JPH1087644A - Production of high-purity cyclohexene oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production process for cyclohexene oxide which can produce cyclohexene oxide of high purity from cyclohexene in high yield with industrial advantage, as the formation of by-products, CPAL and CPCA which causes bad smells, is inhibited as much as possible. SOLUTION: In the production process for cyclohexene oxide comprising the first reaction step in which an aqueous solution of hypochlorite salt and an acid are allowed to react with cyclohexene to form 2-chlorohexanol and the second reaction step in which an alkali is allowed to act on the 2- chlorocyclohexanol to form cyclohexene oxide, the reaction in the first reaction step is carried out at (30-70 deg.C, as the hydrogen ion concentration is maintained in the range of 7<= pH <= 9.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing cyclohexene oxide from cyclohexene as a raw material, and particularly to cyclopentanecarbaldehyde (hereinafter referred to as "C").
PAL) and cyclopentanecarboxylic acid (hereinafter abbreviated as “CPCA”). Cyclohexene oxide obtained by the present invention is an additive such as a solvent,
It is a useful compound that can be used for applications such as intermediates for medical and agricultural chemicals and intermediates for polymer raw materials.

[0002]

2. Description of the Related Art As a method for producing high purity cyclohexene oxide, hydrochloric acid and hydrogen peroxide are allowed to act on cyclohexene, caustic soda is acted on 2-chlorocyclohexanol produced, and the resulting cyclohexene oxide is purified by distillation. A method for obtaining a cyclohexene oxide having a purity of 99% by weight (gas chromatography analysis) is known (for example, JP-A-46-226).
No. 1).

[0003] This method is excellent in that cyclohexene oxide having a purity of more than 99% by weight can be easily produced from cyclohexene as a raw material, but the obtained cyclohexene oxide has an odor due to impurities (there is no description about impurities). ), And it cannot be said that the production method is always satisfactory in this respect.

The present inventors have conducted intensive studies on the odor-causing substance of cyclohexene oxide of this product. As a result, the direct causative substance of this odor was converted from cyclohexene to cyclohexene oxide (boiling point: 130
° C), which is by-produced during the production process, is difficult to separate and remove easily by distillation, is a small amount of CPCA contained as an impurity in cyclohexene oxide, and is an indirect cause of this odor. CPAL (boiling point: 136 ° C), which is a by-product of cyclohexene oxide production, is difficult to separate and remove by distillation, is contained as an impurity in cyclohexene oxide, and is oxidized by contact with air to produce CPCA Ascertained.

As a method for obtaining a product of cyclohexene oxide having a low odor, CPAL which is contained as an impurity in the cyclohexene oxide and is oxidized to change to CPCA which is a direct cause of the odor is prevented from being air-oxidized. Therefore, a method of adding a phenol-based, sulfur-based, phosphorus-based and hindered amine-based antioxidant has been proposed (Japanese Patent Application No. 8-186155).

According to the method of adding an antioxidant,
Prevents CPAL from being oxidized to CPCA by air oxidation, thereby resulting in CPC which is contained in the product cyclohexene oxide and directly causes odor.
This method has the advantage of reducing the content of A and preventing the generation of odors, but this method reduces by-products of odor-causing substances (including direct-causing substances and indirect-causing substances). However, the addition of an antioxidant lowers the purity, and is not suitable for applications requiring high purity.

As a method for separating and removing odor-causing substances, hydroxylamine is allowed to act on cyclohexene oxide containing CPAL and CPCA, and the treatment liquid is purified by distillation, for example, with a CPAL content of 12 pp.
m and CPCA content less than 5 ppm and purity 9
A method for obtaining high-purity cyclohexene oxide having a low impurity content of 9.8% (gas chromatography analysis) was proposed (Japanese Patent Application No. 8-186154).

This method is superior in that CPAL and CPCA, which are substances causing odor contained in cyclohexene oxide, are removed as much as possible to obtain high-purity cyclohexene oxide. Is a purification distillation method for separating and removing impurities, particularly odor-causing substances, which requires additional steps of hydroxylamine treatment and purification distillation in order to re-purify cyclohexene oxide isolated from the reaction mixture. In a typical production, there is a problem that the number of facilities and the number of working processes are inevitably increased, and the production cost is increased, which is not economical.

[0009]

From the above viewpoint, the present inventors have further studied and found that CPCA and CPAL, which are odor-causing substances in the production process of producing cyclohexene oxide from cyclohexene as a raw material, are subordinate. As a result, high purity cyclohexene can be prevented not only from the problem of odor as in the prior art described above, but also from the problems of the previously proposed antioxidant addition method and purification distillation method. A method by which oxides can be produced industrially advantageously was studied.

Therefore, first, an aqueous solution of sodium hypochlorite and sulfuric acid are added to cyclohexene at a hydrogen ion concentration of 2%.
<PH <7 and reaction temperature of 30-70 ° C. to produce 2-chlorocyclohexanol (JP-A-7-1995).
JP-A-196567), and then the obtained 2-chlorocyclohexanol was treated with alkali to produce cyclohexene oxide. As a result, cyclohexene oxide was obtained in a yield based on the consumed cyclohexene of 78.3% by weight, and this was distilled. Purity 9 obtained by purification
9.3% (gas chromatography) cyclohexene oxide had a CPAL concentration of 3200 ppm and a CPCA concentration of 600 ppm, and the odor at this point was considerably improved. However, this cyclohexene oxide has a CPAL concentration of 3200 pp.
m, and contacted with air increased the CPCA concentration and worsened the odor.

Then, as a result of further study, it was surprisingly found that 2-hexyl chloride obtained by reacting cyclohexene with an aqueous solution of sodium hypochlorite and sulfuric acid under the condition of a hydrogen ion concentration of 7 ≦ pH ≦ 9 was obtained. When cyclohexene oxide is produced using cyclohexanol, a substance C directly causing odor in the obtained cyclohexene oxide C
Not only PCA but also the indirect causative substance CPAL can significantly reduce by-products up to a total of 1000 ppm or less, whereby high-purity cyclohexene oxide with odor generation suppressed as much as possible. Has been found to be industrially advantageous.

