration reaction system. The inventors have found that the yield of cycloalkanol is significantly improved when the compounds are used alone or in combination of two or more kinds, and the present invention has been accomplished. That is, the gist of the present invention is a method for producing a cycloalkanol by mixing an oil phase containing a cycloalkene and an aqueous phase in the presence of a solid acid catalyst to produce a cycloalkanol, wherein the reaction system contains an aqueous phase of cycloalkene. A method for producing a cycloalkanol, characterized in that a substance having an effect of increasing the distribution ratio to cycloalkanol is present alone or together with a substance having an action of increasing the distribution ratio of cycloalkanol produced by a hydration reaction to an organic phase. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Examples of the cycloalkene include cyclopropene, cyclopentene, methylcyclopentenes, cyclohexene, methylcyclohexenes, cyclooctene, cyclododecene, and the like, with preference given to cycloalkenes having a 5- to 8-membered ring.

The solid acid catalyst is a substance having a solid acidity, and is usually a strongly acidic ion exchange resin containing a zeolite, a sulfonic acid group or the like, an inorganic oxide such as zirconium dioxide, titanium dioxide, aluminum oxide or silicon dioxide,
An ion exchange type layered compound obtained by treating a layered compound such as smectite, kaolinite, vermiculite or the like with one or more kinds of metal oxides selected from aluminum, silicon, titanium and zirconium is used, and zeolite is preferable.

Specific examples of the zeolite include ZS having an MFI structure such as mordenite, erionite, ferrierite, ZSM-5 and ZSM-11 announced by Mobil.
Examples thereof include crystalline aluminosilicates such as M-type zeolite and metalloaluminosilicates and metallosilicates containing foreign elements such as boron, iron, gallium, titanium, copper and silver. As the exchangeable cation species of zeolite, a proton exchange type (H type) is usually used.
g, Ca, Sr, or another alkaline earth metal, La, Ce, or other rare earth element, or Fe, Co, Ni, Ru, Pd, Pt, or any other group 8 to 10 group element exchanged with at least one cation species, Alternatively, Ti, Zr, Hf, Cr, Mo,
Those containing W, Th, etc. are also effective. Particularly preferably, H-type zeolite having a pentasil structure, especially H-type gallosilicate is preferable.

The present invention is characterized in that a substance having an action of increasing the distribution ratio of cycloalkene to the aqueous phase (hereinafter referred to as "cycloalkene aqueous phase dissolution accelerator") is added and coexisted in the reaction system. The reason why the yield of cycloalkanol is significantly improved by coexisting the cycloalkene aqueous phase dissolution accelerator in the reaction system is considered as follows.
That is, the hydration reaction of cycloalkene is generally carried out by mixing an oil phase mainly composed of a starting material cycloalkene and an aqueous phase as described below, and a suspension state, for example, an oil phase in a continuous aqueous phase It is performed in a state of being dispersed in a droplet state. The cycloalkene hydration reaction itself is considered to proceed in an aqueous phase in which a catalyst is present. Therefore, it is assumed that the higher the concentration of cycloalkene as a reaction raw material in the aqueous phase, the faster the reaction proceeds, but in general, the solubility of cycloalkene in the aqueous phase is very low, and the cycloalkene aqueous phase dissolution promotion is promoted. It is only about 0.01% by weight under normal hydration reaction conditions in which no agent is added. On the other hand, by coexisting a significant amount of the cycloalkene aqueous phase dissolution accelerator, the dissolution distribution ratio of cycloalkene to the aqueous phase is increased, and the cycloalkene concentration in the aqueous phase is at least 2 times or more, preferably 5 times or more, 1 in some cases
It can be 0 to 100 times. As a result, it is presumed that the hydration reaction is promoted and the yield of cycloalkanol is significantly improved. It should be noted that the method for evaluating the solubility of cycloalkene in the aqueous phase is preferably based on the assumption of an actual reaction system.
Such a method can be adopted.

