JPH09278706A - Production of gondoic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce high-purity gondoic acid highly purified by a simple process by using a fatty acid mixture containing gondoic acid as a raw material. SOLUTION: (A) A fatty acid mixture containing gondoic acid and urea are dissolved in an organic solvent and cooled. The precipitated crystal is separated and removed. (B) The solution of the organic solvent is mixed with water and the formed oil layer is separated and recovered. Or (D) urea is dissolved in the solution of the organic solvent and cooled and the precipitated crystal is collected. The crystal is mixed wit water to give an oil layer, which is separated and recovered. (C) The oil layer thus separated and recovered is dissolved in a polar solvent, partially neutralized and cooled. The precipitated crystal of the acidic salt of the fatty acid is collected and is decomposed with an acid to produce high-purity gondoic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing high-purity gondoic acid from a fatty acid mixture containing gondoic acid.

[0002]

BACKGROUND OF THE INVENTION Gondoinic acid, known as cis-11-eicosenoic acid, has recently been revealed to have many excellent properties such as physical, chemical and physiological properties. It is expected to be applied to fields such as cosmetics.

[0003] Gondoinic acid is contained in jojoba oil known as wax ester in an amount of about 35% by weight. When this jojoba oil is hydrolyzed, a fatty acid mixture containing gondoinic acid and higher alcohol are produced. By separating the both, a fatty acid mixture containing gondoic acid can be obtained.

In this method, higher alcohols and fatty acid alkali metal salts by hydrolysis (Japanese Patent Application Laid-Open No. 50-15184) are used.
No. 8, JP-A No. 2-56442), fatty acid alkaline earth metal salts (JP-A No. 51-60207, JP-A No. 4-266998) or fatty acid lower alcohols.
It is known to use a mixture of luster (Japanese Patent Laid-Open No. 6-212187) to separate by liquid-liquid or solid-liquid extraction.

[0005]

However, in any of these methods, the fatty acid mixture and the higher alcohol can be separated, but the fatty acid species cannot be separated. Therefore, the gondoic acid in the fatty acid mixture cannot be separated. Purity is 70% by weight
To obtain high-purity gondoin acid,
More steps have to be taken.

[0006] In view of this point, the present invention aims to provide a method for producing highly purified gondoin acid, which is highly purified from this, by using a fatty acid mixture containing gondoin acid as a raw material in a simple process. I am trying.

[0007]

Means for Solving the Problems As a result of intensive studies on the above objects, the present inventors have found that when a raw material fatty acid mixture is subjected to a specific treatment such as reaction with urea, a high purity is obtained. The present inventors have completed the present invention by knowing that gondoinic acid can be easily produced.

That is, according to the present invention, (a) a fatty acid mixture containing gondoic acid and urea are dissolved in an organic solvent and then cooled, the precipitated crystals are separated and removed, and (b) the resulting organic solvent solution is treated with water. The oil layer generated by adding the
(C) This oil layer is dissolved in a polar solvent to partially neutralize it, and then cooled, and the precipitated acid salt crystals of fatty acid are separated and acid-decomposed (claim). 1) and in this method, in place of the step (b), (d) urea was added to the obtained organic solvent solution and dissolved, and then cooled, and the precipitated crystals were separated and water was added thereto. The present invention relates to a method for producing gondoinic acid (claim 2), characterized in that the oil layer produced by the addition of the above is separated and recovered, and this is introduced into the step (c).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The fatty acid mixture containing gondoic acid according to the present invention is usually obtained by hydrolyzing jojoba oil or the like by a method such as high-pressure hydrolysis, saponification or enzymatic decomposition, and then using a higher alcohol content. The product obtained by separating and removing is used, but this product may have been subjected to any purification treatment such as re-saponification, washing with water, distillation and adsorption, in which the higher alcohol content is It may be included to some extent.

In the present invention, first, in step (a), the above-mentioned fatty acid mixture containing gondoic acid is dissolved in an organic solvent together with urea and then cooled, and the precipitated crystals are separated and removed. The cooling temperature is 30 ° C or lower, preferably 20 to 0 ° C. The crystal is an adduct of urea with a monoene unsaturated fatty acid having a carbon number higher than that of saturated fatty acid or gondoic acid. The crystals are separated and removed by usual means such as filtration and centrifugation. Usually, this step (a) is sufficient for one operation, but it may be repeated twice or more in order to enhance the efficiency of removing the crystals.