Accordingly, an object of the present invention is to provide a method for producing cyclohexene oxide using cyclohexene as a raw material, wherein CPAL and CPCA which are substances causing odor are used.
It is an object of the present invention to provide a method for producing a high-purity cyclohexene oxide, which can industrially and advantageously produce a high-purity cyclohexene oxide in a high yield by preventing by-products of the product as much as possible.

[0013]

That is, the present invention provides a first reaction step in which cyclohexene is reacted with an aqueous solution of hypochlorite and an acid to produce 2-chlorocyclohexanol, and the first reaction step. And a second reaction step of producing cyclohexene oxide by reacting the obtained 2-chlorocyclohexanol with an alkali, wherein the reaction in the first reaction step is carried out by reducing the hydrogen ion concentration of the reaction system to 7%. ≦ pH ≦ 9
This is a method for producing a high-purity cyclohexene oxide which can be carried out under the conditions of a reaction temperature of 30 to 70 ° C. while keeping the reaction temperature within the range described above, whereby the by-products of impurities such as CPAL and CPCA can be suppressed as much as possible.

In the method of the present invention, the starting material cyclohexene used in the first reaction step is not particularly limited, but may be any of those produced by various methods, for example, those obtained by dehydrating cyclohexanol and chlorocyclohexane. Examples thereof include those that have been dehydrochlorinated and those that have been partially hydrogenated with benzene. The cyclohexene may contain raw materials and by-products derived from its production. Examples of such raw materials and by-products include cyclohexanol, chlorocyclohexane, benzene, cyclohexane, methylcyclopentane, and methylcyclopentane. Cyclopentene and the like can be mentioned, and the content thereof is from several weight% to the same amount, and in some cases, even if it is present several times in amount with respect to cyclohexene, it can be used as it is. These raw materials and by-products can be easily separated and removed in a post-treatment step after completion of the reaction in the first reaction step or the second reaction step.

Although the aqueous solution of hypochlorite used in the method of the present invention is not particularly limited, an aqueous solution of sodium hypochlorite is usually used, and the aqueous solution of sodium hypochlorite is generally a sodium hydroxide solution. Examples thereof include those produced by introducing chlorine gas into an aqueous solution and those produced by electrolyzing an aqueous sodium chloride solution. In the present invention, the concentration of sodium hypochlorite in the aqueous sodium hypochlorite solution is usually 2 to 40% by weight, preferably 5 to 30% by weight. If the concentration of sodium hypochlorite is too low, the concentration of 2-chlorocyclohexanol produced will be low and the production efficiency will decrease. Conversely, if the concentration of sodium hypochlorite is too high, 1,2-dichloro By-products such as cyclohexane and 2,2′-dichlorocyclohexyl ether increase and the yield of the desired 2-chlorocyclohexanol decreases, which is not preferable.

Examples of the acid for neutralizing hypochlorite to produce free hypochlorous acid for chlorohydrination include strong acids such as sulfuric acid, phosphoric acid, and nitric acid, and are preferred. The use of sulfuric acid is not preferred. When sodium hypochlorite is neutralized with hydrochloric acid and chlorohydrination of cyclohexene is performed, the concentration of free hypochlorous acid produced decreases, and the concentration of 2-chlorocyclohexanol in the reaction mixture after the reaction is completed. Not only lowers production efficiency, but also increases by-products such as 1,2-dichlorocyclohexane and 2,2'-dichlorocyclohexyl ether, and decreases the yield of 2-chlorocyclohexanol. .

In the present invention, the acid is usually used as an aqueous solution.
For example, when the acid aqueous solution is a sulfuric acid aqueous solution, usually 3 to 70
% By weight, preferably 5 to 60% by weight. If the acid concentration is too low, the concentration of the produced 2-chlorocyclohexanol will be low and the production efficiency will decrease. Conversely, if the acid concentration is too high, 1,2-dichlorocyclohexane and 2,2'-dichloro By-products such as cyclohexyl ether increase, and the yield of 2-chlorocyclohexanol decreases, which is not preferable.

In the method of the present invention, in the first reaction step, it is necessary to maintain the hydrogen ion concentration pH of the reaction system at 7 ≦ pH ≦ 9. When the hydrogen ion concentration becomes lower than pH 7, the content of impurities in the finally obtained cyclohexene oxide increases, and the odor-causing substance CPA is increased.
It is difficult to suppress the content of L and CPCA to the target of 1000 ppm or less, preferably 800 ppm or less. Conversely, if the hydrogen ion concentration exceeds pH 9, the reactivity is significantly reduced, which is not preferable. From the viewpoint of increasing the yield of 2-chlorocyclohexanol,
When the hydrogen ion concentration of the reaction system is in the range of 2 <pH <7, particularly 3
It is desirable to control the pH within the range of <6, but from the viewpoint of reducing the contents of the odor-causing substances CPAL and CPCA in the finally obtained cyclohexene oxide as much as possible, some yield may be obtained. Even at the cost of sacrificing, it is necessary to maintain the hydrogen ion concentration of the reaction solution at 7 ≦ pH ≦ 9, further reduce the contents of CPAL and CPCA as much as possible, and reduce the yield of 2-chlorocyclohexanol. From the viewpoint of increasing as much as possible, it is preferable that the pH of the hydrogen ion concentration be weakly alkaline, that is, 7 <pH ≦ 8.

In the first reaction step, the reaction temperature is maintained at 30 to 70 ° C., preferably 35 to 60 ° C. Although the reaction temperature does not affect the reactivity and yield even when the reaction temperature is 30 ° C or lower, the cost required for cooling the reaction system increases, and when the reaction temperature exceeds 70 ° C,
By-products such as 1,2-dichlorocyclohexane and 2,2'-dichlorocyclohexyl ether increase to lower the yield of 2-chlorocyclohexanol, and the odor-causing substance C in the finally obtained cyclohexene oxide
The content of PAL and CPCA increases.

