JPH0499753A - Production of omega-hydroxy fatty acid ester - Google Patents

Abstract

PURPOSE:To use inexpensive raw materials and to efficiently produce the title compound by a relative simple process at low cost by reducing a long-chain diacid monoester with hydrogen in the presence of a ruthenium-based and/or a rhenium-based catalyst. CONSTITUTION:A long-chain diacid monoester (e.g. pentadecane diacid monomethyl ester) shown by formula I (R is alkyl; n is 8-16 integer) is brought into contact with hydrogen in the presence of a ruthenium-based catalyst (especially preferably one containing ruthenium and tin) and/ or a rhenium-based catalyst (especially preferably one containing rhenium and tin) to give an omega- hydroxy fatty acid ester (e.g. omega-hydroxypentadecanoic acid methyl ester) shown by formula II. Advantageously the compound shown by formula I is readily produced. The omega-hydroxy fatty acid ester is useful as a raw material for drugs, a synthetic raw material for macrocyclic lactones and a raw material for polymers, etc.

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 also has a wide range of applications as a raw material for polymers. The present invention relates to a method for producing fatty acid ester.

[Prior art] Conventionally, as a method for producing a2 of ω-hydroxy fatty acids, ω-
Hydroxy or ω-acyloxy-alkyl-γ-
A method of catalytically reacting butyrolactone in the presence of a hydrogen cracking catalyst and in the coexistence of hydrogen gas (Japanese Patent Publication No. 61-3776
), or 13-oxa-bicyclo[10,4
,0]-Hexadecene[1(12)] is converted into a lactone, and the lactone ring is opened by the Wolffukisiner method or the van-minolone method (Japanese Patent Publication No. 131-21474), etc. have been proposed. ing.

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 Unexamined Patent Publication No. 63-88154) or a cobalt catalyst (Japanese Unexamined Patent Publication No. 63-301845). has been done.

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

[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- and droxy 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 uses a long chain dimonoester represented by the following general formula (1) % formula % (1) (wherein R represents an alkyl group and n represents an integer of 8 to 16) to ruthenium. The following general formula (IT) R-0-C-+CIIz +o CH20H(II) is characterized in that it is brought into contact with hydrogen in the presence of a rhenium-based catalyst and/or a rhenium-based catalyst.
(The formula is RSn is the same as that in formula (1)) ω-
This is a method for producing hydroxy fatty acid ester.

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

This monoester can be easily obtained by esterifying an alkanedioic acid with an alcohol, converting it into a barium monosalt 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 separated and purified.

Note that alkanedioic acids are produced at relatively low prices by oxidizing alkanes having the corresponding number of carbon atoms in the presence of microorganisms.

The rhenium-based catalyst used in the present invention refers to a rhenium metal 11 substance, a rhenium compound, or a mixed catalyst of this and other metal catalysts such as tin, ruthenium, etc. Most preferably used are rhenium-based catalysts containing rhenium and soot.

Further, the ruthenium-based catalyst used in the present invention refers to a ruthenium metal alone, a compound thereof, or a mixed catalyst of this and other metal catalysts such as soot, rhenium, etc. Most preferably used in the present invention is It is a ruthenium-based catalyst that contains ruthenium and soot.

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 organic melt. 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 easily soluble in organic solvents, and react with aluminum compounds, silicon compounds, titanium compounds, zirconium compounds, or niobium compounds to dissolve them in organic solvents. Any of the following 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 soot is in the range of 0.5vt% to 30vt% for ruthenium or rhenium, and 0.5vt% to 70vt% for tin, when each is considered as a metal. It is preferable to set the usage amount as follows. Regarding the relative content of ruthenium or rhenium and soot, the atomic ratio of tin/ruthenium or rhenium is 0. 10 from old, 0 for more details
．． 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.

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 ℃. The reaction pressure is hydrogen pressure 1O~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 78 m2 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/cw+2 or more, no significant improvement in reaction rate can be expected, and a hydrogen pressure higher than this is not preferable from the economical and safety standpoints.

