JP2651291B2 - Method for producing ω-hydroxy fatty acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as a raw material for a macrocyclic lactone used as a raw material for pharmaceuticals or a flavor, and has a wide variety of uses as a raw material for polymers.
The present invention relates to a method for producing ω-hydroxy fatty acid.

[0002]

2. Description of the Related Art Conventionally, ω-hydroxy or ω-acyloxy-
A method in which an alkyl-γ-butyrolactone is subjected to a catalytic reaction in the presence of a hydrogenolysis catalyst in the presence of hydrogen gas (Japanese Patent Publication No.
No. 61-3776) or 13-oxa-bicyclo [1
0,4,0] -hexadecene [1 (12)] is converted to lactone,
A method of opening the lactone ring of the lactone by the Wolfoxiner method or the van-Minron method (Japanese Patent Publication No. 61-1986)
No. 21474) has been proposed.

[0003] In each of the above methods, since a complex compound is used as a starting material, an expensive raw material is used, and there has been a problem that the production cost is increased.

[0004] In addition, a method of contacting a monoalkyl dicarboxylate with hydrogen in the presence of a copper-chromium oxide catalyst (JP-A-63-88154) or a cobalt-based catalyst (JP-A-63-301845) is known. Proposed.

In these methods, a dicarboxylic acid monoalkyl ester derived from a long-chain aliphatic dicarboxylic acid, which is more readily available than the above-mentioned starting materials, is used as a starting material, but a monoalkyl ester is produced from a dicarboxylic acid. In addition, there is a problem that the production cost of the ω-hydroxy fatty acid is increased. Further, in the presence of a cobalt catalyst which has been sintered at a temperature in the range of 1000 to 1750 ° C. and which has been subjected to a post-reduction treatment, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms has the same carbon number as that of 0.3 to 20 times the weight thereof. A method has also been proposed in which hydrogen is brought into contact with an aliphatic glycol having a carboxylic acid (Japanese Patent Publication No. 47-44204), but this method also requires the preparation of an aliphatic glycol having the same number of carbon atoms as the aliphatic dicarboxylic acid used in the reaction. There was a busy.

[0006]

DISCLOSURE OF THE INVENTION The present invention has solved the above-mentioned drawbacks of the above-mentioned method, and an object of the present invention is to provide a macrocyclic lactone which is useful as a raw material for pharmaceuticals or a perfume. An object of the present invention is to provide a method for advantageously producing ω-hydroxy fatty acid which has a wide range of uses as a polymer raw material.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, obtained from a long-chain aliphatic dicarboxylic acid which is easily available as a direct raw material, high selectivity and high yield of ω-hydroxy fatty acid. It was found that it can be manufactured.

That is, the present invention provides (1) a long-chain saturated aliphatic compound represented by the following general formula (I): HOOC (CH ₂ ) _n COOH (I) (wherein n is an integer of 8 to 16) The following general formula (II) characterized by contacting a dicarboxylic acid with hydrogen in the presence of a ruthenium-based catalyst (but not containing rhenium): HOOC (CH ₂ ) _n CH ₂ OH (II) (2) Ruthenium-based catalyst (but not containing rhenium)
Wherein ruthenium and tin are contained, (3) the method for producing ω-hydroxy fatty acids according to the above (1), (3) HOOC (CH ₂ ) _n COOH (I) wherein n is 8 A long chain saturated aliphatic dicarboxylic acid represented by the following formula: tin: ruthenium-based catalyst containing tin in which the ruthenium is in the range of 0.01 to 10 and / or tin atom: Rhenium is 0.01 ~
And contacting with hydrogen in the presence of a rhenium-based catalyst containing tin in the range of 10 characterized by the following general formula (I
I) HOOC about _{(CH 2) n CH 2 OH} (II) (n is the formula (I) preparation of the represented ω- hydroxy fatty acid in the same) to that of. The raw material long-chain aliphatic dicarboxylic acid used in the present invention may be any compound as long as it is a compound represented by the general formula (I). These are produced relatively inexpensively by oxidizing alkanes of corresponding carbon numbers in the presence of microorganisms.

The rhenium-based catalyst used in the present invention is:
Rhenium metal alone or a rhenium compound or a mixed catalyst thereof with other metal catalysts, such as tin, ruthenium, etc., is most preferably used in the present invention.Rhenium is a rhenium-based catalyst containing tin. is there.

The ruthenium-based catalyst used in the present invention refers to a ruthenium metal alone or a compound thereof or a mixed catalyst thereof with another metal catalyst such as tin or rhenium, but is most preferably used in the present invention. This is a ruthenium-based catalyst containing ruthenium and tin.

The above rhenium and ruthenium catalysts may be prepared by a conventional method such as an impregnation method, a precipitation method and a conventional sol-gel method using a colloid sol as a starting material.
In addition, a chemical mixing method (or an improved sol-
Gel method) or the like.