The reaction of cyclohexene with sodium hypochlorite and acid in the first reaction step is sufficiently fast, for example, it is not necessary to take a particularly long time even at a temperature of 10 ° C. or lower. If the reaction rate is increased to increase the reaction rate, the by-products increase and the yield of 2-chlorocyclohexanol decreases, or the vapor pressure of cyclohexene increases and the control of the reaction becomes difficult. Since the reaction in the first reaction step is accompanied by evaporation, cooling to an ambient temperature or lower requires a large amount of equipment and cooling equipment for cooling. However, in the method of the present invention, since the hydrogen ion concentration pH of the reaction system is maintained at 7 ≦ pH ≦ 9,
Even without cooling, or with very little cooling, 2-chlorocyclohexanol can be obtained at ambient temperature or higher but not extremely high without significant reduction in yield.

In the first reaction step of the present invention, as long as the hydrogen ion concentration of the reaction system is maintained within the range of 7 ≦ pH ≦ 9, all the raw materials may be simultaneously charged into the reactor and reacted. Alternatively, each reaction raw material may be appropriately dispersed and added to the reactor. For example, in the case of performing a batch reaction, a predetermined amount of cyclohexene is first charged into a reactor, and then a predetermined amount of hypochlorous acid is added while controlling the hydrogen ion concentration of the reaction mixture to be in a range of 7 ≦ pH ≦ 9. A method in which a sodium aqueous solution and sulfuric acid are simultaneously added, or a method in which a predetermined amount of cyclohexene and a sodium hypochlorite aqueous solution are previously charged in a reactor, so that the hydrogen ion concentration of the reaction mixture is in the range of 7 ≦ pH ≦ 9. A method of adding sulfuric acid while controlling the temperature is exemplified.

The reaction time in the first reaction step is as follows:
Although it depends on the charge amount, the reaction temperature, and the like, the necessary raw materials are usually added sequentially in 10 minutes to 100 hours, and then the reaction may be further performed in 1 minute to 10 hours. The progress of the reaction is 30
Even at a temperature of about ° C, it is sufficiently fast, and it is not necessary to take a long time.

Performing the reaction in the first reaction step continuously is one of the desirable modes. That is, cyclohexene, hypochlorite aqueous solution and acid are simultaneously and continuously supplied to the reactor, and a reaction mixture containing 2-chlorocyclohexanol is continuously withdrawn from the reactor. As a method of extracting the reaction mixture from the reactor, an overflow method may be used from the upper part of the reactor, or a method of extracting the reaction mixture at a constant speed from an outlet attached to the lower part or the side surface of the reactor. The reaction time in the case of this continuous reaction,
That is, the residence time also varies depending on the reaction temperature and the like, but is usually in the range of 1 minute to 10 hours.

Further, in the first reaction step, the reaction is carried out at the interface between the oil phase composed of cyclohexene and the aqueous phase composed of the aqueous solution of hypochlorite and the acid, so that this reaction can be carried out efficiently and smoothly. Is preferably carried out in an emulsion state in which both coexist in a good contact state. To this end, the reaction is preferably carried out under a good mixed state, and a surfactant not involved in the reaction may be added as necessary. .

Next, the second reaction step of the present invention is a step of reacting 2-chlorocyclohexanol produced in the first reaction step with an alkali to produce cyclohexane oxide. In the second reaction step, the reaction mixture of the first reaction step may be used as it is, or the reaction mixture may be separated into oil and water to recover an oil phase containing 2-chlorocyclohexanol. The oil phase of the mixture may be used as a raw material as it is, and further, 2-chlorocyclohexanol is separated from the oil phase of the reaction mixture,
This 2-chlorocyclohexanol may be purified or used as a raw material without purification.

Alkali used in the second reaction step is a hydroxide of an alkali metal or an alkaline earth metal,
Carbonates and the like are preferred, and specific examples include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, and the like. These can be used alone or as a mixture of two or more. The method of adding the alkali is not particularly limited, but it is usually used in the form of an aqueous solution or suspension for the reaction, and its use amount is not particularly limited, but it is usually used in the first reaction step. It is at least 0.9 times the molar equivalent of chlorite. If the amount of alkali added is less than this, unreacted 2-chlorocyclohexanol increases and the yield decreases.

The reaction between 2-chlorocyclohexanol and alkali in the second reaction step is also sufficiently fast as in the reaction between cyclohexene, hypochlorite and acid in the first reaction step, for example, at 10 ° C. or lower. It is not necessary to spend a particularly long time at the temperature. For example, when the oil phase of the reaction mixture obtained in the first reaction step is used as it is, there is no particular need for heating and cooling, and even if it is slightly cooled if necessary. Often, even if the reaction temperature is lower than 30 ° C., the reactivity and yield are hardly affected. Therefore, the reaction temperature is usually maintained at 30 to 70 ° C, preferably 35 to 60 ° C. Lowering the reaction temperature below 30 ° C increases the cost for unnecessary cooling, and conversely. To
When the reaction temperature exceeds 70 ° C., the product cyclohexene oxide is secondarily reacted with water as a side reaction,
Problems such as formation of cyclohexanediol,
By-products increase and the yield of cyclohexene oxide decreases.

Since the reaction in the second reaction step also proceeds at the interface between the water phase and the oil phase, as in the reaction in the first reaction step, both are good in order for this reaction to proceed efficiently and smoothly. It is preferable to carry out the reaction in an emulsion state which coexists in a good contact state. For this purpose, it is preferable to carry out the reaction under a good mixing state, and if necessary, a surfactant which does not participate in the reaction may be added.

The reaction time varies depending on the reaction conditions such as the reaction temperature and stirring conditions, but may be between 1 minute and 10 hours.
However, if the reaction time is longer than necessary,
The product, cyclohexene oxide, is not preferable because it causes a problem of by-products such as secondary reaction with water to form 1,2-cyclohexanediol.

In the present invention, the method for recovering the desired cyclohexene oxide from the reaction mixture obtained in the second reaction step is not particularly limited, but is usually carried out by the following method.

That is, first, the reaction mixture obtained in the second reaction step is separated into oil and water to recover the oil phase of the reaction mixture containing cyclohexene oxide. The oil phase of the reaction mixture can be recovered by centrifuging the reaction mixture as it is, or by allowing it to stand still to separate the aqueous phase and the oil phase to separate oil and water. Is extracted, and organic components containing cyclohexene and cyclohexene oxide in the aqueous phase are recovered. Examples of the organic solvent used for this purpose include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof, and these may be used alone or in combination. A particularly preferred organic solvent is to use the raw material cyclohexene, thereby purifying cyclohexene oxide, recovering unreacted cyclohexene,
Time and effort for recovery of the extraction solvent and the like can be reduced.