Such reaction conditions are appropriately selected depending on the type of long-chain dimonoester used as a raw material, the activity of the catalyst used, 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 vL%, preferably 5 to 50 vt%.

The reaction time varies depending on the above reaction conditions, but is approximately 10 to 10
This can be done in about 0 hours.

[Example] The method of the present invention will be specifically explained below using Examples. Identification and quantification of the products in this reaction were performed by gas chromatography, but since polyester was produced as a by-product in the reaction product, it was hydrolyzed by a conventional method to form a tetramethylsilane derivative, and then analyzed. I did it.

Example 1 1.5 g of ruthenium trichloride hydrate and 8.95 g of tin tetrachloride hydrate were dissolved in 301 and 501 ethanol, respectively, and then mixed. This solution was synthesized by hydrolyzing aluminum isopropoxide in hexylene glycol, and added to 28.64 g of alumina that had been heated and exhausted at 150°C under reduced pressure at room temperature. After stirring overnight at 150 °C under reduced pressure.
Dry at °C.

4g of dry gel was placed in a quartz tube and heated using a horizontal ring furnace.
After firing at 00° C. for 2 hours and cooling to room temperature, activation was performed by heating at 400° C. for 4 hours while flowing hydrogen. Next, this was mixed with 50.0 g of betadecane, oxidized monomethyl ester and 100.0 g of betadecane. After charging Og of decahydronaphthalene into an autoclave with an internal volume of 5,001 kg, the inside of the container was sufficiently replaced with hydrogen gas, heating was started, and when the temperature reached 250°C, the internal pressure of the container was increased to 6 ℃ with hydrogen gas.
The reaction was started by increasing the pressure to 0 kg/cm'. During the reaction,
Stirring was performed using an electromagnetic induction rotary system at 1500 rpm. After 27.0 hours from the start of the reaction, the supply of hydrogen gas was stopped and the mixture was cooled to stop the reaction. Yield 39, 5% ω-
Hydroxypentadecanoic acid methyl ester was obtained.

Analytical values Conversion rate 43.1% Selectivity 91.6% Yield 39.5% Example 2 8. Og of trisacetylacetonateruthenium complex was suspended in 30ml of ethanol aqueous solution, and 30g of it was suspended in 30ml of ethanol aqueous solution.
of concentrated nitric acid was added and stirred at 80 to 90°C for 2 hours. Next, add another 23 g of concentrated nitric acid, and wash the complex adhering to the vessel wall into the solution with as little acetic acid as possible.
Warmed to ~100°C for 3-4 hours. During this time, nitrogen oxide gas evolved and the suspension liquefied to a clear red solution. After drying this solution, 163.7 g of hexylene glycol and 142 g of aluminum isopropoxide were added thereto, and the mixture was stirred at 80 to 90° C. for 4 hours. Furthermore, add 4 to this solution.
．． After adding 5 g of tetraethoxytin and stirring at the same temperature for 1 hour, 65 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.

4.0 g of the dried gel was taken, and in the same manner as in Example 1, a hydrogenation reaction of bentadecane dimonomethyl ester was started. 26.0 hours after the start of the reaction, the reaction was stopped in the same manner as in Example 7. The contents were analyzed.

Analytical values Conversion rate 71.5% Selectivity 88.4% Yield 63.2% Example 3 2. Og of trisacetylacetonate toruthenium complex was suspended in 151 of ethanol aqueous solution, and 27g of concentrated nitric acid was added to it. The mixture was added and stirred at 80 to 90°C for 1 hour. Next, add another 15 g of concentrated nitric acid, and wash the complex adhering to the vessel wall 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 evolved and the suspension softened to a clear red solution. After drying this solution, 74.17 g of hexylene glycol and 63.29 g of aluminum isopropoxide were added thereto, and the mixture was stirred at 100° C. for 2 hours. Furthermore, add 1,50 to this solution.
g of tetraethoxytin was added, and after 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 180° C. under reduced pressure.

