JP4248693B2 - Process for producing 3-hydroxy-1-cycloalkene - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing 3-hydroxy-1-cycloalkene. More specifically, the present invention relates to a production method for obtaining 3-hydroxy-1-cycloalkene from 1,2-dichlorocycloalkane.
[0002]
[Prior art]
Until now, as a method for producing 3-hydroxy-1-cyclohexene, as a method using cyclohexene as a starting material, a temperature range of 125 to 175 ° C. in an autoclave in US Pat. No. 2,678,338, a pressure of 25 to 75 atm. A range of methods for producing 3-hydroxy-1-cyclohexene from cyclohexene via cyclohexenyl hydroperoxide by oxidation with air or oxygen is disclosed. However, in this method, the conversion rate of cyclohexene is as low as about 40 mol%, and the selectivity for 3-hydroxy-1-cyclohexene is low, such as the production of by-product 1-cyclohexen-3-one in a large amount.
[0003]
In this method, when the conversion rate of cyclohexene is increased, the selectivity of 1-cyclohexen-3-one as a by-product increases. Therefore, the selectivity of 3-hydroxy-1-cyclohexene is suppressed while suppressing the conversion rate of cyclohexene. The book “Oxidation and reduction of organic compounds” edited by Yoshiro Ogata, Nanedo is described. In this method, 3-hydroxy-1-cyclohexene is obtained in high yield from cyclohexenyl hydroperoxide produced by oxidation of cyclohexene by a decomposition reaction of peroxide with an aqueous alkaline solution. In this method, cyclohexenyl hydroperoxide is decomposed with a 1.5% aqueous sodium hydroxide solution, extracted with ether, and distilled to obtain 3-hydroxy-1-cyclohexene in a yield of 65 mol% from cyclohexenyl hydroperoxide. ing.
[0004]
However, these methods cannot raise the conversion rate from cyclohexene, and cyclohexenyl hydroperoxide has a risk of explosion, and there is a problem that it requires careful storage and handling.
On the other hand, it is already known that 3-hydroxy-1-cyclohexene can be easily obtained by hydrolysis in a method using 3-halocyclohexene as a starting material. 3-Chloro-1-cyclohexene is obtained by chlorination of cyclohexene, but it is known that 1,2-dichlorocyclohexane and 4-chlorocyclohexane are formed at the same time.
[0005]
For example, Poutsma et al. Produce 3-chlorocyclohexene, 1,2-dichlorocyclohexane and 4-chlorocyclohexene in a ratio of 1.00: 1.95: 0.60 when chlorinated in cyclohexene at 25 ° C. in the dark. It is reported that. Thus, 1,2-dichlorocyclohexane is the main product of chlorination of cyclohexene (J. Am. Chem. Soc., 87 (10) P. 2161 (1965)). Therefore, when 3-hydroxy-1-cyclohexene is obtained via 3-chloro-1-cyclohexene using cyclohexene as a raw material, the yield of 3-hydroxy-1-cyclohexene from cyclohexene is low.
In addition, 3-bromo-1-cyclohexene can be obtained in a high yield by reacting cyclohexene with N-bromosuccinimide, but at the same time, equimolar succinimide is by-produced and a large amount of waste is generated.
[0006]
By the way, a method for producing 3-hydroxy-1-cyclohexene from 1,2-dihalocyclohexane has not been reported. Further, although the present inventors hydrolyzed 1,2-dichlorocyclohexane under the conditions generally used for the hydrolysis of 3-chlorocyclohexene, the desired 3-hydroxy-1-cyclohexene was not obtained at all. I couldn't.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing 3-hydroxy-1-cyclohexene in a high yield from the main product 1,2-dihalocyclohexane produced by halogenation of cyclohexene.
[0008]
[Means for Solving the Problems]
As a result of intensive studies by the inventor in order to solve the above problems, surprisingly, when 1,2-dihalocycloalkane is subjected to a dehydrohalogenation reaction in the presence of a base using a dipolar aprotic solvent. It has been found that 3-hydroxy-1-cycloalkene can be easily produced in a high yield from 1,2-dihalocycloalkane by adding water to the reaction system and allowing the reaction to proceed under specific reaction temperature conditions. This has led to the present invention.