Examples of the organic solvent include methanol and ethanol.
Lower alcohols such as phenol, n-propanol, and isopropanol, acetone, acetonitrile, and a solvent obtained by mixing these are used. The amount of the organic solvent to be used cannot be unconditionally determined depending on the target purity, the yield, the setting of the number of crystallizations, etc., but is preferably 0.5 to 10 times the weight of the fatty acid mixture. When the amount is less than 0.5 times by weight, the removal efficiency of monoene unsaturated fatty acid having a higher carbon number than that of saturated fatty acid or gondoic acid is lowered, and when the amount is more than 10 times by weight, the concentration of fatty acid is lowered and the production efficiency is lowered.

The amount of urea used can be appropriately set depending on the fatty acid composition, target purity, yield, crystallization temperature, amount of solvent and the like. Usually, 3 to 30 times by weight of the total amount of the saturated fatty acid and the monoene unsaturated fatty acid having a carbon number higher than that of gondoic acid in the fatty acid mixture is preferable. If it is less than 3 times by weight, the removal of saturated fatty acids and the above-mentioned monoene unsaturated fatty acids will be insufficient, and if it is more than 30 times by weight, the yield of gondoin acid will decrease.

Next, as the step (b), the above (a)
Water is added to the organic solvent solution obtained in the step to separate and collect the resulting oil layer. The oil layer is a fatty acid mixture containing gondoinic acid, which is collected by static separation or centrifugation. The amount of water used is preferably 3 times or more the weight of the organic solvent solution. At this time, addition of a small amount of polybasic acid such as oxalic acid or citric acid can prevent emulsification during washing with water.

Further, instead of the step (b), as a step (d), urea is added again to the organic solvent solution obtained in the step (a) to dissolve by heating and then cooled, and the precipitated crystals are collected. It is also possible to separate and collect the oil layer produced by adding water to this. The crystal here is an adduct of gondoic acid and urea, which is collected by a usual means such as filtration or centrifugation. When water is added to the crystals to decompose them, gondoic acid is separated as an oil layer, which is recovered by a stationary separation layer or centrifugation. According to this step (d), the purity of gondoic acid can be further increased.

The amount of urea used in step (d) is appropriately selected depending on the fatty acid composition in the organic solvent solution obtained in step (b), the target purity, yield, crystallization temperature, amount of solvent, etc. Can be set. Usually, it is preferably 3 to 20 times by weight the amount of gondoic acid. If it is less than 3 times by weight, the yield of gondoinic acid will be reduced, and if it is more than 20 times by weight, fatty acids other than gondoinic acid will be crystallized as urea adducts, and crystals of urea simple substance will be generated. Becomes worse. Further, the amount of water used may be at least an amount capable of hydrolyzing the crystals of the urea adduct, in which case a small amount of oxalic acid,
Addition of a polybasic acid such as citric acid can prevent emulsification during washing with water.

In the present invention, then, in step (c), the oil layer separated and recovered in step (b) or (d) above is dissolved in a polar solvent, partially neutralized and then cooled to precipitate the fatty acid. The crystals of the acidic salt of are collected and acid decomposed.
The formation of an acid salt of a fatty acid by partial neutralization increases the concentration of gondoinic acid in crystals that are cooled and precipitated, and by the acid decomposition thereof, highly purified gondoinic acid can be produced.

Examples of alkaline substances used for partial neutralization include hydroxides and carbonates of lithium, sodium, potassium, ammonia and the like. The neutralization rate is 30 to 60 with respect to the acid equivalent of the fatty acid mixture containing gondoic acid.
%, Preferably 40 to 50%. If less than 30%,
If the yield of gondoinic acid decreases and exceeds 60%, the separation efficiency of other fatty acids becomes poor, and the crystalline state of the acid salt of the crystallized fatty acid becomes poor, making filtration difficult and the purity of gondoinic acid. descend.

Examples of the polar solvent include lower alcohols such as methanol, ethanol, n-propanol and isopropanol, acetone, acetonitrile, tetrahydrofuran, water and a mixed solvent thereof. Used. The amount of the polar solvent used cannot be determined unconditionally depending on the target purity, yield, setting of the number of crystallizations, etc., but is preferably 2 to 10 times the weight of the raw material fatty acid. If it is less than 2 times by weight, the separation effect will be reduced, and if it is more than 10 times by weight, the fatty acid concentration will be low and the production efficiency will be lowered. The cooling temperature of the solution obtained by dissolving the oil layer in this polar solvent and partially neutralizing it is preferably 20 ° C. or lower. If the temperature exceeds 20 ° C, the amount of acidic salt deposited will decrease.