Next, the oil phase of the reaction mixture thus recovered is subjected to distillation to separate and recover the desired cyclohexene oxide. This distillation may be a batch type or a continuous type, and unreacted cyclohexene and organic solvent other than the target substance recovered by the distillation are usually reused.

In the present invention, the reaction system in the first reaction step in which the aqueous solution of hypochlorite and an acid are allowed to act on cyclohexene is maintained at a hydrogen ion concentration of 7 ≦ pH ≦ 9 to carry out a chlorohydrination reaction. -Synthesis of chlorocyclohexanol. Here, the hydrogen ion concentration is considered to be a factor that governs the form of hypochlorite ion present in the reaction system.
chnology, 3rd Ed., Vol. 8, pp. 680, John Wiley & So
According to ns, Inc. 1979, hypochlorite ion changes its form depending on the pH, and changes from chlorine to hypochlorite to hypochlorite in order from acidic side to alkaline side. I do.

By the way, a method for producing 2-chlorocyclohexanol by reacting an aqueous solution of sodium hypochlorite and sulfuric acid on cyclohexene (JP-A-7-196567)
Publication), the hydrogen ion concentration of the reaction system is 2 <
When pH <7, preferably 3 <pH <6, 2-
Chlorocyclohexanol is obtained in good yield. Therefore, from the correlation between the hydrogen ion concentration of this reaction system and the yield of 2-chlorocyclohexanol, the reactive species in this chlorohydrination reaction would be hypochlorous acid instead of chlorine or hypochlorite ion. It is also known that when chlorine acts on cyclohexene, 1,2-dichlorocyclohexane is produced.

From these facts, maintaining the hydrogen ion concentration in the reaction system in the first reaction step within the range of 7 ≦ pH ≦ 9 of the present invention is based on the hypochlorous acid which is a reactive species in the chlorohydrination reaction of cyclohexene. , Which leads to milder conditions for the chlorohydrination reaction, which suppresses the side reactions that result in the formation of impurities and the resulting cyclohexene It is considered that the formation of impurities in oxides, particularly CPAL and CPCA, which are substances causing odor, or the production of their precursors is suppressed, and the contents of these CPAL and CPCA are reduced.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be specifically described below based on examples and comparative examples.

Example 1 Cyclohexene was used in an amount 1.3 times the mol of sodium hypochlorite, and the hydrogen ion concentration of the reaction solution was 7 ≦ p.
A continuous chlorohydrination reaction was carried out using sulfuric acid so that H ≦ 9 at a reaction temperature of 50 ° C. and a residence time of 3 hours (first reaction step), and the resulting reaction mixture containing 2-chlorocyclohexanol was removed. The reaction mixture was taken out of the reactor, and then the reaction mixture was charged with 1.2 times mol of caustic soda based on the starting material cyclohexene.
An epoxidation batch reaction was performed at 2 ° C. (second reaction step), the obtained reaction mixture was separated into oil and water, and the oil phase of the reaction mixture was distilled to obtain a desired cyclohexene oxide.

[Chlorohydrination reactor] 1000 m
The mechanical stirrer, the thermometer, and the pH meter were set in a 1-liter 5-neck flask. A silicone rubber tube was attached to each of the three dropping funnels for supplying raw materials, and the ends of the tubes were introduced into the flask through a tube pump. On the other hand, a silicone rubber tube was introduced from the flask through a tube pump into a 1000 ml measuring cylinder for extracting the reaction solution.

[Epoxidation reactor] 1000 ml of 5
A mechanical stirrer and a thermometer were set in the neck flask. A silicone rubber tube was attached to one dropping funnel for supplying raw materials, and the tip of the tube was introduced into the flask via a tube pump. [Purification distillation apparatus] A vacuum (normal to reduced pressure) distillation apparatus equipped with a distillation column (inner diameter 10 mm x height 150 mm) packed with a spiral packing made of stainless steel was used.

[Reaction solution for chlorohydrin preparation] A reaction solution separately prepared by using 3 mol of sodium hypochlorite for charging was separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition in 73.0 g of the oil phase corresponding to 0.5 mol of sodium hypochlorite is 8.52 g of cyclohexene and 5 parts of 2-chlorocyclohexanol.
1.0 g, and the composition in 433 g of the same aqueous phase was 2.63 g of 2-chlorocyclohexanol. Total 2-chlorocyclohexanol was 53.6 g.

[Continuous chlorohydrination reaction]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3 h), 282 g / 3 h of sodium hypochlorite aqueous solution (concentration 13.2 wt%, 0.500 mol / 3 h), and for sulfuric acid (20 wt%), the hydrogen ion concentration of the reaction mixture is The pH was controlled so as to be 7 ≦ pH ≦ 9, and the reaction solution withdrawal speed was controlled so that the amount of the reaction solution was constant. The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used is 6
It was 42 g (1.31 mol).

The reaction solution every three hours and the reaction solution in the flask after completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition in the total reaction liquid oil phase of 468 g was 80.6 g of cyclohexene and 261 g of 2-chlorocyclohexanol, and the total aqueous phase of the reaction liquid was 2355 g.
The composition in g was 9.8 g of 2-chlorocyclohexanol. Total 2-chlorocyclohexanol was 271 g.

The product of the continuous reaction portion was converted into 72.1 g (0.878 mol) of cyclohexene and 217 g (1.61 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore,
272 g of cyclohexene used in the continuous part (3.25
(Mole), the average reaction result of the continuous portion was a conversion of cyclohexene of 73% and a selectivity of 2-chlorocyclohexanol of 68%.

