JPH0499752A - Production of omega-hydroxy fatty acid ester - Google Patents

Abstract

PURPOSE:To produce the title compound useful as a raw material for macrocyclic lactone, polymer raw material, etc., in high selectivity and in high yield by bringing a readily obtainable long-chain diacid monoester as a raw material into contact with hydrogen in the presence of water and a solid catalyst under a mild reaction condition. CONSTITUTION:A long-chain diacid monoester (e.g. pentadecane diacid monomethyl ester) shown by formula I (R is alkyl; n is 8-16C integer) is brought into contact with hydrogen in the presence of water and a solid catalyst (especially ruthenium-based and/or rhenium-based catalyst, specially preferably ruthenium, tin or rhenium) to advantageously give an omega-hydroxy fatty acid ester (e.g. omega-hydroxypentadecanoic acid methyl ester) shown by formula II. The starting compound shown by formula I is readily obtained by esterifying an alkane diacid with an alcohol, then converting into a barium mono salt and replacing the salt with an acid. The omega-hydroxy fatty acid ester is useful as a starting raw material for drugs and perfume and a raw material for polymers.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is useful as a raw material for the synthesis of macrocyclic lactones used as raw materials for pharmaceuticals or fragrances, etc., and has also been widely used as a raw material for polymers. The present invention relates to a method for producing hydroxy fatty acid ester.

[Prior Art] A conventional method for producing ω-hydroxy fatty acids is a method in which ω-hydroxy or ω-acyloxyalkyl-γ-butyrolactone is subjected to a catalytic reaction in the presence of a hydrogen cracking catalyst in the coexistence of hydrogen gas. (Special Publication No. 3776), or 13-oxa-bicyclo[10,4,0
Converting 1-hexadecene [1(12)] to a lactone,
A method of opening the lactone ring by the Wolffukisiner method or the Huang Minlong method (Tokuko Showel
-21474) etc. have been proposed.

Since all of the above methods use complex compounds as starting materials, they have had the problem of using expensive raw materials, which in turn increases production costs.

In addition, a method has been proposed in which dicarboxylic acid monoalkyl ester is brought into contact with hydrogen in the presence of a copper-chromium oxide catalyst (Japanese Patent Application Laid-open No. 63301845) or a cobalt catalyst (Japanese Patent Application Laid-open No. 63301845). There is.

However, these methods require a hydrogen pressure of 150 kg/e1
Since the reaction requires relatively high pressure of 2 or more, it requires equipment that can withstand the high pressure, and it is economical because it requires a large amount of catalyst of 5 to 10% by weight as a metal oxide. was disadvantageous.

Furthermore, although a reaction solvent is used in the method of JP-A No. 63-301843, the purpose of its use is to carry out the reaction smoothly, and organic solvents inert to the reaction, such as ether, aliphatic hydrocarbon, Cycloaliphatic hydrocarbons, aromatic hydrocarbons or mixtures thereof were mentioned.

[Problems to be Solved by the Invention] The present invention solves the drawbacks of the above-mentioned methods, and an object of the present invention is to provide a method useful as a raw material for the synthesis of macrocyclic lactones used as raw materials for pharmaceuticals or fragrances, etc. The object of the present invention is to provide a method for advantageously producing ω-hydroxy fatty acid esters, which have a wide range of uses as polymer raw materials.

[Means for Solving the Problems] As a result of intensive studies to solve the problems, the present inventor has found that
We have discovered that ω-hydroxy fatty acid esters can be produced with high selectivity and yield under mild reaction conditions in the presence of a specific catalyst.

That is, the present invention relates to a long chain diacid monoester represented by the following general formula (1)% (1) (wherein R represents an alkyl group and n represents an integer of 8 to 16). Under the coexistence of
The following general formula (II) R-〇-C+Cl12+, CHzO, which is characterized by contacting with hydrogen using a solid catalyst
This is a method for producing an ω-hydroxy fatty acid ester represented by H(II) (formula is R, n is the same as in formula (1)).

The raw material long chain diacid monoester used in the present invention is -
Any compound represented by Wuwei (1) may be used.

This monoester can be obtained in a package by esterifying an alkanniic acid with an alcohol, converting it into a monosalt of barium using, for example, barium hydroxide, and then replacing the barium with an acid.

