JP6278846B2 - Method for producing 7-octene-1,2,3-triol - Google Patents

Description

  The present invention relates to a process for producing 7-octene-1,2,3-triol. Since 7-octene-1,2,3-triol obtained by the method of the present invention has a carbon-carbon double bond at the molecular end and a plurality of hydroxyl groups in the molecule, for example, as a polyolefin modifier, etc. Useful.

  As a method for producing 7-octene-1,2,3-triol, 4-pentenylmagnesium bromide is allowed to act on glyceraldehyde in which two hydroxyl groups are acetal protected, followed by deprotection of the acetal group with 20% acetic acid. The method (refer nonpatent literature 1) which refine | purifies a mixture by silica gel column chromatography is mentioned.

Agricultural Biological Chemistry, 1985, 49, 3, pp. 643-649

  The method described in Non-Patent Document 1 has a high reactivity of magnesium metal used in the preparation of 4-pentenylmagnesium bromide, which is a Grignard reagent, and may ignite in air. There is concern about heat generation during the treatment and explosion due to generation of hydrogen, and it is necessary to pay the latest attention to safety throughout the reaction. Further, purification by silica gel column chromatography takes time, and it is difficult to say that it is an industrial production method because it is difficult to scale up from the viewpoint of productivity.

  An object of the present invention is to provide a method capable of industrially easily producing 7-octene-1,2,3-triol in good yield and high purity.

According to the present invention, the above object is achieved by providing the following [1] to [4].
[1] Step 1 of obtaining 2,3-epoxy-7-octen-1-ol by epoxidizing the carbon-carbon double bond at the 2-position to 3-position of 2,7-octadien-1-ol; A step 2 of hydrating the 2,3-epoxy-7-octen-1-ol obtained in step 1;
A process for producing 7-octene-1,2,3-triol, comprising:
[2] 7-octene-1,2,3-triol of [1], further comprising step 3 of further refining the 7-octene-1,2,3-triol obtained in step 2 by recrystallization. A method for producing 3-triol.
[3] React with hydrogen peroxide in the presence of a tungstic acid compound and a quaternary ammonium salt to epoxidize the carbon-carbon double bond at positions 2 and 3 of 2,7-octadien-1-ol. Process for producing 7-octene-1,2,3-triol according to [1] or [2], wherein Step 1 is performed.
[4] 7-octene-1, 2 according to any one of [1] to [3], wherein step 2 is performed by heating 2,3-epoxy-7-octen-1-ol in water. , 3-Triol production method.

According to the method of the present invention, 7-octene-1,2,3-triol can be easily produced industrially in good yield.
Furthermore, high-purity 7-octene-1,2,3-triol can be obtained by a simple operation without causing undesired side reactions such as isomerization and polymerization by heating for a long time such as distillation.

  Hereinafter, the present invention will be described in detail. First, step 1 for obtaining 2,3-epoxy-7-octen-1-ol by epoxidizing the carbon-carbon double bond at the 2-position to 3-position of 2,7-octadien-1-ol will be described. .

  The product of Step 1, 2,3-epoxy-7-octen-1-ol, is 2,7-octadien-1-ol, for example, preferably in the presence of a tungstate compound and a quaternary ammonium salt. It can manufacture by performing the process 1 which makes it react with hydrogen peroxide and epoxidizes the carbon-carbon double bond of 2-position-3 position.

  Examples of the tungstic acid compound include alkali metal salts of tungstic acid such as sodium tungstate and potassium tungstate; inorganic salts of tungstic acid such as ammonium tungstate; and tungsten-containing heteropolyacids such as phosphotungstic acid and silicotungstic acid. It is preferable to use alkali metal salts of tungstic acid such as sodium tungstate and potassium tungstate. As the tungstic acid compound, a commercially available one can be used as it is. Although there is no restriction | limiting in particular in the usage-amount of a tungstic acid compound, Usually, it is preferable that it is the range of 0.001-100 mol% with respect to 1 mol of 2,7- octadien-1-ol, and operativity and economical efficiency are preferable. From a viewpoint, the range of 0.01-50 mol% is more preferable, and the range of 0.1-10 mol% is further more preferable.