In the preparation of the catalyst in the impregnation method, any of ruthenium, rhenium and tin compounds can be used as long as they are easily dissolved in water and an organic solvent. Examples of the ruthenium compound include, for example, ruthenium trichloride hydrate, trisacetylacetonatoruthenium, ruthenium tetroxide, ruthenium carbonyl, ruthenium ammonium chloride and the like. Examples of the rhenium compound include, for example, rhenium chloride, rhenium oxychloride, rhenium bromide, rhenium oxybromide, rhenium heptaoxide, ammonium perrhenate and the like.

Examples of the tin compound include, for example, tin (II) chloride, tin (II) chloride, tin bromide, tin acetate and other organic acid tin, tin tetraethoxide and other tin alkoxides. However, the compounds are not limited to these exemplified compounds as long as they are soluble in water and an organic solvent.

Further, as the carrier, diatomaceous earth, alumina,
Any known materials such as silica gel, zirconia, titania and the like can be used.

In the preparation of the catalyst in the chemical mixing method, the ruthenium compound, the rhenium compound and the tin compound are easily dissolved in an organic solvent or react with an aluminum compound, a silicon compound, a titanium compound, a zirconium compound or a niobium compound to react with the organic solvent. Any one that is soluble in water can be used. Examples of ruthenium compounds include, for example, ruthenium trichloride hydrate, trisacetylacetonatoruthenium, ruthenium tetroxide,
Examples of ruthenium compounds include, for example, rhenium chloride, rhenium oxychloride, rhenium bromide, rhenium oxybromide, rhenium heptaoxide, ammonium perrhenate, and the like, and examples of tin compounds include tin chloride. , Tin bromide, organic acid tin including tin acetate, tin alkoxide such as tin tetraethoxide, and the like, but may be any as long as they are soluble in organic solvents, and are limited to these exemplified compounds. It is not something to be done.

In 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 preparing the catalyst are not particularly limited. However, if the amount used is too small, the content of ruthenium or rhenium and tin in the finally obtained solid catalyst will decrease and the activity of the catalyst will decrease, and if it is too large, the catalyst will be too expensive and impractical. When the content of ruthenium or rhenium in the finally obtained catalyst and the content of tin were each viewed as a metal, the content of ruthenium or rhenium was 0.5w.
It is preferable to set the amount to be used in a range from t% to 30% by weight and for tin from 0.5% to 70% by weight. The relative content of ruthenium or rhenium and tin is preferably such that the atomic ratio of tin / ruthenium or rhenium is between 0.01 and 10, more particularly between 0.03 and 3.

The catalyst is used after performing operations such as calcination and reduction as needed.

In the present invention, any method of a suspension bed, a fluidized bed, and a fixed bed can be appropriately employed. In such a case, the catalyst is formed into a mold suitable for each reaction method.

The method for hydrogenating and reducing ω-hydroxy fatty acids is carried out under the following reaction conditions. Reaction temperature is 150-3
Although 50 ° C. is preferred, particularly preferred is 200-300 ° C. The reaction pressure is preferably a hydrogen pressure of 10 to 300 kg / cm ² , and particularly preferably 20 to 150 kg / cm ² . The reduction reaction is not limited to the above condition range, but the hydrogen pressure is reduced to 10 kg.
/ cm ² or less, when the temperature and 0.99 ° C. or less, the reduction reaction rate becomes slow, there is practically no undesirable because the reaction time prolonged. The higher the reaction temperature and hydrogen pressure, the better the reaction rate. However, if the reaction temperature exceeds 350 ° C., it is not preferable because the raw materials and products are decomposed and the yield decreases. or,
When the hydrogen pressure is set to 300 kg / cm ² or more, a remarkable improvement in the reaction rate cannot be expected, and a hydrogen pressure higher than this is not preferable in terms of economy and safety. Such reaction conditions are appropriately selected depending on the kind of the raw material long-chain diacid, the activity of the catalyst to be used, the solvent and the like.

Although the method of the present invention can be carried out without using a solvent, an appropriate solvent can be used.
There is no particular limitation on the solvent used as long as it is inert to the reaction, and organic solvents used in the reduction reaction, that is, ethers, aliphatic hydrocarbons, alicyclic hydrocarbons, or mixtures thereof can be used.

The concentration of the raw material in the solvent is 1 to 80% by weight, preferably 5 to 50% by weight. The reaction time varies depending on the above reaction conditions, but can be carried out for about 1 to 100 hours.

[0022]

EXAMPLES The method of the present invention will be specifically described below with reference to examples. The identification and quantification of the product in this reaction were performed by gas chromatography.However, since polyester was produced as a by-product in the reaction product, it was hydrolyzed by a conventional method to obtain a tetramethylsilane derivative. Analysis was carried out.

Example 1 A solution of 3.00 g of ruthenium trichloride hydrate in ethanol and 3.37 g of ethanol in tetraethoxytin were added to 252.77 g of hexylene glycol.
218.43 g of aluminum isopropoxide was added to this solution, and the mixture was stirred at 80 to 90 ° C. for 3 hours to obtain a homogeneous solution. Next, 77.21 g of water was added to this solution, and after heating at the same temperature for 1.5 hours, the obtained gel was dried at 130 ° C. under reduced pressure.