[Epoxylation batch reaction] Oil phase 4 of the whole reaction liquid
68 g (261 g of 2-chlorocyclohexanol, 1.
780 g (20.0% by weight, 3.90 mol) of an aqueous solution of caustic soda was added to 2355 g of the aqueous phase (94 mol) and 2355 g (9.8 g of 2-chlorocyclohexanol, 0.07 mol) of the whole reaction solution at 50 ° C. for 1 hour. Was added. Total reaction liquid oil phase 389
The composition in g was 80.1 g of cyclohexene and 182 g (1.86 mol) of cyclohexene oxide, and the composition in 3195 g of the aqueous phase of the whole reaction solution was 12.8 g (0.13 mol) of cyclohexene oxide. Total cyclohexene oxide was 195 g (1.99 mol). 100% conversion of 2-chlorocyclohexanol
And the selectivity for cyclohexene oxide was 99%.

[Distillation of epoxidation reaction oil phase] 389 g of the whole reaction liquid oil phase was charged into a purification distillation apparatus, and was subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. An azeotrope of cyclohexene and water at an overhead temperature of 60 to 82 ° C 8
5.0 g were obtained. 25 ° C at a pressure of 80 mmHg
, The distillation was restarted by raising the temperature of the distillation can, and the first distillation of cyclohexene oxide was performed at a tower top temperature of 40 to 60 ° C.
g of cyclohexene oxide (distillation yield: 95%) was obtained at an overhead temperature of 64-65 ° C. The CPAL content of the obtained cyclohexene oxide is 500
ppm, the content of CPCA was 100 ppm, and the purity was 99.6%.

COMPARATIVE EXAMPLE 1 Cyclohexene was used in an amount 1.3 times the molar amount of sodium hypochlorite, and the reaction solution had a hydrogen ion concentration of 6 <p.
A continuous chlorohydrination reaction was carried out using sulfuric acid so that H <7 at a reaction temperature of 50 ° C. and a residence time of 1 hour, and the resulting reaction mixture containing 2-chlorocyclohexanol was withdrawn from the reactor. The reaction mixture was charged with 1.2 times mol of caustic soda with respect to cyclohexene as a starting material, and an epoxidation batch reaction was carried out at a reaction temperature of 50 ° C., and the obtained reaction mixture was separated into oil and water. Was recovered and distilled to obtain cyclohexene oxide.

[Reaction / Distillation Apparatus] The same apparatus as in Example 1 was used. [Chlorohydrin preparation reaction solution] The same reaction solution as in Example 1 was used.

[Continuous Reaction of Chlorhydrination]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3h), 282 g / h of sodium hypochlorite aqueous solution (concentration 13.2% by weight, 0.500 mol /
h), the sulfuric acid (20% by weight) was controlled so that the hydrogen ion concentration of the reaction mixture was 6 <pH <7, and the reaction solution withdrawal speed was such that the amount of the reaction solution was constant. The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. Total amount of sulfuric acid used is 686g
(1.40 mol).

The reaction solution every three hours and the reaction solution in the flask after completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition in the total reaction liquid oil phase of 470 g is 57.5 g of cyclohexene and 323 g of 2-chlorocyclohexanol, and the total aqueous phase of the reaction liquid is 2395 g.
The composition in g is 10.2 g of 2-chlorocyclohexanol
Met. 333 g of total 2-chlorocyclohexanol
Met.

The product of the continuous reaction portion was converted into 49.0 g (0.598 mol) of cyclohexene and 269 g (2.00 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore,
272 g of cyclohexene used in the continuous part (3.25
(Mol), the average reaction result of the continuous portion was a cyclohexene conversion of 82% and a 2-chlorocyclohexanol selectivity of 75%.

[Epoxidation batch reaction] Oil phase 4 of the whole reaction liquid
70 g (323 g of 2-chlorocyclohexanol, 2.
40 mol) and 800 g (20.0% by weight, 4.00 mol) of an aqueous caustic soda solution in 2395 g (10.2 g of 2-chlorocyclohexanol, 0.08 mol) of the aqueous phase of the whole reaction solution.
Was added at about 50 ° C. over 1 hour. Total reaction oil phase 39
The composition in 0 g is 56.9 g of cyclohexene and 226 g (2.31 mol) of cyclohexene oxide,
The composition in 3255 g of the aqueous phase of the whole reaction solution was 14.4 g (0.15 mol) of cyclohexene oxide. Total cyclohexene oxide was 240 g (2.46 mol). 100% conversion rate of 2-chlorocyclohexanol
And the selectivity for cyclohexene oxide was 99%.

[Distillation of epoxidation reaction oil phase] 390 g of the above-mentioned reaction liquid oil phase was charged into a purification distillation apparatus and subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. An azeotropic mixture of cyclohexene and water at an overhead temperature of 60 to 82 ° C 6
1.9 g were obtained. 25 ° C at a pressure of 80 mmHg
The distillation was restarted by raising the temperature of the distillation still from the beginning, and the first distillation of cyclohexene oxide was carried out at a column head temperature of 40 to 60 ° C. 8.0.
g of cyclohexene oxide was obtained at a top temperature of 64-65 ° C. (distillation yield: 94%). The cyclohexene oxide obtained has a Cpal content of 150
It was 0 ppm, the content of CPCA was 350 ppm, and the purity was 99.5%.

Comparative Example 2 Cyclohexene was used at 1.1 times the molar amount of sodium hypochlorite, and the hydrogen ion concentration of the reaction solution was 4 <pH <6.
Chlorohydrin continuous reaction was carried out using sulfuric acid under the conditions of a reaction temperature of 50 ° C. and a residence time of 1 hour,
The reaction mixture containing the formed 2-chlorocyclohexanol was withdrawn from the reactor, and then 1.2 times mol of caustic soda was added to the reaction mixture with respect to the starting material cyclohexene, and the epoxidation batch reaction was carried out at a reaction temperature of 50 ° C. The reaction mixture was subjected to oil-water separation, and the oil phase of the reaction mixture was distilled to obtain a desired cyclohexene oxide.

[Reaction / Distillation Apparatus] The same apparatus as in Example 1 was used. [Chlorohydrin preparation reaction solution] The same reaction solution as in Example 1 was used.