Examples of the quaternary ammonium salt include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tetraoctylammonium ion, dimethyldiethylammonium ion. Ion, dimethyldibutylammonium ion, dimethyldioctylammonium ion, dimethyldibenzylammonium ion, diethyldipropylammonium ion, diethyldibutylammonium ion, diethyldibenzylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylbutylammonium ion Trimethylbenzylammonium ion, triethylmethylammonium ion, triethylpropylammonium ion, triethylbutylammonium ion, triethylbenzylammonium ion, tributylmethylammonium ion, tributylethylammonium ion, tributyloctylammonium ion, tributylbenzylammonium ion, tripentylmethylammonium ion , Tripentylethylammonium ion, tripentylpropylammonium ion, tripentylbenzylammonium ion, trihexylmethylammonium ion, trihexylethylammonium ion, trihexylpropylammonium ion, trihexylbenzylammonium ion, triheptylmethyl Ammonium ion, triheptylethylammonium ion, triheptylpropylammonium ion, triheptylbenzylammonium ion, trioctylmethylammonium ion, trioctylethylammonium ion, trioctylpropylammonium ion, trioctylbenzylammonium ion, methylpyridinium ion, ethylpyridinium ion Ammonium cations such as ions, butylpyridinium ions, cetylpyridinium ions, chloride ions (Cl ⁻ ), bromide ions (Br ⁻ ), iodide ions (I ⁻ ), hydrogen sulfate ions (HSO ₄ ⁻ ), trifluoromethanesulfone acid ion _(CF 3 SO ₃ ^-), trifluoromethane sulfonate ion _{(CF 3 C 6 H 4 SO} 3 -), hydroxide Ion (OH ^-) salts formed from the anion of such. These quaternary ammonium salts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular in the usage-amount of a quaternary ammonium salt, Usually, it is preferable that it is the range of 0.3-10 mol times with respect to 1 mol of tungstic acid compounds, and from a viewpoint of economical efficiency, operativity, and reaction rate. Is more preferably in the range of 0.5 to 5 mol times, and still more preferably in the range of 0.5 to 3 mol times.

  As the hydrogen peroxide, an aqueous solution of 10 to 60% by mass which is usually commercially available can be used as it is. The amount of hydrogen peroxide used is usually preferably in the range of 0.1 to 10 moles per mole of 2,7-octadien-1-ol, and 0.5 to 2 from the viewpoint of reaction efficiency. The range of molar times is more preferable, and the range of 0.8 to 1.5 molar times is more preferable.

  Step 1 can be performed in the presence or absence of a solvent. Solvents that can be used are not particularly limited as long as they do not adversely affect the reaction in Step 1. For example, water; saturated hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane; toluene, Examples include aromatic hydrocarbons such as xylene and mesitylene. When a solvent is used, the amount used is not particularly limited, but it is preferably in the range of 0.01 to 100 times by mass with respect to 2,7-octadien-1-ol, and the operability, volumetric efficiency and economy are preferred. From the viewpoint of property, a range of 0.01 to 10 times by mass is more preferable, and a range of 0.05 to 5 times by mass is more preferable.

  In the reaction of Step 1, an acid component can be further added to the reaction system for the purpose of adjusting the pH of the reaction solution from the viewpoint of maintaining the catalytically active species that cause the epoxidation reaction to proceed in the reaction system. Examples of the acid component include phosphoric acid, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium hydrogen phosphate, sulfuric acid, sodium hydrogen sulfate, and the like. Can be mentioned. These acid components may be used alone or in combination of two or more. When the acid component is further added, the amount is not particularly limited, but from the viewpoint of stability of the product 2,3-epoxy-7-octen-1-ol in the reaction system, It is preferable to use an amount capable of adjusting the pH of 3 to 6 in a range of 0.2 to 10 mol times with respect to 1 mol of tungstic acid compound.