[0009]
That is, the present invention
(1) When performing dehydrohalogenation reaction of 1,2-dihalocycloalkane using a dipolar aprotic solvent in the presence of a base, water is added to the reaction system and the reaction is performed at 80 ° C. or higher and lower than 160 ° C. A process for producing 3-hydroxy-1-cycloalkene, characterized by reacting at a temperature,
(2) The method for producing 3-hydroxy-1-cycloalkene according to (1) above, wherein the base is at least one selected from the group consisting of alkali metal or alkaline earth metal hydroxides and carbonates. ,
(3) 1,2-Dihalocycloalkane is 1,2-dichlorocyclohexane or 1,2-dibromocyclohexane, wherein 3-hydroxy-1-cyclo of (1) or (2) above Alkene production method,
(4) The method for producing 3-hydroxy-1-cycloalkene according to the above (1), (2) or (3), wherein the dipolar aprotic solvent is an amide compound and / or a sulfoxide compound,
(5) The process for producing 3-hydroxy-1-cycloalkene according to any one of (1) to (4) above, wherein the dipolar aprotic solvent is 1-methyl-2-pyrrolidinone,
(6) The 1,2-dihalocycloalkane is a 1,2-dihalocycloalkane containing a 3-halocycloalkene, and any one of the 3- (1) to (5) above Production method of hydroxy-1-cycloalkene,
(7) Any one of (1) to (6) above, wherein the amount of water added to the reaction system is 0.1 to 1000 times mol with respect to 1,2-dihalocycloalkane A process for producing such 3-hydroxy-1-cycloalkene,
It is.
[0010]
Hereinafter, the present invention will be described in detail.
The 1,2-dihalocycloalkane used in the present invention is preferably a 5-membered to 12-membered dihalocycloalkane, specifically 1,2-dichlorocyclopentane, 1,2-dibromocyclohexane. Pentane, 1,2-diiodocyclopentane, 1,2-dichlorocyclohexane, 1,2-dibromocyclohexane, 1,2-diiodocyclohexane, 1,2-dichlorocycloheptane, 1,2-dibromocycloheptane, 1 , 2-diiodocycloheptane, 1,2-dichlorocyclooctane, 1,2-dibromocyclooctane, 1,2-diiodocyclooctane, 1,2-dichlorocyclononane, 1,2-dibromocyclononane, 1,2-diiodocyclononane, 1,2-dichlorocyclodecane, 1,2-dibromocyclodecane, 1,2- Iodocyclodecane, 1,2-dichlorocycloundecane, 1,2-dibromocycloundecane, 1,2-diiodocycloundecane, 1,2-dichlorocyclododecane, 1,2-dibromocyclododecane, 1,2, -Diiodocyclododecane. Preferred are 1,2-dichlorocyclohexane and 1,2-dibromocyclohexane. 1,2-Dihalocycloalkane has a cis form and a trans form, both of which are used as raw materials.
[0011]
In the present invention, 1,2-dihalocycloalkane may contain 95 mol% or less of 3-halocycloalkene. 3-Halocycloalkene is easily hydrolyzed by water to produce 3-hydroxy-1-cyclohexene. Such a 1,2-dihalocycloalkane can be produced by various methods. For example, as described in the section of the prior art, distillation from a halide mixture obtained by halogenation of a cycloalkene can be performed. It can be obtained through purification.
[0012]
Examples of the dipolar aprotic solvent used in the present invention include ketones, sulfoxides, nitriles, oxyethers, amides, and phosphoric acid triamides. Specific examples include acetone, 3-pentanone, 4-heptanone, 5-nonanone, dimethyl sulfoxide (DMSO), acetonitrile, fumaronitrile, ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DIGLYME), triethylene glycol dimethyl ether (TRIGLYME), tetra Methylene glycol dimethyl ether, dimethylformamide (DMF), dimethylacetamide (DMAC), diethylformamide, diethylacetamide, tetramethylurea, hexamethylphosphoric triamide (HMPA), 1-methyl-2-pyrrolidinone (NMP), 1,3- Examples include dimethyl-2-imidazolidinone. These solvents mix with both water and organic solvents. Of these, amide-based and sulfoxide-based solvents are preferable, and 1-methyl-2-pyrrolidinone is more preferable. 1-methyl-2-pyrrolidinone can be mixed with water and organic substances, particularly 1,2-dihalocycloalkane, in any proportion, and inorganic salts can be dissolved to some extent. Further, even if the temperature is increased to 160 ° C. in the presence of a base, the decomposition rate of 1-methyl-2-pyrrolidinone as a solvent is low, which is preferable. These solvents may be used alone or as a mixed solvent of two or more.