To decompose the acid salt crystals of fatty acid with an acid,
Acid is used. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid and boric acid, acetic acid, oxalic acid, malonic acid, succinic acid, malic acid,
Organic acids such as tartaric acid and citric acid are used. The amount of the acid used is equal to or more than the equivalent of the base constituting the acid salt of the fatty acid, and preferably 1.2 equivalent or more. After acid decomposition, the acid used for acid decomposition remaining in the fatty acid is removed by washing with water. When a small amount of polybasic acid such as oxalic acid or citric acid is added during this water washing, emulsification during water washing can be prevented, and acid decomposition of the acid salt of fatty acid can be carried out completely.

By repeating this step (c), fatty acids other than gondoic acid and trace impurities can be further removed. After this step, purification is performed by methods such as dehydration, distillation, molecular distillation, and adsorption to obtain gondoin acid as a final product.

The gondoic acid thus obtained is
Highly pure, colorless and odorless, does not contain trace impurities such as oxidation products that cause deterioration, has excellent stability to heat, oxygen and chemicals, and is highly safe for living organisms. It has characteristics such as physical properties peculiar to gondoic acid such as various crystal polymorphisms, and can be used in a wide range of fields such as pharmaceuticals, cosmetics, and biochemicals.

[0022]

Next, an embodiment of the present invention will be described in more detail. In addition, "raw material fatty acid mixture A to C" (fatty acid mixture containing gondoic acid) used in the following Examples was obtained in Preparation Examples 1 to 3 below.

<Preparation Example 1> Refined jojoba oil (saponification value 9
2.2) 3,000 g, 387 g of sodium hydroxide
(1.5 equivalents), add 2,400 g of water and add
In the flask, saponification reaction was performed under pressure at 160 ° C. for 6 hours. After the reaction, an aqueous solution prepared by dissolving 10.5 kg of ethyl acetate and 714 g (1.5 equivalents) of calcium chloride dihydrate in 3,000 g of water was added to the saponified product, and the mixture was stirred at 50 ° C. for 30 minutes, and by metathesis reaction, Sodium soap was converted to calcium soap (metal soap). The reaction product was allowed to stand overnight at 20 ° C. to separate it into an organic solvent layer, an intermediate layer and an aqueous layer.

The three layers were separated by decantation and filtration. An aqueous hydrochloric acid solution was added to the intermediate layer metal soap to adjust the pH to 3.2, the aqueous layer was separated, the oil layer was washed with water to remove hydrochloric acid, and dehydrated to obtain 1,462 g of a fatty acid mixture. This was subjected to molecular distillation at 0.01 mmHg to obtain a fatty acid mixture containing gondoinic acid (purity of gondoinic acid 7
2.2 wt%) was obtained. This was used as raw material fatty acid mixture A.

<Preparation Example 2> 1,476 g of a fatty acid mixture obtained by the same procedure as in Preparation Example 1 (saponification reaction of refined jojoba oil to washing and dehydration of the oil layer formed from the intermediate layer) Under nitrogen gas blowing, 1mmHg, 25
Distilled at 0 ° C. or below to obtain a fatty acid mixture containing gondoinic acid (purity of gondoinic acid: 82.3% by weight)
g was obtained. This was used as raw material fatty acid mixture B.

<Preparation Example 3> 15 kg of purified jojoba oil was heated to 250 ° C. in a pressure vessel, steam of 60 kg / cm ² was blown therein, and the reaction was carried out for 3 hours to obtain a hydrolyzate of jojoba oil (acid value 89.4). ) 15.4 Kg was obtained. Methanol 42.
It is dissolved in 8 kg and heated to 50 ° C., and 492 g of anhydrous sodium hydroxide (0.5 times the fatty acid equivalent) is added to water of 2.2.
What was dissolved in 5 kg (sodium hydroxide concentration 18% by weight) was added, and dissolved by heating to make a uniform solution, which was cooled to 5 ° C. with stirring and then filtered to obtain crystals of a fatty acid mixture containing gondoinic acid 3. 940 g were recovered.

To this was added 11.8 kg of a 5% by weight phosphoric acid aqueous solution, and the mixture was heated to undergo acid decomposition. The obtained oil layer was thoroughly washed with a 0.1 wt% citric acid aqueous solution and then dehydrated to give a crude fatty acid mixture containing gondoic acid (acid value 149.7,
2,830 g of a saponification value of 156.0) was obtained. This is distilled under nitrogen gas blowing at 1 mmHg and 250 ° C. or less,
1,340 g of a fatty acid mixture containing gondoic acid (purity of gondoic acid 92.9% by weight) was obtained. This was used as raw material fatty acid mixture C.