[Continuous Chlorohydrination Reaction]
Cyclohexene, an aqueous solution of sodium hypochlorite, and sulfuric acid were simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 moles, and the reaction solution was withdrawn while the reaction components were added dropwise to continue the continuous reaction for 6 hours. Carried out. The dripping speed is
46.1 g / h of cyclohexene (purity 98%, 0.55
0 mol / h), 282 g of an aqueous solution of sodium hypochlorite /
h (concentration 13.2% by weight, 0.500 mol / h) and sulfuric acid (20% by weight) were controlled so that the hydrogen ion concentration of the reaction mixture was 4 <pH <6. Was adjusted so that the amount of the reaction solution was constant.
The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used is 819 g (1.60 mol)
Met.

The reaction solution every one hour and the reaction solution in the flask after the completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition of the total reaction liquid oil phase in 485 g was 46.5 g of cyclohexene and 337 g of 2-chlorocyclohexanol.
The composition in 1 g is 2-chlorocyclohexanol 14.2
g. 352 total 2-chlorocyclohexanol
g.

The product of the continuous reaction portion was converted into 38.0 g (0.462 mol) of cyclohexene and 298 g (2.21 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore,
277 g of cyclohexene used in the continuous part (3.30
(Mol), the average reaction result of the continuous portion was a conversion of cyclohexene of 86% and a selectivity of 2-chlorocyclohexanol of 78%.

[Epoxidation batch reaction] Oil phase 4 of the whole reaction liquid
85 g (337 g of 2-chlorocyclohexanol, 2.
792 g (20.0% by weight, 3.96 mol) of an aqueous solution of caustic soda in 2801 g (14.2 g, 2-chlorocyclohexanol) of 2801 g (50 mol) and the total aqueous phase of the reaction solution.
Was added at about 50 ° C. over 1 hour. Total reaction liquid oil phase 43
The composition in 8 g is 37.4 g of cyclohexene and 238 g (2.43 mol) of cyclohexene oxide,
The composition in 3620 g of the aqueous phase of the whole reaction solution was 15.2 g (0.15 mol) of cyclohexene oxide. Total cyclohexene oxide was 253 g (2.58 mol). 100% conversion of 2-chlorocyclohexanol
And the selectivity for cyclohexene oxide was 99%.

[Distillation of epoxidation reaction oil phase] 438 g of the whole reaction liquid oil phase was charged into a purification distillation apparatus and subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. An azeotrope of cyclohexene and water at an overhead temperature of 60 to 82 ° C.
2.9 g were obtained. 25 ° C at a pressure of 80 mmHg
The distillation was restarted by raising the temperature of the distillation still from the beginning, and the first distillation of cyclohexene oxide was carried out at a top temperature of 40 to 60 ° C. and 6.0.
g of cyclohexene oxide was obtained at a top temperature of 64-65 ° C. (distillation yield: 94%). The cyclohexene oxide obtained has a Cpal content of 320.
It was 0 ppm, the content of CPCA was 600 ppm, and the purity was 99.4%.

Comparative Example 3 Reaction temperature of 50 ° C. and residence time using cyclohexene 1.3 times mol of sodium hypochlorite and sulfuric acid so that the hydrogen ion concentration of the reaction solution becomes pH ≒ 1. 3
A continuous chlorohydrination reaction was carried out under the conditions of time, a reaction mixture containing the produced 2-chlorocyclohexanol was withdrawn from the reactor, and then the reaction mixture was charged with 1.2 times mol of caustic soda with respect to cyclohexene. An epoxidation batch reaction was performed at a temperature of 50 ° C., the obtained reaction mixture was separated into oil and water, and the oil phase of the reaction mixture was distilled to obtain a target cyclohexene oxide.

[Reaction / Distillation Apparatus] The same apparatus as in Example 1 was used. [Chlorohydrin preparation reaction solution] The same reaction solution as in Example 1 was used.

[Continuous Chlorohydrination Reaction]
Cyclohexene, an aqueous solution of sodium hypochlorite, and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are dropped, and a continuous reaction is performed for 15 hours. did. The dripping speed is
Cyclohexene 54.5 g / 3h (purity 98%, 0.6
50mol / 3h) 282g of sodium hypochlorite aqueous solution
/ 3h (concentration 13.2% by weight, 0.500 mol / 3
h) For sulfuric acid (20% by weight), the hydrogen ion concentration of the reaction mixture was controlled to be pH ≒ 1, and the reaction solution withdrawal speed was constant for the amount of the reaction solution. The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used is 922 g (1.88
Mol).

The reaction solution every 3 hours and the reaction solution in the flask after completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition of the total reaction liquid oil phase in 473 g was 83.3 g of cyclohexene and 248 g of 2-chlorocyclohexanol.
The composition in g is 13.2 g of 2-chlorocyclohexanol.
Met. 261 g of total 2-chlorocyclohexanol
Met.

The product of the continuous reaction portion was converted into 74.8 g (0.910 mol) of cyclohexene and 208 g (1.54 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore,
272 g of cyclohexene used in the continuous part (3.25
(Mol), the average reaction result of the continuous portion was a cyclohexene conversion of 72% and a 2-chlorocyclohexanol selectivity of 66%.

[Epoxylation Batch Reaction] Oil Phase 4 of All Reaction Liquids
73 g (248 g of 2-chlorocyclohexanol, 1.
84 mol) and 2,628 g of the aqueous phase of the entire reaction solution (13.2 g of 2-chlorocyclohexanol, 0.10 mol) and 780 g of an aqueous sodium hydroxide solution (20.0% by weight, 3.90 mol).
Was added at about 50 ° C. over 1 hour. Total reaction oil phase 39
The composition in 2 g is 74.3 g of cyclohexene and 176 g (1.80 mol) of cyclohexene oxide,
The composition in 3505 g of the aqueous phase of the whole reaction solution was 12.2 g (0.12 mol) of cyclohexene oxide. Total cyclohexene oxide was 188 g (1.92 mol). 100% conversion of 2-chlorocyclohexanol
Wherein the selectivity of cyclohexene oxide is 99%
Met.