[0024] 10.0 g of the dried gel is placed in a quartz tube, fired at 400 ° C for 2 hours using a horizontal ring furnace, cooled to room temperature, and then heated at 400 ° C for 4 hours while flowing hydrogen to activate. did. Next, 1.50 g of the activated catalyst is
Charge the autoclave together with 15.0 g of pentadecanoic acid and 30.0 g of decahydronaphthalene into an autoclave having an internal volume of 100 ml, sufficiently replace the inside of the vessel with hydrogen gas, start heating, and when the temperature reaches 280 ° C., reduce the pressure inside the vessel to hydrogen gas. At 100
The reaction was started up to kg / cm ² . During the reaction, stirring was performed at 500 rpm using an electromagnetic induction rotary system. 6.0 hours after the start of the reaction, the supply of hydrogen gas was stopped to cool, and the reaction was stopped. Ω-Hydroxypentadecanoic acid was obtained with a yield of 62.3%.

Analytical values Conversion 94.4% Selectivity 66.0% Yield 62.3% Example 2 0.94 g of rhenium trichloride and 2.25 g of stannic chloride hydrate
After dissolving in 30 ml and 50 ml of ethanol, respectively, they were mixed. This solution was synthesized by hydrolyzing aluminum isopropoxide in hexylene glycol and subjected to a heat treatment at 150 ° C. under reduced pressure while heating.
g of alumina was added at room temperature under reduced pressure, stirred overnight at normal temperature and normal pressure, and dried at 150 ° C. under reduced pressure. Take 4 g of the dried gel in a quartz tube and use a horizontal ring furnace to flow hydrogen for 400
Activated by heating at 4 ° C. for 4 hours.

Next, 15.0 g of pentadecandioic acid and
Charge the autoclave together with 30.0 g of decahydronaphthalene into an autoclave with an internal volume of 100 ml, start heating after sufficiently replacing the inside of the container with hydrogen gas, and when the temperature reaches 280 ° C, increase the pressure inside the container to 100 kg / cm ² with hydrogen gas. The reaction was started. During the reaction, stirring was performed using an electromagnetic induction rotary method, and 500 rotations /
Went in minutes. 6.0 hours after the start of the reaction, the supply of hydrogen gas was stopped to cool, and the reaction was stopped. Ω-hydroxypentadecanoic acid was obtained with a yield of 59.2%.

Analytical value Conversion rate 98.2% Selectivity 60.3% Yield 59.2% Comparative Example 1 Monomethyl pentadecanoate 1 as a reaction raw material
The hydrogenation reaction of pentadecandioic acid monomethyl ester was carried out in the same manner as in Example 1 except that 5.0 g was used.

Analytical value Conversion rate 47.7% Selectivity 88.5% Yield 42.2% Comparative Example 2 Dimethyl pentadecandioate 15.0 as a reaction raw material
g in the same manner as in Example 1 except that hydrogenation reaction of dimethyl pentadecandioate was carried out.

Analysis value Conversion 43.1% Selectivity 79.8% Yield 34.4%

[0030]

According to the present invention, a long-chain saturated aliphatic dicarboxylic acid is hydrogen-reduced in the presence of a ruthenium-based catalyst and / or a rhenium-based catalyst, so that inexpensive raw materials can be used and a simple process can be performed. Thus, the production cost is low and the ω-hydroxy fatty acid can be produced efficiently.

 ──────────────────────────────────────────────────続 き Continued on the front page Examiner Makiko Iwase (56) References JP-A-48-15821 (JP, A) JP-A-48-39432 (JP, A)

Claims (3)

(57) [Claims] 1. A long-chain saturated aliphatic dicarboxylic acid represented by the following general formula (I) HOOC (CH ₂ ) _n COOH (I) (wherein n is an integer of 8 to 16) is a ruthenium-based catalyst (II) HOOC (CH ₂ ) _n CH ₂ OH (II) wherein n is the same as that of the formula (I), characterized by contacting with hydrogen in the presence of (but not containing rhenium) )). 2. The process for producing ω-hydroxy fatty acids according to claim 1, wherein the ruthenium-based catalyst (but not containing rhenium) contains ruthenium and tin. 3. A long-chain saturated aliphatic dicarboxylic acid represented by the following general formula (I), HOOC (CH ₂ ) _n COOH (I), wherein n is an integer of 8 to 16. Tin / ruthenium based ruthenium-based catalyst containing tin in the range of 0.01 to 10 and / or atomic ratio tin / rhenium in the range of 0.01 to 10
And contacting with hydrogen in the presence of a rhenium-based catalyst containing tin in the range of 10 characterized by the following general formula (I
I) A method for producing an ω-hydroxy fatty acid represented by HOOC (CH ₂ ) _n CH ₂ OH (II) (n is the same as that of the formula (I)).