The above cycloalkene aqueous phase dissolution accelerator is
The kind of the substance is not particularly limited as long as it has a function of significantly increasing the distribution ratio of cycloalkene to the aqueous phase, but a water-soluble substance that substantially partitions to the aqueous phase is usually used. Here, "substantially distributed in the aqueous phase" means, for example, among the added cycloalkene aqueous phase dissolution accelerators,
A substance whose distribution ratio in the aqueous phase exceeds 99%. Specific examples of the cycloalkene aqueous phase dissolution accelerator include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, octanesulfonic acid, dodecanesulfonic acid, cetylsulfonic acid, and other alkylsulfonic acids having about 1 to 20 carbon atoms, Alternatively, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, phosphomolybdovanadic acid, phosphomolybdotungstovanadic acid, phosphotungstovanadic acid, silicomolybdic acid, silicomolybdotungstic acid, silicomolybdo tungstovanadic acid,
Heteropoly acids such as borotungstic acid, cobalt molybdic acid, cobalt tungsten arsenic molybdic acid, and arsenic tungstic acid can be mentioned. In addition, the heteropolyacid is usually molybdenum (M
o), at least one element selected from tungsten (W) and vanadium (V), and other elements such as niobium (Nb) and thallium (Ta) as a condensation coordination element. I mean. The central element of this heteropolyacid is usually P, Si, As, G
e, Ti, Ce, Th, Mn, Ni, Te, I, Co,
It is selected from the group consisting of Cr, Fe, Ga, B, V, Pt and Be, and among them, the atomic ratio of condensed coordination element / central element in the heteropolyacid is usually preferably 2.5 to 12. Furthermore,
The heteropolyacid is not limited to a monomer, and a polymer such as a dimer or trimer can be used.

Even if the amount of the cycloalkene aqueous phase dissolution accelerator added to the reaction system is relatively small, the effect of increasing the yield of the hydration reaction is recognized, and the amount ratio of each component of the reaction system and the reaction conditions are Therefore, the optimum range may vary, but is usually 0.01 to 40% by weight, preferably 0.1 to 10% by weight, based on the cycloalkene. Note that the above cycloalkene aqueous phase dissolution accelerator has two
You may use it as a mixture of more than one kind.

The effect of the cycloalkene aqueous phase dissolution accelerator can be recognized even when used alone, but a substance having an action of increasing the distribution ratio of cycloalkanol produced by the hydration reaction to the organic phase (hereinafter referred to as "cycloalkanol"). The effect can be further enhanced by using it together with an “oil phase extraction accelerator”. Generally, the cycloalkanol is mostly present in the oil phase in the reaction system, but the cycloalkanol itself is considered to be produced in the water phase, and
Even in the aqueous phase, up to about 10% of the oil phase can be distributed and dissolved. Such a cycloalkanol oil phase extraction accelerator has an extraction ratio of cycloalkanol to the oil phase of at least 1.0.
It can be increased 5 times, preferably 1.1 times or more. As a result, in the reaction system, the above-mentioned cycloalkene aqueous phase dissolution accelerator also acts synergistically to affect the reaction equilibrium of the hydration reaction, etc., and to exert the effect of significantly increasing the yield of cycloalkanol. Presumed. It should be noted that the method for evaluating the solubility of cycloalkanol in the oil phase is preferably based on the assumption of an actual reaction system, but a method such as Reference Example 3 described later can be simply adopted.

The cycloalkanol oil phase extraction accelerator is not particularly limited in kind as long as it is a substance having an action of increasing the distribution ratio of cycloalkanol to the organic phase.
A lipophilic polar substance is used. Such organic additives include aromatic carboxylic acids, phenols, cyclic saturated carboxylic acids, heterocyclic carboxylic acids, alcohols, oxygen-containing compounds such as esters thereof, amides and nitriles, and the like. Examples thereof include nitrogen organic compounds, aromatic sulfonic acids, and sulfur-containing organic compounds such as thiols. Generally, aromatic carboxylic acids, phenols or cyclic saturated carboxylic acids are preferable.

As aromatic carboxylic acids, benzene,
Examples of those derived from naphthalene or the like and having about 1 to 4 carboxyl groups include benzoic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and the like. Further, among the aromatic carboxylic acids, not only those in which a carboxyl group is directly bonded to an aromatic ring, but also mandelic acid, benzylic acid, 2-phenyl-2,
Also included are α-hydroxycarboxylic acids such as 2-dihydroxyacetic acid and α-ketocarboxylic acids such as phenylglyoxylic acid. Regarding the carboxyl group of the aromatic carboxylic acids as described above, those which form an ester or an amide may be used, and an alkyl group, a halogen group, a phenyl group, a hydroxyl group, or a thiol group having a nuclear substituent. Good.