  Step 1 may be performed in the air, but is preferably performed in an inert gas atmosphere such as nitrogen or argon from the viewpoint of safety. The reaction temperature is preferably in the range of −30 ° C. to 200 ° C., more preferably in the range of 30 ° C. to 100 ° C., and in the range of 40 ° C. to 80 ° C. from the viewpoints of safety, hydrogen peroxide stability, and reaction rate. Further preferred.

  Step 1 can be carried out either batchwise or continuously. For example, 2,7-octadien-1-ol, a quaternary ammonium salt and a solvent as necessary are mixed, and the tungstic acid compound is added to this solution as it is or dissolved in a solvent such as water, followed by a predetermined temperature. Then, hydrogen peroxide is preferably added as an aqueous solution and stirred. When an acid component is added to adjust the pH of the reaction solution, the acid component may be added in advance before adding hydrogen peroxide, or after adding hydrogen peroxide, the pH of the reaction solution is adjusted. You may add suitably, observing.

  The 2,3-epoxy-7-octen-1-ol obtained in Step 1 can be isolated and purified by a method usually performed in the isolation and purification of organic compounds. For example, after completion of the reaction, a reducing agent such as sodium sulfite is added to the reaction solution, or the reaction solution is washed with water to remove residual peroxide, and if necessary, concentrated, and then purified by distillation or the like.

  Next, step 2 in which the 2,3-epoxy-7-octen-1-ol obtained in step 1 is hydrated will be described. By this step 2, 7-octene-1,2,3-triol is obtained. Preferably, step 2 is performed by heating 2,3-epoxy-7-octen-1-ol in water. This will be described in detail below.

  Step 2 may be performed in the air, but is preferably performed in an inert gas atmosphere such as nitrogen or argon from the viewpoint of safety. There is no restriction | limiting in particular in reaction pressure, Any of pressurization, atmospheric pressure, and pressure reduction may be sufficient, and when it carries out under atmospheric pressure, an apparatus becomes simple and preferable.

  The heating temperature in Step 2 is preferably in the range of 80 ° C to 120 ° C, more preferably in the range of 90 ° C to 110 ° C, and further preferably in the range of 90 ° C to 100 ° C. When the temperature is lower than 80 ° C., the progress of the reaction in Step 2 tends to be extremely slow. When the temperature is higher than 120 ° C., 2,3-epoxy-7-octene-1-is a raw material existing in the reaction system of Step 2. Various compounds such as all and 7-octene-1,2,3-triol, which is the target product, tend to have a high boiling point.

  The amount of water used in Step 2 is not particularly limited as long as it is 1 equivalent or more with respect to 2,3-epoxy-7-octen-1-ol, and other solvents may coexist. However, in consideration of the efficiency, productivity and selectivity of the reaction in Step 2, it is preferable to perform heating only in water without coexisting other solvents, that is, in water. , 3-epoxy-7-octen-1-ol is preferably in the range of 1-100 equivalents, more preferably in the range of 5-50 equivalents.

  Step 2 in the production method of the present invention is an acidic substance or a basic substance from the viewpoint of easily obtaining 7-octene-1,2,3-triol, which is the target product of the method of the present invention, in Step 3 described later. It is preferable to carry out without coexisting reaction accelerators such as. However, when 2,3-epoxy-7-octen-1-ol is subjected to a hydration reaction, the reaction in step 2 is carried out in the presence of these reaction accelerators if necessary, and the recrystallization method in step 3 to be described later It may be removed by washing or the like before performing.