[Distillation of epoxidation reaction oil phase] 392 g of the whole reaction liquid oil phase was charged into a purification distillation apparatus and subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. An azeotrope of cyclohexene and water at an overhead temperature of 60 to 82 ° C.
9.0 g were obtained. 25 ° C at a pressure of 80 mmHg
The distillation was restarted by raising the temperature of the distillation vessel from the above, and the first distillation of cyclohexene oxide was carried out at a column top temperature of 40 to 60 ° C.
g of cyclohexene oxide (distillation yield: 94%) was obtained at an overhead temperature of 64-65 ° C. The cyclohexene oxide obtained has a Cpal content of 540.
It was 0 ppm, the content of CPCA was 1100 ppm, and the purity was 98.9%.

Comparative Example 4 A reaction temperature of 50 ° C. and a residence time of 1.3 times mol of cyclohexene with respect to sodium hypochlorite, and sulfuric acid so that the hydrogen ion concentration of the reaction solution was 9 <pH. 3
A continuous chlorohydrination reaction was carried out under the conditions of time, a reaction mixture containing the produced 2-chlorocyclohexanol was withdrawn from the reactor, and then the reaction mixture was charged with 1.2 times mol of caustic soda with respect to cyclohexene. An epoxidation batch reaction was performed at a temperature of 50 ° C., the obtained reaction mixture was separated into oil and water, and the oil phase of the reaction mixture was distilled to obtain a target cyclohexene oxide.

[Reaction / Distillation Apparatus] The same apparatus as in Example 1 was used. [Chlorohydrin preparation reaction solution] The same reaction solution as in Example 1 was used.

[Continuous Chlorohydrination Reaction]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3h) aqueous sodium hypochlorite solution 2
82g / 3h (concentration 13.2% by weight, 0.500 mol /
3h) With respect to sulfuric acid (20% by weight), the hydrogen ion concentration of the reaction mixture was controlled so as to be 7 ≦ pH ≦ 9, and the reaction solution withdrawal speed was controlled so that the amount of the reaction solution was constant. The reaction temperature is about 50 minutes by heating the flask in an oil bath.
° C. The total amount of sulfuric acid used is 617g
(1.26 mol).

The reaction solution every 3 hours and the reaction solution in the flask after completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition in 422 g of the oil phase of the total reaction liquid was 155.4 g of cyclohexene and 185 g of 2-chlorocyclohexanol, and the aqueous phase of the total reaction liquid was 238 g.
The composition in 0 g is 6.9 g of 2-chlorocyclohexanol.
Met. 192 g of total 2-chlorocyclohexanol
Met.

The product of the continuous reaction portion was converted into 146.9 g (1.788 mol) of cyclohexene and 138 g (1.02 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore, 272 g of cyclohexene (3.
Based on 25 mol), the average reaction result of the continuous portion was a conversion of cyclohexene of 45% and a selectivity of 2-chlorocyclohexanol of 70%.

[Epoxidation batch reaction] Oil phase 4 of the whole reaction liquid
22 g (185 g of 2-chlorocyclohexanol, 1.
780 g (20.0% by weight, 3.90 mol) of an aqueous solution of caustic soda was added to 2380 g (6.9 g, 2-chlorocyclohexanol, 0.05 mol) of the aqueous phase of the entire reaction mixture at 37 ° C. over 1 hour at about 50 ° C. Was added. Total reaction oil phase 356
The composition in g was 146.1 g of cyclohexene and 129 g (1.32 mol) of cyclohexene oxide, and the composition in 3206 g of the aqueous phase of the whole reaction solution was 9.0 g (0.09 mol) of cyclohexene oxide. Total cyclohexene oxide was 138 g (1.41 mol).
The conversion of 2-chlorocyclohexanol was 100% and the selectivity for cyclohexene oxide was 99%.

[Distillation of epoxidation reaction oil phase] 422 g of the whole reaction liquid oil phase was charged into a purification distillation apparatus and subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. At an overhead temperature of 60 to 82 ° C., an azeotropic mixture of cyclohexene and water 14
9.5 g were obtained. 25 ° C at a pressure of 80 mmHg
, The distillation was restarted by raising the temperature of the distillation can, and the first distillation of cyclohexene oxide was carried out at a column top temperature of 40 to 60 ° C.
g of cyclohexene oxide (distillation yield: 93%) was obtained at an overhead temperature of 64-65 ° C. The cyclohexene oxide obtained has a Cpal content of 700.
ppm, the content of CPCA was 120 ppm, and the purity was 99.6%.

Comparative Example 5 Using 1.3 times mol of cyclohexene with respect to sodium hypochlorite, the hydrogen ion concentration of the reaction solution was 7 ≦ pH ≦ 9.
Chlorohydrin continuous reaction was carried out using sulfuric acid under the conditions of a reaction temperature of 75 ° C. and a residence time of 3 hours,
The reaction mixture containing the formed 2-chlorocyclohexanol was withdrawn from the reactor, and then charged with 1.2 times mol of caustic soda based on cyclohexene, and an epoxidation batch reaction was carried out at a reaction temperature of 50 ° C.
The obtained reaction mixture was subjected to oil-water separation, and the oil phase of the reaction mixture was distilled to obtain a desired cyclohexene oxide.

[Reaction / Distillation Apparatus] The same apparatus as used in Example 1 was used. [Chlorohydrin preparation reaction solution] The same reaction solution as in Example 1 was used.

[Continuous Reaction of Chlorhydrination]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3 h) and an aqueous solution of sodium hypochlorite 282 g / 3 h (concentration 13.2 wt%, 0.500 mol / 3 h). For sulfuric acid (20 wt%), the hydrogen ion concentration of the reaction mixture Was controlled so that 7 ≦ pH ≦ 9, and the reaction solution withdrawal speed was controlled so that the amount of the reaction solution was constant. The reaction temperature was controlled at about 75 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used was 637 g (1.30 mol).

The reaction solution every 3 hours and the reaction solution in the flask after the completion of the reaction were separated into an oil phase and an aqueous phase, and each was analyzed by gas chromatography. The composition in 422 g of the total reaction liquid oil phase was 102.0 g of cyclohexene and 208 g of 2-chlorocyclohexanol, and the total water phase of the reaction liquid was 239 g.
The composition in 5 g is 7.6 g of 2-chlorocyclohexanol.
Met. Total 2-chlorocyclohexanol is 216
g.