0.0 g of the dried gel was taken, and the hydrogenation reaction of pentadecane dimonomethyl ester was started in the same manner as in Example 1. 21.0 hours after the start of the reaction, the reaction was stopped in the same manner as in Example 1, and the contents were analyzed.

Analysis values Conversion rate 83.8% Selectivity 75.8% Yield 63.5% Example 4 Ethanol solution in which 4.0g of ruthenium trichloride hydrate was dissolved and IO, 54g of stannic chloride hydrate was added to 117.30 g of hexylene glycol. 101.36 g of aluminum isopropoxide was added to this solution and stirred at 80 to 90°C for 3 hours to obtain a homogeneous solution. Next, 48.51 g of water was added to this solution, and after warming at the same temperature for 1.5 hours, the resulting gel was dried at 130° C. under reduced pressure.

3.0 g of the dried gel was taken, and the hydrogenation reaction of pentadecane dimonomethyl ester was started in the same manner as in Example 1. Example 1 17.7 hours after the start of the reaction
The reaction was stopped and the contents were analyzed in the same manner as above.

Analysis values Conversion rate 50.1% Selectivity 73.5% Yield 36.8% Comparative example Pentadecane dimonomethyl ester 5.73g (20%
gmol), copper-chromium oxide catalyst (Cu044wt%
, Cr 20342vt%, B a 06.7vt%,
M u 03.8wt%, surface N4D ~ G[1m'
/g) 0.29g.

Autoclave with 2001 volumes of dioxane 251.

Place it in-house and fill it with hydrogen to an initial hydrogen filling pressure of 120 kg.
/cm', and was allowed to react for 6 hours while heating at a temperature of 215°C, and the contents were analyzed.

Analytical values Conversion rate 76.096 Selectivity 71.3% Yield 54,296 Example 5 0.94 g of rhenium trichloride and 2.25 g of stannic chloride hydrate were added to 301 and 50-1 ethanol, respectively. After dissolving, they were mixed. This solution was synthesized by hydrolyzing aluminum isopropoxide in a hexylene grill, and added to 28.64 g of alumina that had been heated and exhausted at 150°C under reduced pressure at room temperature. After stirring overnight, it was dried at 150°C under reduced pressure. 4 g of the dry gel was placed in a quartz tube and activated by heating at 400° C. for 4 hours while flowing hydrogen using a horizontal ring furnace.

Next, this was charged into an autoclave with an internal volume of 5001 cm along with 50.0 g of pentadecane dimonomethyl ester and loo and og decahydronaphthalene, and after the inside of the container was sufficiently replaced with hydrogen gas, heating was started and heated to 250°C.
At that point, increase the internal pressure of the container to 80 kg/c with hydrogen gas.
m 2 and the reaction was started. During the reaction, an electromagnetic induction rotary type was used for stirring at 1500 revolutions/rotation. After 24.0 hours from the start of the reaction, the supply of hydrogen gas was stopped and the reaction was stopped. ω-hydroxypentadecanoic acid methyl ester was obtained with a yield of 44.6%.

Analytical values Conversion rate 51.5% Selectivity 86.6% Yield 44.6% Example 6 0.94 g of rhenium trichloride was heated and dissolved in 300 ml of ethanol solution containing 132.8 g of hexylene glycol. To this solution was added an ethanol solution of 301 in which 114.76 g of aluminum isopropoxide and O, Ilg stannic chloride hydrate were dissolved, and the mixture was stirred at 80° C. for 3 hours. Next, 46 g of water was added to this solution to form a gel. After aging the gel at the same temperature for 1 hour, it was dried at 170° C. under reduced pressure.

4.0 g of the above dried gel was taken, and in the same manner as in Example 5, a hydrogenation reaction of pentadecanoic acid monomethyl ester was started. Example 5 23.0 hours after the start of the reaction
The reaction was stopped in the same manner as above, and the contents were analyzed.