  By concentrating the reaction solution after completion of the reaction in Step 2, crude 7-octene-1,2,3-triol can be obtained easily and safely as compared with the conventional method. As a result of detailed investigations by the present inventors, when purifying by a heating operation such as distillation for a long time to obtain 7-octene-1,2,3-triol having a high purity, isomerization or polymerization is performed in such operation. It was found that undesired side reactions such as 7-octene-1,2,3-triol did not increase and the purification yield also decreased. As a result of further examination from the viewpoint of avoiding such a problem, it was found that the crude 7-octene-1,2,3-triol obtained in Step 2 as Step 3 could be purified by a recrystallization method. . Hereinafter, step 3 will be described.

  Examples of the solvent that can be used in the recrystallization method in Step 3 include various polar solvents and nonpolar solvents. Examples of polar solvents include alcohols such as methanol, ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; esters such as ethyl acetate; acetonitrile and benzonitrile. Nitriles such as dimethyl sulfoxide; sulfoxides such as dimethyl sulfoxide; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Nonpolar solvents include, for example, aliphatic hydrocarbons such as hexane, petroleum ether, decalin, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride. Can be mentioned.

  Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, it is preferable that it is 0.5-30 mass times with respect to the crude 7-octene-1,2,3-triol obtained at the process 2, and in recrystallization From the viewpoint of recovery yield and volumetric efficiency, it is more preferably 1 to 5 times by mass. The method for recrystallizing 7-octene-1,2,3-triol is not particularly limited, but a solvent having a large solubility difference depending on temperature, for example, alcohol such as methanol, ethanol, isopropanol; acetone, methyl ethyl ketone, methyl isobutyl ketone , Ketones such as cyclohexanone; ethers such as diethyl ether, tetrahydrofuran, dioxane and diglyme; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide; N, N-dimethylformamide and N, N-dimethyl Recrystallization using amides such as acetamide and N-methylpyrrolidone; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride alone, as well as 7-octene-1,2,3 Triol is a solvent having high solubility of 7-octene-1,2,3-triol (good solvent: alcohol such as methanol, ethanol and isopropanol; ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, tetrahydrofuran, Ethers such as dioxane and diglyme; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; A halogenated hydrocarbon such as methylene, chloroform, carbon tetrachloride, etc.) at 10 to 120 ° C., preferably 25 to 70 ° C. to obtain a solution, and 7-octene-1,2 is added to the solution. A solvent having a low solubility of 3-triol (poor solvent: aliphatic hydrocarbon such as hexane, petroleum ether, decalin, cyclohexane, etc .; aromatic hydrocarbon such as benzene, toluene, xylene, etc.) is usually preferably 10 to 120 ° C., More preferably, after adding at 25 to 70 ° C., precipitation is performed by cooling to −10 to 30 ° C., preferably 0 to 25 ° C., to obtain high-purity 7-octene-1,2,3-triol. This is preferable. In addition, there is no restriction | limiting in particular in the combination of the solvent in the case of performing the recrystallization method of the process 3 combining the said good solvent and a poor solvent, and also about the usage-amount of each solvent, 7-octene-1,2,3. -It can set suitably according to the desired purity of triol. Furthermore, the recrystallization method in step 3 may be performed once or a plurality of times.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited at all by these Examples. In addition, the gas chromatography analysis conditions in an Example etc. are as follows.
Analytical instrument: GC14A (manufactured by Shimadzu Corporation)
Detection equipment: FID (hydrogen flame ionization detector)
Column used: CBP-20 (manufactured by Shimadzu LLC)
Analysis conditions: Injection Temp. 250 ° C
Detection Temp. 250 ° C
Temperature rising condition: 120 ° C (2 minutes) → (temperature rising at 10 ° C / min) → 250 ° C