The product of the continuous reaction portion was converted into 93.5 g (1.138 mol) of cyclohexene and 162 g (1.20 mol) of 2-chlorocyclohexanol by subtracting the composition of the charged reaction solution from the total reaction solution composition. Become. Therefore,
272 g of cyclohexene used in the continuous part (3.25
(Mol), the conversion of the continuous portion was 65% in cyclohexene conversion and 57% in 2-chlorocyclohexanol selectivity.

[Epoxidation Batch Reaction] Oil Phase 4 of All Reaction Liquids
22 g (208 g of 2-chlorocyclohexanol, 1.
780 g (20.0% by weight, 3.90 mol) of an aqueous solution of caustic soda was added to 2395 g of the aqueous phase (55 mol) and 2395 g (7.6 g of 2-chlorocyclohexanol, 0.06 mol) of the whole reaction solution at 50 ° C. for 1 hour. Was added. All reaction liquid oil phase 351
The composition in g was 92.8 g of cyclohexene and 146 g (1.49 mol) of cyclohexene oxide, and the composition in 3226 g of the aqueous phase of the whole reaction solution was 9.8 g (0.10 mol) of cyclohexene oxide. Total cyclohexene oxide was 156 g (1.59 mol). 2
The conversion of -chlorocyclohexanol was 100% and the selectivity for cyclohexene oxide was 99%.

[Distillation of epoxidation reaction oil phase] 351 g of the whole reaction liquid oil phase was charged into a purification distillation apparatus and subjected to 25 ° C at normal pressure.
Then, the temperature of the distillation can was raised to start distillation. An azeotrope of cyclohexene and water at an overhead temperature of 60 to 82 ° C 9
6.5 g were obtained. 25 ° C at a pressure of 80 mmHg
The distillation was restarted by raising the temperature of the distillation still from the beginning, and the first distillation of cyclohexene oxide was carried out at a column head temperature of 40 to 60 ° C.
g of cyclohexene oxide (distillation yield 94%) was obtained at an overhead temperature of 64 to 65 ° C. The cyclohexene oxide obtained has a Cpal content of 170
It was 0 ppm, the content of CPCA was 400 ppm, and the purity was 99.4%.

The results of Example 1 and Comparative Examples 1 to 5 are summarized in Table 1 below.

[Table 1]

[0082]

According to the method of the present invention, in a method for producing cyclohexene oxide using cyclohexene as a raw material, by-products of odor-causing substances, CPAL and CPCA, can be prevented as much as possible. Cyclohexene oxide having a high purity can be produced with high yield. Moreover, there is no need to use various antioxidants to prevent or prevent odors, and it is not necessary to repeat purification using a removal aid such as hydroxyamine. It is free from impurities and is extremely advantageous for production on an industrial scale.

[Procedure amendment]

[Submission date] July 18, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

COMPARATIVE EXAMPLE 1 Cyclohexene was used in an amount 1.3 times the molar amount of sodium hypochlorite, and the reaction solution had a hydrogen ion concentration of 6 <p.
A continuous chlorohydrination reaction was carried out using sulfuric acid so that H <7 at a reaction temperature of 50 ° C. and a residence time of 3 hours , and the resulting reaction mixture containing 2-chlorocyclohexanol was withdrawn from the reactor. The reaction mixture was charged with 1.2 times mol of caustic soda with respect to cyclohexene as a starting material, and an epoxidation batch reaction was carried out at a reaction temperature of 50 ° C., and the obtained reaction mixture was separated into oil and water. Was recovered and distilled to obtain cyclohexene oxide.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

[Continuous Reaction of Chlorhydrination]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3h), 282 g / 3 h of sodium hypochlorite aqueous solution (concentration 13.2% by weight, 0.500 mol / 3h ), and for sulfuric acid (20% by weight), the hydrogen ion concentration of the reaction mixture was The pH was controlled so as to be 6 <pH <7, and the rate of withdrawing the reaction solution was such that the amount of the reaction solution was constant. The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used is 6
86 g (1.40 mol).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction contents]

[Continuous Chlorohydrination Reaction]
Cyclohexene, an aqueous solution of sodium hypochlorite and sulfuric acid are simultaneously added dropwise while sufficiently stirring the reaction solution of the oil phase and the aqueous phase equivalent to 00 mol, and the reaction solution is withdrawn while the reaction components are added dropwise, and a continuous reaction is performed for 15 hours. Carried out. The dropping rate was 54.5 g / 3h of cyclohexene (purity 98%,
0.650 mol / 3h) aqueous sodium hypochlorite solution 2
82g / 3h (concentration 13.2% by weight, 0.500 mol /
3h) For sulfuric acid (20% by weight), control was performed so that the hydrogen ion concentration of the reaction mixture was 9 <pH ,
The reaction solution withdrawal speed was set so that the amount of the reaction solution was constant. The reaction temperature was controlled at about 50 ° C. by heating the flask in an oil bath. The total amount of sulfuric acid used is 617 g (1.2
6 mol).

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Yoshihiro Ogita, Inventor Yoshihiro Ogita 2-2-1, Nihonbashi Muromachi, Chuo-ku, Tokyo, Toray Industries, Inc. 1. Toray Industries, Inc. Nagoya Office

Claims (3)

[Claims] 1. A first reaction step in which cyclohexene is reacted with an aqueous hypochlorite solution and an acid to produce 2-chlorocyclohexanol, and an alkali is added to the 2-chlorocyclohexanol obtained in the first reaction step. A second reaction step of acting to produce cyclohexene oxide, the method comprising the steps of:
The reaction in the first reaction step was carried out at a reaction temperature of 30 while maintaining the hydrogen ion concentration of the reaction system within the range of 7 ≦ pH ≦ 9.
A process for producing high-purity cyclohexene oxide, which is carried out at a temperature of from 70 to 70 ° C. 2. The method for producing high-purity cyclohexene oxide according to claim 1, wherein the acid used in the first reaction step is sulfuric acid. 3. The reaction in the first reaction step comprises continuously supplying cyclohexene, an aqueous solution of hypochlorite and an acid to the reactor and continuously producing a reaction mixture containing 2-chlorocyclohexanol produced from the reactor. The method for producing high-purity cyclohexene oxide according to claim 1 or 2, wherein the reaction is a continuous reaction which is selectively extracted.