Analytical values Conversion rate 32.5% Selectivity 89.5% Yield 29.1% Example 7 120.41g of 2.Og ammonium perrhenate
hexylene glycol and dissolved as much as possible at 80 to 100°C. About 80 g of the supernatant of this solution was added 1.
11 g of tetraethoxytin, 104.05 g of aluminum isopropoxide, and 30.0 g of hexylene glycol were added and heated to 80 to 110° C. to obtain a homogeneous solution. Dissolve the remaining ammonium perrhenate and approximately 40 g of hexylene glycol in a mixture of 5. A homogeneous solution of Og added with water and dissolved at 80°C was added to the above reaction solution,
The mixture was stirred at 80°C for 1 hour. Next, 31.7 g of water was added to this solution, and after warming at 80°C overnight, the resulting gel was dried at 140°C under reduced pressure.

4.0 g of the dried gel was taken, and the hydrogenation reaction of pentadecanedioic acid monomethyl ester was started in the same manner as in Example 1. After 36.0 hours from the start of the reaction, the reaction was stopped and the contents were analyzed in the same manner as in Example 5.

Analytical values Conversion rate 82.4% Selectivity 73.190 Yield 60.2% Example 8 1.00g of nyrenium oxide was placed in 67.69g of hexylene glycol and dissolved by stirring at 80-100°C. . To this solution was added an ethanol solution of 201 containing 0.036 g of soot chloride hydrate, and after stirring at 80°C for 0.5 hour, 58.49 g of aluminum isopropoxide was added to the same solution. Stir overnight at warm 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.

Take 4.0g of the above dry gel and activate it with hydrogen for 20 minutes.
The hydrogenation reaction of pentadecanedioic acid monomethyl ester was started in exactly the same manner as in Example 1 except that it was carried out at 0°C. After 11.0 hours from the start of the reaction, the reaction was stopped in the same manner as in Example 5, and the contents were analyzed.

Analytical values Conversion rate 629% Selectivity 71.99ci Yield 45,296 Example 9 4.0 g of 2% ruthenium-alumina catalyst (manufactured by N.E. Chemcat Co., Ltd.) was taken and the following procedure was performed in exactly the same manner as in Example 5. Then, the hydrogenation reaction of pentadecanedioic acid monomethyl ester was started.

After the start of the reaction, the reaction was stopped at 31,0 intercostals in the same manner as in Example 5, and the contents were analyzed.

Analytical values Conversion rate 336% Selectivity 82.4% Yield 27.79ci Comparative example Pentadecanedioic acid monomethyl ester 5.73g (20
mnol), copper-chromium oxide catalyst (Cu044V [%
, Cr 20342vt%, B a O6,7vt%,
M u O3, 8 wt%, surface area 40-60 m'/
g) 0.29g.

Put dioxane 251 into a 20On+ml autoclave device, fill it with hydrogen, and set the initial hydrogen charging pressure to 120k.
g/cm2, and was allowed to react for 6 hours while heating at a temperature of 215°C, and the contents were analyzed.

Analytical values Conversion rate 76.0% Selectivity 71.396 Yield 54.2°6 [Effects of the invention] The present invention converts long chain dimonoesters into ruthenium-based catalysts and/or rhenium-based catalysts. Since we decided to reduce hydrogen to 'F, we can use the less expensive HA, and we can produce ω-hydroxy fatty acid esters in a relatively simple process, at low production costs, and more efficiently. I can do it.

Claims (3)

[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.) The following general formula (II), which is characterized by contacting acid monoester with hydrogen in the presence of a ruthenium-based and/or rhenium-based catalyst ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (The formula is R, (n is the same as in formula (I)) A method for producing an ω-hydroxy fatty acid ester represented by: (2) The method for producing an ω-hydroxy fatty acid ester according to claim (1), wherein the ruthenium-based catalyst contains ruthenium and tin. (3) The method for producing an ω-hydroxy fatty acid ester according to claim (1), wherein the rhenium-based catalyst contains rhenium and tin.