Example 1
Step 1: In a three-necked flask with a volume of 5 L, under a nitrogen atmosphere, 1199 g (9.50 mol) of 2,7-octadien-1-ol, 38.5 g (0.095 mol) of trioctylmethylammonium chloride, sodium tungstate 2 31.4 g (0.095 mol) of hydrate, 18.7 g (0.191 mol) of phosphoric acid, and 950 g of water were charged. While stirring this mixture, the internal temperature was raised to 40 ° C., and 30% by mass. 11.10 g (9.80 mol) of an aqueous hydrogen peroxide solution was added dropwise over 2.5 hours while maintaining the temperature of the reaction solution at around 40 ° C., and the mixture was further stirred at 40 ° C. for 2 hours. The reaction solution was cooled to room temperature and the aqueous layer was separated, and then the organic layer was washed successively with 200 ml of 2.5M aqueous sodium sulfite solution and water (200 ml × 2). When this organic layer was analyzed by gas chromatography (GC), the conversion of 2,7-octadien-1-ol was 99%, and the selectivity of 2,3-epoxy-7-octen-1-ol was 90%. there were. This organic layer was distilled under reduced pressure, and a fraction of 101-113 ° C. and 440-330 Pa (3.3-2.5 mmHg) was collected to obtain 2,3-epoxy-7- having a purity of 97% (based on GC area ratio). 1037 g (7.29 mol, yield 77%) of octen-1-ol was obtained.
Step 2: A 5-liter three-necked flask was charged with 2851 ml of water under a nitrogen atmosphere and 631 g (1.55 mol / l) of 2,3-epoxy-7-octen-1-ol obtained in Step 1 above. The mixture was stirred at 100 ° C. for 16 hours under atmospheric pressure. The resulting reaction solution was concentrated under reduced pressure to obtain 635 g of crude 7-octene-1,2,3-triol having a purity of 96% (based on GC area ratio). The conversion of 2,3-epoxy-7-octen-1-ol was 100%, and the selectivity for 7-octene-1,2,3-triol was 85%.
Step 3: 283 g of the crude 7-octene-1,2,3-triol obtained in Step 2 was dissolved in 143 g of tetrahydrofuran as a good solvent at 45 ° C., and 73 g of hexane was added to the resulting solution at 45 ° C. By cooling to 25 ° C. and recrystallization, 257 g of 7-octene-1,2,3-triol having a purity of 98% (GC area ratio standard) could be obtained (recovery rate 91%).

Example 2
In Step 3 of Example 1, 9.7 g of the crude 7-octene-1,2,3-triol obtained in Step 2 was dissolved in 2.8 g of methyl isobutyl ketone at 60 ° C., and the resulting solution was added at 25 ° C. 6.8 g of 7-octene-1,2,3-triol having a purity of 98% (GC area ratio standard) could be obtained (recovery rate 70%).

Comparative Example 1
In Step 3 of Example 1, 154 g of the crude 7-octene-1,2,3-triol obtained in Step 2 was distilled under reduced pressure at 172-184 ° C. and 400 Pa (3.0 mmHg). The product became 135 g of 7-octene-1,2,3-triol having a purity of 91% (based on GC area ratio), and the purity rather decreased.

  According to the method of the present invention, 7-octene-1,2,3-triol useful as a polyolefin modifier or the like can be easily produced industrially with good yield and high purity.

Claims (3)

Step 1 of obtaining 2,3-epoxy-7-octen-1-ol by epoxidizing the carbon-carbon double bond at the 2-position to 3-position of 2,7-octadien-1-ol ;
Hydrating the 2,3-epoxy-7-octen-1-ol obtained in step 1; and
Step 3 for further purifying the 7-octene-1,2,3-triol obtained in Step 2 by a recrystallization method;
And having a 7-octene-1,2,3 method for producing a triol. Reacting with hydrogen peroxide in the presence of a tungstic acid compound and a quaternary ammonium salt to epoxidize the carbon-carbon double bond at positions 2 and 3 of 2,7-octadien-1-ol; The method for producing 7-octene-1,2,3-triol according to claim 1, wherein the method is performed. The production of 7-octene-1,2,3-triol according to claim 1 or 2 , wherein step 2 is carried out by heating 2,3-epoxy-7-octen-1-ol in water. Method.