It is preferable to use a lower alcohol having 1 to 4 carbon atoms as the alcohol for the esterification because the esterified product can be easily produced.

Note that alkaniic acid is produced relatively inexpensively by oxidizing an alkane having a corresponding number of carbon atoms in the presence of microorganisms.

The solid catalyst used in the present invention may be any catalyst used for hydrogenation reduction of carboxylic acids and/or esters, such as copper-chromium oxide catalyst, zinc-chromium oxide catalyst, platinum catalyst, etc. Ruthenium-based or rhenium-based catalysts are most preferably used.

The rhenium-based catalyst refers to a rhenium metal fit body, its compound, or a mixed catalyst of this and other metal catalysts such as tin, ruthenium, etc., but the most preferably used in the present invention are rhenium, tin, etc. It is a rhenium-based catalyst containing

Moreover, the above-mentioned ruthenium-based catalyst used in the present invention is
It refers to a catalyst containing ruthenium alone, a compound thereof, or a mixed catalyst of ruthenium and other metal catalysts such as tin, rhenium, etc., but the most preferably used in the present invention is a ruthenium-based catalyst containing ruthenium or tin.

The above rhenium-based and ruthenium-based catalysts may be prepared by conventional methods such as impregnation method, precipitation method, and conventional sol-gel method using colloidal sol as a starting material. or modified sol-gel method).

In preparing the catalyst using the impregnation method, any ruthenium, rhenium, or tin compound can be used as long as it is easily soluble in water and an organic solvent. Examples of the ruthenium compound include ruthenium trichloride hydrate, ruthenium trisacetylacetonate, ruthenium tetroxide, ruthenium carbonyl, and ruthenium ammonium chloride. In addition, examples of rhenium compounds include:
Examples include rhenium chloride, rhenium oxychloride, rhenium bromide, rhenium oxybromide, nyrhenium heptoxide, and ammonium perrhenate.

Examples of tin compounds include stannous chloride,
Examples include tin chloride, tin bromide, organic acids such as tin acetate, and tin alkoxides such as tin tetraethoxide. It is not limited to the exemplified compounds.

In addition, as a carrier, diatomaceous earth, alumina, silica gel,
Any known material such as zirconia or titania can be used.

In the preparation of catalysts using the chemical mixing method, ruthenium compounds, rhenium compounds, and tin compounds are dissolved in organic solvents and reacted with other substances such as aluminum compounds, silicon compounds, titanium compounds, zirconium compounds, or niobium compounds to form organic solvents. Any material that dissolves can be used. Examples of ruthenium compounds include ruthenium trichloride hydrate, ruthenium trisacetylacetonate, ruthenium tetroxide, and ruthenium carbonyl. Examples of rhenium compounds include rhenium chloride, rhenium oxychloride, rhenium bromide, and ruthenium oxychloride. Examples of tin compounds include tin chloride, tin bromide, organic acids such as tin acetate, and tin alkoxides such as tin tetraethoxide. However, the compound is not limited to these exemplified compounds as long as it is soluble in an organic solvent.

In the case of the ruthenium- or rhenium- and tin-containing solid catalyst most preferably used in the present invention, the amounts of the ruthenium- or rhenium compound and the tin compound used for catalyst preparation are as follows:
There are no particular regulations.

However, if the amount used is too small, the content of ruthenium, rhenium, or tin in the final solid catalyst will decrease, reducing the activity of the catalyst, and if it is too large, the catalyst will become too expensive to be practical. In the final catalyst, the content of ruthenium or rhenium and tin is in the range of 0.5vt% to 30vt% for ruthenium or rhenium, and 0.5vt% to yowt% for tin, when each is considered as a metal. It is preferable to set the usage amount to . Regarding the relative content of ruthenium or rhenium and tin, the atomic ratio of tin/ruthenium or rhenium ranges from 0.01 to 0.
．． It is preferable to set the value between 03 and 3.

The catalyst is subjected to operations such as calcination and reduction as necessary.
use.

