JPS6124393B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for concentrating vitamin E, and more specifically, to a method for efficiently separating vitamin E, especially α-tocopherol, from the green leaves of plants of the Carotid family and palm family, which contain vitamin E. It relates to a method of concentration.

Conventionally, the physiological effects of vitamin E are only known to be on the gonads, such as a deficiency in female mice causing infertility and miscarriage of the fetus, and in males causing atrophy of sperm-producing tissue and permanent infertility. However, in recent years, it has become known that its antioxidant power also shows strong antioxidant power in the animal body, preventing cell damage caused by peroxidation and playing an effective role in cell function and metabolism. . Therefore, vitamin E has recently been attracting a lot of attention in the fields of pharmaceuticals, health foods, feed additives, etc., and is also attracting a lot of attention as a non-toxic antioxidant for food packaging plastic films and edible oils. ing.

In addition to α, β-tocopherol, natural vitamin E includes seven types of γ, δ, ε, ζ, η-tocopherol, and α, β, γ, δ-tocopherol with six hydrogen atoms removed from the molecule. Four types of tocotrienols with double bonds introduced are known. Among these, the one with the strongest physiological activity is α-tocopherol, and therefore this α-
Methods for efficiently extracting and synthesizing tocopherols from natural products are being actively researched. In addition, natural α-tocopherol is d-unit, but
Synthetic α-tocopherol is a racemic d,1-isomer.

These vitamin E types are found in plant leaves, stems, seeds, etc., and since the overall content of vitamin E is higher in seeds, it has traditionally been found mainly in wheat germ oil, cottonseed oil, salad oil, etc. It was extracted from seed oil. However, as a result of research by the present inventors, the proportion of α-tocopherol, which has the highest activity, is low among the vitamin E species present in seeds, and
- It was found that the ratio of tocopherols was rather large in leaves and stems, especially in the leaf parts.

Therefore, it is advantageous to use plant leaves and stems as raw materials for obtaining vitamin E rich in α-tocopherol, but the content of vitamin E contained in leaves and stems is very small. Therefore, it is quite difficult to selectively concentrate vitamin E from the tissue. To concentrate vitamin E from leaves and stems, generally, the leaves and stems are first force-dried or sun-dried to remove moisture, and then extracted and concentrated using an organic solvent. Alternatively, a method is used in which water is removed using a water-soluble organic solvent such as a lower alcohol or ketone, and vitamin E is eluted into the solvent and concentrated.

However, the former method of forced drying or sun drying has the disadvantage of loss of vitamin E in the drying process, and the latter method of using a water-soluble organic solvent contains a large amount of water in the solvent. This has the disadvantage that it is difficult to recover the solvent, making it uneconomical.

The present inventors overcame these drawbacks and conducted intensive research on a method for efficiently separating and concentrating vitamin E, especially α-tocopherol, from fresh green leaves without losing them. The present inventors have discovered that the object can be achieved by combining the treatment with an ion exchanger and the treatment with an ion exchanger, leading to the present invention.

That is, according to the present invention, after pulverizing the green leaves of a plant and removing the water produced at the time, the green leaves are treated with a non-polar organic solvent that is insoluble in water and forms an azeotrope with water. The vitamin E contained in the green leaves is eluted into the solvent while the remaining moisture is azeotropically distilled off with the solvent, and then the solvent is distilled off from the eluate, and the remaining liquid is treated with an ion exchanger. By processing with , it is possible to obtain a concentrate of vitamin E containing α-tocopherol as a main component.

The raw materials used in the method of the present invention include, for example, rice,
Suitable are grains such as wheat and corn, leaves of plants of the family Heliaceae such as Hijiba, which grow wild in the wilderness, or plants of the palm family.

These leaves have a lower content of vitamin E than the fruit, but are characterized by an extremely high content of α-tocopherol in the vitamin E.

Furthermore, the non-polar organic solvent used in the present invention is water-insoluble and forms an azeotrope with water, such as n-
Examples include hydrocarbon solvents such as hexane, n-heptane, benzene and toluene, and halogen solvents such as trichlene carbon tetrachloride.

Next, as the ion exchanger used in the present invention,
A basic anion exchanger is suitable, and this can be used in any form such as film, fiber, or granule. Particularly suitable are Organo's Amberlyte IRA 401CL type anion exchange resin and Organo's Amberlyte A-26 anion exchange resin for non-aqueous solutions.

Next, an example of an embodiment of the present invention will be described. First, fresh leaves of a plant of the Coconutaceae family or a Coconut family plant are used as a raw material, and after the leaves are thoroughly crushed, the water produced at that time is filtered through compression etc. Twist and remove. Next, the above-mentioned non-polar organic solvent is added and heated at an azeotropic temperature, and while water remaining in the raw material is azeotropically distilled off with the solvent, vitamin E contained in the plant tissue is eluted into the solvent. . Next, the fibers and the vitamin E-containing solution are separated by filtration or the like, and then the solvent in the solution is distilled off to obtain a concentrate.

This concentrate contains components other than vitamin E, so lower alcohols such as methanol and ethanol are added and heated to remove resinous substances insoluble in alcohol, and the alcohol solution is converted into an ion exchanger. The vitamin E in it comes into contact with
Then, using an ethanol solution containing acetic acid as an eluent, for example, vitamin E adsorbed on the ion exchanger is eluted. Next, a non-aqueous solvent such as n-hexane is added to this vitamin E-containing solution, followed by thorough washing with saturated saline, followed by drying with anhydrous salt water, etc.
The solvent is distilled off to obtain the desired vitamin E-containing concentrate.

The concentrate thus obtained contains about 70% or more of vitamin E, mainly α-tocopherol.