Example 1 1,316 g of the starting fatty acid mixture A (purity of gondoic acid of 72.2% by weight) and 1,632 g of urea were dissolved in 9,212 g of methanol, cooled to 15 ° C. and then precipitated. The crystals of the urea adduct were separated and removed by suction filtration. To the filtrate, 32.4 kg of a 1 wt% citric acid aqueous solution was added, and the temperature was 50 ° C.
After heating and stirring, the mixture was allowed to stand to separate layers to obtain 921 g of a fatty acid mixture (acid value 180.6) containing gondoic acid.

Next, this fatty acid mixture and 59.3 g of sodium hydroxide (50% equivalent of the fatty acid mixture) were added to 6 parts of water.
What was dissolved in 4.2 g (sodium hydroxide concentration 48% by weight) was mixed with 4,605 g of methanol, dissolved by heating, cooled to 5 ° C. with stirring, and then filtered off.
633 g of crystals of the acid salt of the fatty acid mixture were obtained. 5 to this
A weight% hydrochloric acid aqueous solution (4,431 g) was added, and the mixture was heated while being acid decomposed. The obtained oil layer was thoroughly washed with a 0.1% weight citric acid aqueous solution, and then dehydrated to give gondine having a purity of 99.0% by weight. 452 g of acid are obtained.

Example 2 1,033 g of raw material fatty acid mixture B (purity 82.3% by weight of gondoic acid) and 878 g of urea were added to methanol 7,2.
After dissolving in 31 g and cooling to 15 ° C., the precipitated urea adduct crystals were separated and removed by suction filtration. 1 in the filtrate
After adding 25.9 kg of an aqueous solution of citric acid in weight% and heating to 50 ° C. and stirring, the mixture was allowed to stand and separate to obtain 826 g of a fatty acid mixture (acid value 180.5) containing gondoic acid.

This fatty acid mixture and sodium hydroxide 5
3.1 g (50% equivalent of fatty acid mixture) of water 57.5 g
Dissolved in (sodium hydroxide concentration 48% by weight)
Was mixed with 4,130 g of methanol and dissolved by heating,
After cooling to 5 ° C. with stirring, the crystals were filtered off to obtain 563 g of crystals of an acid salt of a fatty acid mixture. 5% by weight to this
An aqueous hydrochloric acid solution (3,941 g) was added, mixed and heated to undergo acid decomposition, and the obtained oil layer was thoroughly washed with a 0.1 wt% citric acid aqueous solution and then dehydrated to give 402 g of gondoic acid having a purity of 99.3 wt%. Got

Example 3 1,340 g of a raw material fatty acid mixture C (purity of gondoinic acid: 92.9% by weight) and 1,059 g of urea were dissolved in 9.38 kg of methanol, cooled to 15 ° C. and then precipitated. The crystals of the urea adduct were separated and removed by suction filtration. To the filtrate, 35.3 kg of a 1% by weight citric acid aqueous solution was added, and the mixture was warmed to 50 ° C. and stirred, and then the layers were allowed to stand, and 1,203 g of a fatty acid mixture containing gondoic acid (acid value 180.4) was added. Obtained.

This fatty acid mixture and sodium hydroxide 7
7.4 g (50% equivalent of the acid value of the fatty acid mixture) was added to water 8
What was dissolved in 3.8 g (sodium hydroxide concentration 48% by weight) was mixed with 6,015 g of methanol, dissolved by heating, cooled to 5 ° C. with stirring, and then filtered.
962 g of crystals of the acid salt of the fatty acid mixture were obtained. 5 to this
A weight% hydrochloric acid aqueous solution (6,734 g) was added, and the mixture was heated while being acid decomposed. The obtained oil layer was thoroughly washed with a 0.1% weight citric acid aqueous solution and then dehydrated to give a gondine having a purity of 99.5% by weight. 818 g of acid were obtained. This was distilled under a nitrogen gas blow at 1 mmHg and 250 ° C. or lower to obtain a purity of 99.6.
736 g of gondoic acid of weight% were obtained.