[0013]
Examples of the base used in the present invention include alkali metal, alkaline earth metal, lanthanide metal hydroxide, carbonate, hydrogen carbonate, hydride, alkyl metal, and the like. Specific examples include hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate. And hydrides such as sodium hydride and calcium hydride. Of these, alkali metal hydroxides are preferred, and sodium hydroxide is more preferred. When the reaction is carried out using sodium hydroxide as a base, the yield is higher than other metal salts. These bases may be used alone or in a mixture of two or more.
[0014]
The amount of the base used is preferably 1.5 to 20 times, more preferably 1.8 to 10 times the mole of 1,2-dihalocycloalkane. When the amount of the base used is small, the reaction rate of 1,2-dihalocycloalkane decreases and a satisfactory yield cannot be obtained. Conversely, when the amount of the base is increased, the reaction rate is increased and the conversion rate is also improved. However, even if the amount used is more than 20 times, the effect of accelerating the reaction is small, and most of the base is wasted.
[0015]
In order to further accelerate the reaction, a phase transfer catalyst may be added. Examples of phase transfer catalysts include quaternary ammonium salts such as tricaprylylmethylammonium chloride, phosphonium salts such as hexadecyltri-n-butylfosphonium bromide, and crown ethers such as 18-crown-6-ether. It is done. The phase transfer catalyst is involved only in the reaction rate, and by adding the phase transfer catalyst, the conversion rate of the raw material 1,2-dihalocycloalkane is improved.
[0016]
In the present invention, the amount of water added to the reaction system is preferably 0.1 to 1000 times mol and more preferably 1 to 100 times mol with respect to 1,2-dihalocycloalkane. It is particularly preferable that the amount be 5 to 50 times mol. The reaction solution is preferably separated into two layers of an aqueous layer and an organic layer containing 1,2-dihalocycloalkane at the reaction temperature of the present invention. If the amount of water is less than 0.1 times mol, the reaction rate becomes extremely slow, which is not preferable. On the other hand, if the amount exceeds 1000 times mol, the conversion rate of 1,2-dihalocycloalkane becomes slow and the amount of solvent for the reaction substrate increases, which is wasted.
[0017]
The amount of the dipolar aprotic solvent with respect to 1,2-dihalocycloalkane is not particularly limited, but is preferably 0.5 to 100 times mol. More preferably, it is 1 to 50 times mol. Since 1,2-dihalocycloalkane is almost insoluble in water, increasing the amount of dipolar aprotic solvent mixed in any proportion with both water and 1,2-dihalocycloalkane The conversion rate of dihalocycloalkane is increased. Therefore, it is not preferable that the amount of the dipolar aprotic solvent with respect to 1,2-dihalocycloalkane is less than 0.5 mole because the conversion rate of 1,2-dihalocycloalkane becomes slow. On the other hand, when the amount is 100 times or more, the amount of the solvent is excessively increased.
[0018]
In the reaction of the present invention, 1,2-dihalocycloalkane, water, dipolar aprotic solvent and base may be charged all at once to raise the temperature, or water, dipolar aprotic solvent and base are charged. In this case, 1,2-dihalocycloalkane may be added after raising the reaction temperature. However, when 1,2-dihalocycloalkane is added after raising the reaction temperature, 1,2- Since the reaction between the dihalocycloalkane and the base is an exothermic reaction, it must be added little by little.
[0019]
The reaction temperature in the present invention is in the range of 80 ° C. or higher and lower than 160 ° C., and desirably 120 ° C. or higher and lower than 160 ° C. When the reaction temperature is less than 80 ° C., the raw material 1,2-dihalocycloalkane is hardly converted. As the reaction temperature increases, the conversion rate of 1,2-dihalocycloalkane tends to increase. At a temperature of 160 ° C. or higher, the production ratio of 3-hydroxy-1-cycloalkene is low and 1,3-cycloalkadiene is produced as the main product, which is not preferable.
In the present invention, the reaction pressure is preferably in the range of 1 to 100 atm, more preferably in the range of 2 to 50 atm. Only the vapor pressure of water or the like naturally applied during the reaction may be used, or the pressure in the system may be increased by nitrogen or air.
[0020]
The 3-hydroxy-1-cycloalkene produced by the reaction of the present invention is by-produced by this reaction, and after removing the halide of the precipitated base that has not completely dissolved in the mixed solution by filtration, it is isolated by a purification operation such as distillation. be able to.