According to the method for concentrating vitamin E of the present invention, vitamin E, especially α-tocopherol, can be separated and concentrated from green leaves of plants very efficiently.

In addition, the obtained concentrate contains approximately 70% or more of vitamin E, mainly α-tocopherol, and can be used as it is as a pharmaceutical, health food, or feed additive, or as edible oil, food packaging film, etc. It can be used as a non-toxic antioxidant.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1 kg of fresh leaves of Hijishiba, a herbaceous plant that grows naturally in the wilderness, was crushed, and the water produced at that time was removed by compression filtration. Attach a cooler and attach a separatory funnel for moisture separation at the bottom of this cooler)
Add 700ml of benzene and heat at around 70℃ for 2 hours.The distilled water and benzene are introduced into a separating funnel attached to the bottom of the condenser.The water is taken out of the system, and the benzene is removed from the flask. The mixture was refluxed to extract the benzene-soluble portion in the fibers.

After the extraction, the benzene solution was cooled to room temperature, filtered under suction to separate the fibers and the benzene solution, and then the benzene solution was concentrated to 300 ml, cooled to room temperature, and the precipitated gel-like substance was filtered for 7000 r.
After sedimentation and removal using a PM centrifuge, benzene was distilled off to obtain 80 g of a greenish-brown benzene extract. 100 ml of methanol was added to this extract, heated while stirring, cooled to around 0°C, and precipitated resinous compounds were separated by suction filtration.
After warming the methanol solution to around room temperature (25°C), it is passed through a glass column layer filled with 300 ml of basic anion exchange resin (Amberlite I/R/A401CL type anion exchange resin manufactured by Organo) to extract vitamin E. were adsorbed. Next, this ion exchange resin was washed with 300 ml of ethanol, and then vitamin E was desorbed from the ion exchange resin with 300 ml of an ethanol solution containing 10% acetic acid. After adding 300 ml of n-hexane to this solution, it was desorbed with saturated saline. Wash to remove acetic acid and ethanol, then n
- After adding anhydrous sulfur salt to a hexane solution and drying it, n
- Hexane was distilled off to obtain 2.5 g of a viscous liquid. The content of vitamin E in this viscous liquid was determined by high performance liquid chromatography and was found to be approximately 70%, consisting mainly of α-tocopherol.

Example 2 1 kg of fresh leaves of oil palm, a tropical palm tree
After sufficiently pulverizing the water produced at that time and removing it by compression filtration, it was placed in the same extraction flask as used in Example 1, and further added with 700 g of n-heptane.
ml was added and heated at around 80°C for 2 hours, and vitamin E was extracted while removing water that azeotroped with n-heptane from the system.

After the extraction, the n-heptane solution was cooled to room temperature, filtered under suction to separate the fibrous material from the n-heptane solution, and the n-heptane solution was then concentrated to obtain 95 g of a dark greenish-brown sticky residue. Obtained. 400 ml of methanol was added to this sticky residue, heated while stirring, cooled to around 0°C, and the precipitated solid was separated using a centrifuge. The ethanol solution is the same ion exchange resin as in Example 1.
It passed through a 300ml layer to adsorb vitamin E. Next, this ion exchange resin was washed with 500 ml of methanol, and then vitamin E was eluted from the ion exchange resin with 300 ml of an ethanol solution containing 10% acetic acid. After adding 300 ml of n-hexane to this solution, saturated saline was added. The solution is washed with water until the washing liquid becomes neutral, and then anhydrous sulfur salt is added to the n-hexane solution, and after drying, 3 g of activated clay is added and stirred thoroughly to adsorb the green pigment, followed by fractional filtration. The filtered activated clay was washed with 100 ml of n-hexane, the washing liquid and the filtrate were combined, and the n-hexane was distilled off. 2.5 g of a viscous pale green liquid was obtained. When this product was analyzed by high performance liquid chromatography, the content of vitamin E whose main component is α-tocopherol was about 70%.

Example 3 Using 1 kg of Angelica utilis leaves,
By carrying out the same treatment as in Example 1, a viscous dark and colored liquid containing 20% isositol and 12% α-tocopherol was obtained.

Reference example: 1 kg of oil palm leaves, cut into approximately 1 cm square pieces and from which water has been removed, and 5 kg of toluene are placed in a 10-volume flask equipped with a water separation tube, heated to 84°C, and the water in the leaves is removed. Extraction was carried out for 3 hours while azeotropically removing. The extract was then filtered to remove leaves and other solids, and the solvent was distilled off. In this way, a concentrate of vitamin E was obtained. At this time, the extraction rate of the total amount of vitamin E was 1.92%.

Next, for comparison, 1 kg of the same raw material and 5 toluene
Kg was charged into a 10 volume flask and the extraction was carried out by stirring at 50° C. for 3 hours without azeotroping. Regarding the concentrate obtained by removing the solvent from this extract, the extraction rate of the total amount of vitamin E was determined to be 0.54%. Furthermore, when extraction was performed under the same conditions except that the solvent was changed from toluene to n-hexane, the extraction rate was 0.46%.

As described above, when the azeotropic operation is not performed, the extraction rate of vitamin E is significantly reduced.

Claims (1)

[Claims] 1. After pulverizing the green leaves of a plant and removing the water generated during the process, the water remaining in the green leaves is removed together with the solvent using a non-polar organic solvent that is insoluble in water and forms an azeotrope with water. While performing azeotropic distillation, vitamin E contained in the green leaves is eluted into the solvent, and then the solvent is distilled off from this eluate, and the remaining liquid is treated with an ion exchanger to obtain α
- A method for concentrating vitamin E, which is characterized by obtaining a concentrate of vitamin E mainly consisting of tocopherols.