Example 4 1,355 g of a raw material fatty acid mixture C (purity of gondoinic acid: 92.9% by weight) and 1,070 g of urea were dissolved in 9,485 g of methanol and cooled to 15 ° C., followed by precipitation. The crystals of the urea adduct were separated and removed by suction filtration. After 2,846 g of urea was dissolved in the filtrate and cooled to 15 ° C., 3,984 g of precipitated urea adduct crystals were recovered. 11.952 kg of a 1% by weight citric acid aqueous solution was added to this, and the mixture was stirred at 50 ° C. and then stir-separated to separate the fatty acid mixture containing gondoic acid (acid value 180.6).
24 g was obtained.

This fatty acid mixture and sodium hydroxide 5
9.5 g (50% equivalent of fatty acid mixture) was added to water 64.5 g
Dissolved in (sodium hydroxide concentration 48% by weight)
Was mixed with 4.62 kg of methanol, dissolved by heating, cooled to 5 ° C. with stirring, and then filtered to obtain 739 g of crystals of an acid salt of a fatty acid mixture. 5,174 g of a 5 wt% hydrochloric acid aqueous solution was added to this, and the mixture was heated while being acid decomposed.
The obtained oil layer was thoroughly washed with a 0.1 wt% citric acid aqueous solution and then dehydrated to obtain 628 g of gondonic acid having a purity of 99.7 wt%. 1mmH under nitrogen gas blowing
g, and distilled at 250 ° C. or lower to obtain 565 g of gondoic acid having a purity of 99.8% by weight.

Example 5 Using the raw material fatty acid mixture C, the same operations as in Example 4 (treatment operations from separation and removal of the urea adduct to acid decomposition of the acid salt of the fatty acid mixture and washing and dehydration of the produced oil phase) were carried out. Gondoin acid having a purity of 99.7% by weight (acid value 180.7) 5
71 g and sodium hydroxide 36.8 g (50% equivalent of fatty acid mixture) dissolved in water 39.9 g (sodium hydroxide concentration 48% by weight) were added to methanol 3,997.
g, dissolved by heating, cooled to 5 ° C. with stirring, and then filtered to obtain 457 g of crystals of an acid salt of a fatty acid mixture.
I got To this, 5,174 g of 5 wt% hydrochloric acid aqueous solution was added, mixed and heated to undergo acid decomposition, and the obtained oil layer was thoroughly washed with 0.1 wt% citric acid aqueous solution and then dehydrated to have a purity of 99.9 wt%. 388 g of% gondoic acid were obtained.

Comparative Example 1 In the method for preparing the starting fatty acid mixture C, crystals of the acid salt of the fatty acid mixture containing gondoic acid were recovered,
The crystals (515 g) were dissolved again in methanol (2060 g) with heating, cooled to 5 ° C. with stirring, and filtered to obtain crystals (245 g). 900 g of 5 wt% hydrochloric acid was added to the crystals, and the mixture was heated while being acid decomposed. The obtained oil layer was thoroughly washed with a 0.1 wt% citric acid aqueous solution and then dehydrated to give a crude fatty acid mixture containing gondoic acid (acid value 165.
1, with a saponification value of 168.3) was obtained. This is distilled under nitrogen gas blowing at 1 mmHg and 250 ° C. or less,
88 g of gondoic acid having a purity of 94.2% by weight was obtained.

As is clear from the above Examples 1 to 5,
According to the method of the present invention, a gondoic acid having a purity of 99% by weight or more can be obtained, but the purity of the gondoic acid is improved only by repeating the crystallization of the acid salt without performing the reaction treatment with urea as in Comparative Example 1. Effect was small, and the yield was reduced to about 65% by weight based on the raw material fatty acid.

[0039]

INDUSTRIAL APPLICABILITY As described above, according to the method of the present invention, 99% by weight or more of very high-purity gondooic acid, which is difficult to prepare by the prior art, can be produced from a fatty acid mixture containing gondooic acid in a simple process. It can be produced and can be used in a wide range of fields such as pharmaceuticals, cosmetics and biochemicals.

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Claims (2)

[Claims] 1. (a) A fatty acid mixture containing gondoic acid and urea are dissolved in an organic solvent and then cooled, the precipitated crystals are separated and removed, and (b) water is added to the resulting organic solvent solution to produce The separated oil layer is separated and collected, and (c) the oil layer is partially neutralized by dissolving it in a polar solvent and then cooled, and crystals of the acid salt of the precipitated fatty acid are separated and acid decomposed. Acid manufacturing method. 2. In the method of claim 1, instead of the step (b), (d) urea is added to the obtained organic solvent solution and dissolved, and then cooled, and the precipitated crystal is separated, A method for producing gondoic acid, characterized in that water is added to this to separate and collect the resulting oil layer, which is then led to step (c).