For example, 1,3-cyclohexadiene can be obtained by dehydrating the obtained 3-hydroxy-1-cyclohexene using an acid catalyst. Further, (1,3-cyclohexadiene) homopolymer having a high average molecular weight can be obtained by polymerizing 1,3-cyclohexadiene by a known method (for example, WO94 / 28038). Moreover, the copolymer containing a 1, 3- cyclohexadiene unit can be obtained by making it copolymerize with another monomer.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples and the like.
[0022]
[Example 1]
In a 50 ml Hastelloy autoclave, 10.53 g (68.8 mmol) of 1,2-dichlorocyclohexane, 10 g (555.6 mmol) of water, 11.25 g (113.5 mmol) of 1-methyl-2-pyrrolidinone, sodium hydroxide 8 .26 g (203 mmol) was charged, and the temperature of the autoclave was raised to 150 ° C., followed by stirring for 4 hours. After cooling to room temperature, the precipitated sodium chloride was removed. When the filtrate was analyzed by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 100%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 89.1 mol%
1,3-cyclohexadiene 5.1 mol%
Benzene 1.6 mol%
2,2′-dicyclohexenyl ether 2.1 mol%
1-chlorocyclohexene 1.7 mol%
[0023]
[Example 2]
The same operation as in Example 1 was conducted except that sodium hydroxide was replaced with potassium hydroxide. The amount of potassium hydroxide charged is 11.36 g (203 mmol). When the filtrate was analyzed by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 85.6%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 90.2 mol%
1,3-cyclohexadiene 4.9 mol%
Benzene 1.1 mol%
2,2'-dicyclohexenyl ether 1.6 mol%
1-chlorocyclohexene 1.6 mol%
[0024]
[Example 3]
The same operation as in Example 2 was conducted except that the amount of potassium hydroxide charged was 7.71 g (137.6 mmol). When the filtrate was analyzed by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 57.0%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 91.9 mol%
1,3-cyclohexadiene 3.7 mol%
Benzene 1.2 mol%
2,2′-dicyclohexenyl ether 1.5 mol%
1-chlorocyclohexene 1.4 mol%
[0025]
[Example 4]
The same procedure as in Example 3 was performed except that 0.45 g (0.89 mmol) of hexadecyltri-n-butylphosphonium bromide was added as a phase transfer catalyst. When the filtrate was analyzed by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 68.3%. The selectivity of the obtained reaction product is as follows.
3-Hydroxy-1-cyclohexene 93.3 mol%
1,3-cyclohexadiene 3.2 mol%
Benzene 1.3 mol%
2,2′-dicyclohexenyl ether 1.2 mol%
1-chlorocyclohexene 0.3 mol%
[0026]
[Example 5]
In a 50 ml Hastelloy autoclave, 8.57 g (56 mmol) of 1,2-dichlorocyclohexane, 3.27 g (28 mmol) of 3-chlorocyclohexene, 11.25 g (625 mmol) of water, 11.25 g of 1-methyl-2-pyrrolidinone ( 113.5 mmol) and 7.84 g (196 mmol) of sodium hydroxide were added, and the temperature of the autoclave was raised to 150 ° C., followed by stirring for 4 hours. After cooling to room temperature and removing the precipitated sodium chloride by filtration, the filtrate was analyzed by gas chromatography. The conversion of 1,2-dichlorocyclohexane and 3-chlorocyclohexene combined was almost 100%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 90.5 mol%
1,3-cyclohexadiene 5.2 mol%
Benzene 1.3 mol%
2,2′-dicyclohexenyl ether 1.5 mol%
1-chlorocyclohexene 1.5 mol%
[0027]
[Example 6]
In a 50 ml Hastelloy autoclave, 12.39 g (68.8 mmol) of 1,2-dichlorocyclooctane, 10 g (555.6 mmol) of water, 11.25 g (113.5 mmol) of 1-methyl-2-pyrrolidinone, sodium hydroxide 8 .26 g (203 mmol) was charged, and the temperature of the autoclave was raised to 150 ° C., followed by stirring for 4 hours. After cooling to room temperature and removing the precipitated sodium chloride, the filtrate was analyzed by gas chromatography. The conversion of 1,2-dichlorocyclooctane was 100%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclooctene 90.0 mol%
1,3-cyclooctadiene 6.5 mol%
1-chlorocyclooctene 3.5 mol%
[0028]
[Comparative Example 1]
A 50 ml Hastelloy autoclave was charged with 10.53 g (68.8 mmol) of 1,2-dichlorocyclohexane, 21.25 g (1181 mmol) of water and 8.26 g (203 mmol) of sodium hydroxide, and the temperature of the autoclave was raised to 150 ° C. After that, it was stirred for 4 hours. Although it cooled to room temperature, the salt did not precipitate and it was isolate | separated into two layers. When the reaction solution was analyzed by gas chromatography, 1,2-dichlorocyclohexane was hardly converted.