Among the aromatic carboxylic acids, benzoic acid is particularly preferable, and benzoic acid; toluic acid, ethylbenzoic acid, propylbenzoic acid, 2,6-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid, etc. Benzoic acid having one or more alkyl groups of 2,3-dimethoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,5-dimethoxybenzoic acid, 2,6-dimethoxybenzoic acid, 3,4-dimethoxybenzoic acid Acid, 3,5-dimethoxybenzoic acid, 2,
3,4-trimethoxybenzoic acid, 2,4,5-trimethoxybenzoic acid, 3,4,5-trimethoxybenzoic acid, 2
-Alkoxybenzoic acid having an alkoxy group having about 1 to 8 carbon atoms such as ethoxybenzoic acid; 6 to 12 carbon atoms such as 2-phenoxybenzoic acid, 3-phenoxybenzoic acid, and 2- (4-tolyloxy) benzoic acid; Aryloxybenzoic acid having a degree of aryloxy group; 1 to 8 carbon atoms such as 2-acetylbenzoic acid and 2-ethylcarbonylbenzoic acid
Alkylcarbonylbenzoic acid having a degree of alkylcarbonyl group; arylcarbonyl having an arylcarbonyl group having about 7 to 13 carbon atoms such as 2-benzoylbenzoic acid, 3-benzoylbenzoic acid, and 2- (4-methyl) benzoylbenzoic acid Benzoic acid; carbon number 2 such as 2-methoxycarbonylbenzoic acid and 2-ethoxycarbonylbenzoic acid
To an alkyloxycarbonylbenzoic acid having an alkyloxycarbonyl group of about 9; an aryloxycarbonyl group having about 7 to 13 carbon atoms such as 2-benzoxycarbonylbenzoic acid and 2- (4-methyl) benzoxycarbonyl) benzoic acid. An aryloxycarbonylbenzoic acid having; an arylbenzoic acid having an aryl group having about 6 to 12 carbon atoms such as 2-phenylbenzoic acid and 2- (4-toluyl) benzoic acid; 2-benzylbenzoic acid, 2-phenethylbenzoic acid 7-18 carbon atoms such as acid and 3-phenethylbenzoic acid
Arylalkyl benzoic acid having a degree of arylalkyl group; 3-fluorobenzoic acid, 3-chlorobenzoic acid
Examples thereof include benzoic acid having a halogen group such as 2,6-ditrifluoromethylbenzoic acid, 2,4,6-trifluoromethylbenzoic acid and pentafluorobenzoic acid.

Among the benzoic acids having these specific substituents, benzoic acid having an alkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group is preferable, and 2-benzoylbenzoic acid is particularly preferable. Acid, 2- (4-methyl) benzoylbenzoic acid, 2-methoxycarbonylbenzoic acid, 2-benzoxycarbonylbenzoic acid and the like can be mentioned.

Specific examples of the phenols include phenol
, Cresol, xylenol, trimethylphenol
, Ethyl phenol, isopropyl phenol, t-
A phenol having an alkyl group such as butylphenol, phenylphenol, toluylphenol, chlorophenol, bromophenol, iodophenol, pyrocatechol, resorcin, hydroquinone, pyrogallol, hydroquinone. Examples thereof include monomethyl ether, nitrophenol, mercaptophenol, phenolsulfonic acid, 1-naphthol and 2-naphthol.
Furthermore, examples of salicylic acids that are both benzoic acids and phenols include salicylic acid and acetylsalicylic acid. Further, 4-hydroxybenzoic acid which is an isomer of salicylic acid may be used.

Specific examples of the cyclic saturated carboxylic acids include:
Examples of cyclohexanecarboxylic acids include cyclohexanemonocarboxylic acid, cyclohexane1,3-dicarboxylic acid, 1-methylcyclohexanemonocarboxylic acid and 2-methylcyclohexanemonocarboxylic acid. Examples of the esters include methyl esters such as aromatic carboxylic acids and cyclic saturated carboxylic acids, ethyl esters, propyl esters, butyl esters, cyclohexyl esters, etc., which have been mentioned above.

Examples of other cycloalkanol oil phase extraction accelerators include alcohols such as t-butyl alcohol, t-amyl alcohol and neopentyl alcohol,
Examples thereof include ethers such as anisole and dicyclohexyl ether, ketones such as cyclopentanone and cyclohexanone, sulfur-containing compounds such as gamma-butyrolactone, phosphoric acid alkyl ester and dimethyl sulfoxide, and halogen-containing compounds such as chlorobenzene.

The amount of the cycloalkanol oil phase extraction accelerator added to the reaction system as described above is recognized to have the effect of increasing the yield of the hydration reaction even in a relatively small amount. The optimum range may vary depending on the reaction conditions, reaction conditions, etc., but is usually 0.00
It is 1 to 100% by weight, preferably 0.1 to 40% by weight. The amount of the cycloalkanol oil phase extraction accelerator used with respect to the cycloalkene aqueous phase dissolution accelerator is usually 0.1.
˜1000, preferably 1 to 100. The above cycloalkanol oil extraction accelerators may be used alone or as a mixture of two or more kinds.