The reason why the coexistence of water in the present invention brings about high selectivity and high yield of ω-hydroxy fatty acid ester is still not fully understood, but one of the reasons is that the ω- It is thought that dehydration condensation between the hydroxy fatty acid ester and the unreacted raw material long-chain diacid monoester is prevented. The amount of water added is not particularly specified, but if the amount added is too small, the effect will be small, and if it is too large, the amount of water in the reaction system will be affected depending on the vapor pressure of water at the reaction temperature when carrying out the present invention. Since this increases the total pressure and unnecessarily increases the cost of the equipment, it is not practical, so the amount is in the range of 0.01 to 50 times the mole of the long-chain diacid monoester used as the raw material, more specifically, 0.
．． It is preferable to add it in an amount of 1 to 10 times the mole.

In the present invention, any of the suspended bed, fluidized bed, and fixed bed methods can be adopted as appropriate, and the catalyst shape in that case is molded into a mold suitable for each reaction method.

The hydrogenation reduction method to ω-hydroxy fatty acid ester is
The reaction is carried out under the following reaction conditions. The reaction temperature is 150-3
The temperature is preferably 50°C, particularly preferably 200 to 300°C.
It is ℃. Reaction pressure is hydrogen pressure 10-300kg/cm
2 is preferred, and particularly preferred is 20 to 150 kg/
cm'. Although the reduction reaction is not limited to the above condition range, if the hydrogen pressure is 10 kg/cm or less and the temperature is 150°C or less, the reduction reaction rate will be slow.
This is practically undesirable because the reaction time is prolonged. It is better to have a higher reaction temperature and hydrogen pressure because the reaction rate will increase.
If the reaction temperature exceeds 350°C, the raw materials and products will decompose and the yield will decrease, which is not preferable.

Further, if the hydrogen pressure is set to 300 kg/c2 or higher, no significant improvement in the reaction rate can be expected, and higher hydrogen pressures are not preferred from the economical and safety standpoints.

Such reaction conditions are appropriately selected depending on the type of long-chain diacid monoester used as a raw material, the activity of the catalyst used, the amount of water added, the solvent, etc.

Although the method of the present invention can also be carried out without using a solvent,
Any suitable solvent may be used. The solvent used is not particularly limited as long as it is inert to the reaction, and organic solvents used in reduction reactions, such as ethers, aliphatic hydrocarbons, alicyclic hydrocarbons, or mixtures thereof can be used.

The concentration of the raw material in the solvent is 1 to 80 wt 9o, preferably 5 to 50 vt%.

The reaction time varies depending on the above reaction conditions.
This can be done in about 0 hours.

U Examples] The method of the present invention will be specifically explained below using Examples. The product in this reaction was identified and quantified by gas chromatography, but since polyester was produced as a by-product in the reaction product, this was hydrolyzed by a conventional method to form a tetramethylsilane rust conductor. Analysis was carried out.

Example 1 2.0 g of trisacetylacetonateruthenium complex was suspended in an aqueous ethanol solution of 151, 27 g of concentrated nitric acid was added thereto, and the mixture was stirred at 80 to 90°C for 1 hour. Next, 15 g of concentrated nitric acid was added to the solution, and the complex adhering to the vessel wall was washed into the solution with as little acetic acid as possible.
It was heated at 100°C for 2 hours. During this time, nitrogen oxide gas was evolved and the suspension turned into a clear red solution. After drying this solution, 74.17 g of hexylene glycol and 63.29 g of aluminum isopropoxide were added to the solution, and the mixture was stirred at 100° C. for 2 hours. Furthermore, add 1. to this solution.
After adding 50 g of tetraethoxytin and stirring at the same temperature for 4 hours, 22.31 g of water was added. The resulting gel was warmed and aged at the same temperature for 2 hours, and dried at 160° C. under reduced pressure.

Dry gel 6, Og was placed in a quartz tube, fired at 400°C for 2 hours using an rA type annular furnace, cooled to room temperature, and then heated at 401)°C for 4 hours without flowing hydrogen. ]
was activated.

Next, this was mixed with 50.0 g of pentadecanedioic acid monomethyl ester and 100.0 g of pentadecanedioic acid monomethyl ester. og of decahydronaphthalene and 10
．． The mixture was charged into an autoclave with an internal volume of 5,001 cm along with 0 g of water, and after the inside of the container was sufficiently replaced with hydrogen gas, heating was started. When the temperature reached 250°C, the internal pressure of the container was increased to HJ/cm' with hydrogen gas to stop the reaction. It started. During the reaction, stirring was performed using an electromagnetic induction rotation system at a rate of 1500 rotations/minute.