[0029]
[Comparative Example 2]
The same procedure as in Example 4 was conducted except that 11.25 g (127.7 mmol) of 1,4-dioxane was used instead of 1-methyl-2-pyrrolidinone. Although it cooled to room temperature, the salt did not precipitate and it was isolate | separated into two layers. When the reaction solution was analyzed by gas chromatography, 1,2-dichlorocyclohexane was hardly converted.
[0030]
[Comparative Example 3]
50 ml of Hastelloy autoclave was charged with 11.25 g (625 mmol) of water, 11.25 g (113.5 mmol) of 1-methyl-2-pyrrolidinone and 5.6 g (140 mmol) of sodium hydroxide, and the autoclave temperature was increased to 180 ° C. After raising, 10.53 g (68.8 mmol) of 1,2-dichlorocyclohexane was added dropwise at a rate of 1 ml / min with a pump and stirred for 4 hours. After cooling to room temperature, the precipitated sodium chloride was removed. When the filtrate was analyzed by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 100%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 3.0 mol%
1,3-cyclohexadiene 89.5 mol%
1,4-cyclohexadiene 0.2 mol%
Cyclohexene 0.8mol%
Benzene 1.6 mol%
2,2′-dicyclohexenyl ether 2.1 mol%
1-chlorocyclohexene 2.8 mol%
[0031]
[Comparative Example 4]
A 100 ml three-necked flask equipped with a Dimroth reflux tube was charged with 6.89 g (45 mmol) of 1,2-dichlorocyclohexane, 15 g (151.3 mmol) of 1-methyl-2-pyrrolidinone, and 3.6 g (90 mmol) of sodium hydroxide. And reacted at 150 ° C. for 4 hours. After cooling to room temperature and measuring the reaction filtrate by gas chromatography, the conversion of 1,2-dichlorocyclohexane was 10%. The selectivity of the obtained reaction product is as follows.
3-hydroxy-1-cyclohexene 10.1 mol%
1,3-cyclohexadiene 53.8 mol%
1,4-cyclohexadiene 10.9 mol%
Benzene 1.0 mol%
1-chlorocyclohexene 23.4 mol%
[0032]
【The invention's effect】
It has become possible to provide a method capable of easily producing 3-hydroxy-1-cycloalkene from 1,2-dihalocycloalkane in high yield.

Claims (7)

When performing dehydrohalogenation reaction of 1,2-dihalocycloalkane in the presence of a base using a dipolar aprotic solvent, adding water to the reaction system and reacting at a reaction temperature of 80 ° C. or higher and lower than 160 ° C. A process for producing 3-hydroxy-1-cycloalkene, characterized in that The process for producing 3-hydroxy-1-cycloalkene according to claim 1, wherein the base is at least one selected from the group consisting of hydroxides and carbonates of alkali metals or alkaline earth metals. The method for producing 3-hydroxy-1-cycloalkene according to claim 1 or 2, wherein the 1,2-dihalocycloalkane is 1,2-dichlorocyclohexane or 1,2-dibromocyclohexane. The method for producing 3-hydroxy-1-cycloalkene according to claim 1, 2 or 3, wherein the dipolar aprotic solvent is an amide compound and / or a sulfoxide compound. The method for producing 3-hydroxy-1-cycloalkene according to any one of claims 1 to 4, wherein the dipolar aprotic solvent is 1-methyl-2-pyrrolidinone. The 3-hydroxy-1- according to any one of claims 1 to 5, wherein the 1,2-dihalocycloalkane is a 1,2-dihalocycloalkane containing a 3-halocycloalkene. A method for producing cycloalkene. The amount of water added to the reaction system is 0.1 to 1000 times mol with respect to 1,2-dihalocycloalkane, according to any one of claims 1 to 6. Process for producing hydroxy-1-cycloalkene.