The hydration reaction targeted by the present invention is carried out in the presence of a solid acid catalyst, a cycloalkene, water and an additive. The method of using the catalyst is not particularly limited, but a fixed bed method, a slurry method or the like is used. When mixing is stopped during the hydration reaction and the water phase and oil phase separate, the water phase mainly contains the solid acid catalyst, and the oil phase contains much of the starting cycloalkene and generated cycloalkanol. Is included. The hydration reaction is carried out by mixing the water phase and the oil phase by stirring or the like, thereby suspending the oil phase, for example, the oil phase dispersed in a droplet state in the continuous water phase. In the hydration reaction, water and cycloalkene are mixed and reacted in the presence of a solid acid catalyst, but when the mixing is weakened during the reaction or in a stopped state, the water phase and the oil phase are separated. The volume ratio of the oil phase to the water phase is usually 0.
It is 01 to 10, preferably 0.1 to 1. If the raw material cycloalkene or water is in a large excess as compared with one, it is not preferable because the separation of the aqueous phase and the oil phase is poor and the reaction rate also decreases. The weight ratio of the catalyst to the cycloalkene is usually 0.01 to 20, preferably 0.05 to 5. When the amount of the catalyst is too small, the reaction rate becomes slow and the reactor becomes large, and when the amount of the catalyst is too large, the catalyst cost becomes large, which is not preferable.

The reaction temperature is preferably low from the viewpoint of equilibrium of the hydration reaction of cycloalkene and from the viewpoint of suppressing side reactions, but from the viewpoint of reaction rate, high temperature is advantageous. The temperature varies depending on the cycloalkene used, but is usually 50 to 300 ° C., and preferably 70 to
200 degreeC, More preferably, it is 80-160 degreeC. The reaction pressure is not particularly limited, but a pressure capable of keeping cycloalkene and water in a liquid phase is preferable, and usually 5 MPa or less, preferably 0.2 to 2 MPa. Furthermore, the reaction time or residence time is usually 0.1 to 10 hours, preferably 0.
5 to 5 hours. The reaction system is preferably kept in an atmosphere of an inert gas such as nitrogen, hydrogen, helium, argon, carbon dioxide, etc. In this case, it is desirable that the content of oxygen in the inert gas is small, and the oxygen content is But usually 10
The amount used is 0 ppm or less, preferably 20 ppm or less.

The reaction solution obtained by the above hydration reaction can usually be phase-separated into an aqueous phase containing a solid acid catalyst and an oil phase containing mainly cycloalkene, cycloalkanol and additives. The aqueous phase containing the catalyst and the cycloalkene aqueous phase dissolution promoter can be separated and then recycled as a catalyst slurry by circulating it to the reactor. The cycloalkanol produced from the separated oil phase can be easily purified and recovered by a known method such as distillation. The residual liquid containing the starting material cycloalkene and the cycloalkanol oil phase extraction promoter after separating the cycloalkanol can be reused as the starting material for the hydration reaction.

[0023]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Reference Example 1 (Preparation Example of Solid Acid Catalyst) First, a raw material liquid having the following composition was prepared.

[0024]

Table 1 (Solution A) Gallium nitrate 4.0 g 95% sulfuric acid 8.8 g Tetrafluoroammonium bromine 13.1 g Water 65 g (Solution B) Water glass 105.5 g Water 65 g (Solution C) Sodium chloride 39.5 g 121 g of water

Next, at room temperature, Solution A and Solution B were simultaneously added dropwise to Solution C. The obtained mixture (charged atomic ratio: Si / Ga
= 25/1) was put into a 1 l autoclave with a Teflon inner cylinder, and after nitrogen substitution, hydrothermal synthesis was carried out at 170 ° C. for 20 hours under its own pressure. After cooling, the product is filtered, washed with water and dried, 5
It was baked at 50 ° C. for 6 hours. It was confirmed by X-ray diffraction of the obtained powder that it had an MFI structure. The Na-type gallosilicate thus obtained was ion-exchanged to H-type with a 1N aqueous ammonium nitrate solution, washed with water, dried, and calcined at 500 ° C. for 4 hours to obtain an H-type gallosilicate. Reference Example 2 (Confirmation of Action of Cyclohexene Aqueous Phase Dissolution Promoter) Cyclohexene 3.89 was placed in a 50 ml eggplant-shaped flask.
g, cyclohexanol 0.74 g, water 9.00 g, or silicotungstic acid was added thereto, and the mixture was heated and stirred at 60 ° C. for 1 hour, and then left standing at room temperature for 15 minutes. The water phase separated into two phases was separated, and the results of gas chromatography analysis are shown in Table 1.