After sampling and starting the reaction, 85.
At 0 hours, the supply of hydrogen gas was stopped, the reaction was cooled, and the reaction was stopped J1. ω-Hydroxypentadecanoic acid methyl ester was obtained with a yield of 72.496.

Comparative Example 1 6.0 g of the dry gel prepared in Example 1 was taken, and the hydrogenation reaction of pentadecanoic acid monomethyl ester was started in exactly the same manner as in Example 1 except that water was not added.

Perform the reaction while sampling, and after starting the reaction, 30.
At 0 hours, the reaction was stopped and the contents were analyzed in the same manner as in Example 1.

The analysis results of Example 1 and Comparative Example 1 are summarized in FIG.

Example 2 Dry gel prepared in Example 19. The amount of water added was set to 2.5 g, and the internal pressure of the container was increased to 100 with hydrogen gas.
The hydrogenation reaction of pentadecanoic acid monomethyl ester was started in exactly the same manner as in Example 1 except that the hydrogenation rate was increased to kg/cs2. After 14.0 hours from the start of the reaction, the reaction was stopped in the same manner as in Example 1, and the contents were analyzed.

Analysis values Addition rate 87.2% Selectivity 69.8% Yield 60.9% Example 3 1.00g of rhenium heptoxide was placed in 67.69g of hexylene glycol and dissolved by stirring at 80-100°C. did. To this solution was added an ethanol solution of 2011 in which 0.036 g of stannic chloride hydrate was dissolved, and the temperature was 0.
．． After stirring for 5 hours, 5111.49 g of aluminum isopropoxide was further added and stirred overnight at the same temperature.

Next, 20.62 g of water was added to this solution to form a gel. After adding 81 hydrazine hydrate to the gel, the gel was aged at 80°C and then dried at 140°C under reduced pressure.

6.0 g of the dried gel was placed in a quartz tube and activated by heating at 200° C. for 4 hours while flowing hydrogen using a horizontal annular furnace.

Next, this was mixed with 50.0 g of pentadecanedioic acid monomethyl ester, 100.0 g of decahydronaphthalene and 5
．． Charge it with 0g of water into an autoclave with an internal volume of 5001cm, and after replacing the inside of the container with hydrogen gas, start heating.When the temperature reaches 250℃, increase the internal pressure of the container to 75kg/cm2 with hydrogen gas and start the reaction. did. During the reaction, stirring was performed at 1500 revolutions/minute using an electromagnetic induction rotation type. Perform the reaction while sampling, and after starting the reaction, 1
After 7.0 hours, the supply of hydrogen gas was stopped, the reaction was stopped, and the contents were analyzed.

Comparative Example 2 4.0 g of the dry gel prepared in Example 3 was taken, and bentadecanyl was prepared in exactly the same manner as in Example 3, except that no water was added and the internal pressure of the container was increased to 65 kg/el' with hydrogen gas. The hydrogenation reaction of the acid monomethyl ester was started. Perform the reaction while sampling, and after starting the reaction, 20.
At 0 hours, the reaction was stopped and the contents were analyzed in the same manner as in Example 3.

The analysis results of Example 3 and Comparative Example 2 are summarized in FIG.

[Effects of the Invention] As explained above, according to the present invention, long-chain diacid monoester is hydrogen-reduced using a solid catalyst in the coexistence of water to produce ω- with high selectivity and high yield. Hydroxy fatty acid esters can be produced.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between yield and addition rate in Example 1 and Comparative Example 1, and FIG. 2 is a diagram showing the relationship between yield and addition rate in Example 3 and Comparative Example 2.

Claims (4)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) (In the formula, R represents an alkyl group, and n represents an integer from 8 to 16.) acid monoester in the presence of water,
The following general formula (II), which is characterized by contact with hydrogen using a solid catalyst ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I
I) (Formula is R, n is the same as that of formula (I)) A method for producing an ω-hydroxy fatty acid ester. (2) The method for producing an ω-hydroxy fatty acid ester according to claim (1), wherein the solid catalyst is a ruthenium-based and/or rhenium-based catalyst. (3) The method for producing an ω-hydroxy fatty acid ester according to claim (2), wherein the ruthenium-based catalyst contains ruthenium and tin. (4) The method for producing an ω-hydroxy fatty acid ester according to claim (2), wherein the rhenium-based catalyst contains rhenium and tin.