[0026]

[Table 2]

Reference Example 3 (Confirmation of Action of Cyclohexanol Oil Phase Extraction Accelerator) 3.89 cyclohexene was added to a 50 ml eggplant type flask.
g, cyclohexanol 0.74 g, water 9.00 g, or cyclohexanol organic phase extractant added thereto,
After heating and stirring at 60 ° C. for 1 hour, the mixture was left standing at room temperature for 1 hour. The oil phase and the aqueous phase that have been separated into two phases are separated, and the results of analysis by gas chromatography are shown in Table 2.

[0028]

[Table 3]

Example 1 15 g of cyclohexene, 30 g of water, 5 g of H-type gallosilicate obtained in Reference Example 1 and 5.2 g of n-octyl sulfonic acid were placed in an autoclave equipped with a 200 ml stirring blade.
5 g (35 wt% with respect to cyclohexene) was added, and the mixture was reacted at 120 ° C. for 1 hour in a nitrogen atmosphere. After the reaction,
The organic phase and aqueous phase of the obtained reaction solution and the ethanol solution from which the catalyst was washed were individually analyzed by gas chromatography. The reaction results are shown in Table 3. The cyclohexene concentration in the aqueous phase was 1.34% by weight. Example 2 The hydration reaction of cyclohexene was carried out in the same manner as in Example 1 except that 5.25 g of n-octylsulfonic acid in Example 1 was replaced with 3.0 g of silicotungstic acid. The reaction results are shown in Table 3.

Comparative Example 1 The hydration reaction of cyclohexene was carried out in the same manner as in Example 1 except that n-octylsulfonic acid was not added in Example 1. The reaction results are shown in Table 3. The cyclohexene concentration in the aqueous phase was 0.013% by weight. Comparative Example 2 The hydration reaction of cyclohexene was carried out in the same manner as in Example 1 except that H-type gallosilicate as a catalyst was not added in Example 1. The reaction results are shown in Table 3.

[0031]

[Table 4] Note) Comparative example 2 uses no zeolite catalyst.

Example 3 The hydration reaction of cyclohexene was carried out in the same manner as in Example 1 except that the amount of n-octyl sulfonic acid was changed to 0.4 g and benzoic acid 4.5 g was added. The reaction results are shown in Table 4. Example 4 The hydration reaction of cyclohexene was carried out in the same manner as in Example 3 except that 0.45 g of n-octylsulfonic acid was replaced with 0.75 g of silicotungstic acid. The reaction results are shown in Table 4. Comparative Example 3 The hydration reaction of cyclohexene was carried out in the same manner as in Example 3 except that n-octylsulfonic acid was not added in Example 3. The reaction results are shown in Table 4.

[0033]

[Table 5]

[0034]

According to the present invention, cycloalkanol can be produced from cycloalkene in high yield.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuji Fujii 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute

Claims (8)

[Claims] 1. A method for producing a cycloalkanol by mixing an oil phase containing a cycloalkene and an aqueous phase in the presence of a solid acid catalyst to produce a cycloalkanol, wherein the cycloalkene is distributed to the aqueous phase in the reaction system. A method for producing a cycloalkanol, which comprises allowing a substance having a function of increasing the rate to coexist. 2. A method for producing a cycloalkanol by mixing an oil phase containing a cycloalkene and an aqueous phase in the presence of a solid acid catalyst to produce a cycloalkanol, wherein the cycloalkene is distributed to the aqueous phase in the reaction system. A method for producing a cycloalkanol, which comprises coexisting a substance having an action of increasing the ratio with a substance having an action of increasing the distribution ratio of the cycloalkanol produced by the hydration reaction to the organic phase. 3. The method according to claim 1, wherein the substance having the action of increasing the distribution ratio of cycloalkene to the aqueous phase is substantially distributed to the aqueous phase. 4. The method according to claim 1, wherein the substance having an action of increasing the distribution ratio of cycloalkene to the aqueous phase is an alkylsulfonic acid or a heteropolyacid. 5. The substance according to claim 2, wherein the substance having the action of increasing the distribution ratio of cycloalkanol to the organic phase is an aromatic carboxylic acid, a phenol or a cyclic saturated carboxylic acid. the method of. 6. The coexisting amount of the substance having an action of increasing the distribution ratio of cycloalkene to the aqueous phase is 0.01 to 40% by weight based on cycloalkene. Either way. 7. The coexisting amount of the substance having the action of increasing the distribution ratio of cycloalkanol to the organic phase is 0.001 to 100% by weight with respect to the cycloalkene. Either way. 8. The method according to claim 1, wherein the cycloalkene is cyclohexene.