JPS58210022A - Method for refining and extracting pure active constituent of adlay and method for determining and assaying the same - Google Patents

Abstract

PURPOSE:To obtain easily and simply a pure substance coixenolide, by using the adsorption fraction method for a component obtained by extracting the whole seeds or pulverized seeds or pressed oily substance of an adlay with an organic solvent, etc. CONSTITUTION:The whole seeds or pulverized seeds or pressed oily substance of an adlay are extracted with a lipophilic organic solvent, e.g. an aromatic hydrocarbon type, aliphatic hydrocarbon type, ether type, ester type or ketone type, to give an extractible oily component. The resultant solution is then adsorbed on a porous adsorbent, e.g. silica gel type (for aromatic hydrocarbon type solvent), alumina type (for petroleum ether type or ether type solvent), activated carbon type (for ester type solvent), etc. and then eluted and refined with a suitable solvent or distilled under a high vacuum (by the jet type high vacuum distillation and purification method) or in combination of both methods to give the aimed coixenolide which is an active constituent of the adlay as a pure substance. EFFECT:The aimed substance can be refined and extracted more economically and advantageously than by the conventional method.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for shipping pure products of Coixenolide, an active ingredient of Coixenolide, which is expected to have various drug activities as a traditional Chinese herbal medicine or a folk medicine. It concerns quantitative assay methods.

The present inventor has separately established the drug activity of pure coixenolide through pharmaceutical implantation and clinical experiments, and has applied for a patent for 17 years.As shown in the patent application, the present inventors have established a method for industrially producing a pure product of coixenolide, an effective ingredient of coix seed, and a standard method for its detection. As a result of many years of research, this is the first time that this has been newly established. Until now, there have been only 2.8 reports in the literature regarding the manufacturing method of this substance, coixenolide, and the contents have not clarified the physicochemical index that is essential for the industrial manufacturing method as a pure product, and furthermore, its quality has not been clarified. There are absolutely no reports on the invention of quantitative analysis methods that are essential for assays, and conventional literature reports indicate that it is extremely difficult and complete to find a practical industrial manufacturing method for pure coixenolide that can be applied to pharmaceuticals, cosmetics, etc. It has been considered impossible. The raw material of the present invention may be whole pearl barley seeds, crushed products, or pressed oily substances. First, a solution containing extractable oily components from raw materials using a ribophilic organic solvent (aromatic hydrogen-based, aliphatic hydrogen-based, ether-based, ester-based, or ketone-based) is used for a long-term, silica gel-based solution. The crystals are deposited on a porous adsorbent such as alumina-based or activated carbon-based adsorbent, and then desorbed and deposited using an appropriate solvent. At this time, in the conventional method, the adsorbent is proportional to the degree of ice crystal purification. Although there have been no reports on combinations based on the correlation between By implementing a combination of ``solvent'', ``petroleum ether type or ether type J for alumina type, and ester type for active carbon type'', it is possible to obtain the highest quality target product economically and in a smaller size compared to conventional methods. I invented something that could be done. Also, noting that quartz is an oily substance (at room temperature) and easily susceptible to high-temperature oxidation, the inventors were able to reduce the crude coixenolide to a pure product using a high-vacuum distillation method for the first time. In other words, although conventional literature reports state that fractional distillation is possible,
There is no mention of those conditions. The present inventors have invented the method of reducing the size of pure coixenolide for the first time by applying the jet high vacuum distillation purification method to prevent oxidation.

In addition, although there have been no reports regarding the purity test or quantitative method for coixenolide as a pure product, the present inventor has conducted the first assay using elemental analysis, infrared absorption, and gas chromatography for coixenolide obtained by the above-mentioned purification. , established and invented the quantitative method.

Example 1 A part of silica gel was added by patch method to a solution in which part of pressed pearl barley yuzu oil was dissolved in part of petroleum ether, and after stirring for 2 hours,
The residue obtained by distilling off and concentrating the volatile components is dissolved in 8 parts of toluene and subjected to silica gel column m. Main eluate 80
The residue obtained by concentrating % is then subjected to column separation again in the same manner to obtain 0.85 parts of a blue-yellow colored oil.

Elemental analysis value Molecular weight RO3S H2O04) Calculated value Experimental value 0 7? , 23 76.88H11,941
1,92 Gas chromatography e-column 8E80.8% Injection temperature 290°C Tictor Column // ///
250 °C carrier
Nitrogen gas nuvede
30-40 Sodium/min Cheer Ape
10 u/min relaxation time 5~
6 minutes (son peak) The infrared absorption 11y7-vector is as shown in the following chart.

Procedural amendment dated October 16, 1980 Submitted by the Commissioner of the Patent Office Shima 1) Haruki Tono 1 Indication of the case Patent Application No. 095258 of 1988 3
Relationship with the case of the person making the amendment Patent applicant 4 Hita of the amendment order September 9, 1980 Akira
[Details] Title of the invention: Method for shipping and quantitative assay of active ingredients of Coix vulgaris 2, Claims: Whole seeds of Coix y, their pulverized product, or their pressed oily substances are used as raw materials, and organic solvent extraction is carried out. A production method for shipping pure coixenolide by conducting an adsorption fractionation method or a high-vacuum distillation method for each component, or by combining a drawing method, and a method for determining its consistency.

3. Detailed Description of the Invention The present invention is characterized by its origin, herbal medicine, and 1. The present invention relates to a novel method for shipping pure products of coixenolide, an active ingredient of coixenolide, which is expected to have various drug activities in conjunction with the folk medicine mulberry, and its quantitative assay.

The present inventor has also established the pharmacological activity of pure coixenolide through clinical experiments and obtained a patent for θIT<,
This is the culmination of many years of research and the first new establishment of a method for commercially detecting pure coixenolides in Coix seed and a method for quantitatively detecting them. Conventionally, regarding the manufacturing method of this substance coixenolide, 1. However, the literature only reports 2.3, and the contents do not clarify the physicochemical index essential for the in-house manufacturing method of T leaves as a pure product, and the quantification that is essential for the quality verification. Since there have been no reports regarding the invention of analytical methods, existing literature reports have shown that it is extremely difficult and impossible to find a practical industrial manufacturing method for pure coixenolide that can be applied to pharmaceuticals, cosmetics, etc. Ta. The raw material of the present invention may be whole pearl barley seeds, crushed products, or pressed oily substances. First, a solution of extractable oily components from raw materials using a ribophilic organic solvent (aromatic hydrocarbon, aliphatic hydrocarbon, ether, ester, or ketone) is used. , alumina-based, activated carbon-based, etc. porous adsorbent, and then a suitable f4w is used to reduce the amount of water leakage. At this time, in the conventional method, the adsorbent is proportional to the degree of ice crystal purification. Although there are no reports on combinations based on the correlation between Solvent 1: By implementing the combination of ``petroleum ether or ether type for alumina type'' and ``ester type for activated carbon type'', it is economically advantageous to ship the highest quality target product compared to conventional methods. I invented something that can be done. Also, the crystal is an oily substance (at room temperature)
Noting that it is easy to undergo high-temperature oxidation, the present inventor used a high-vacuum distillation method to convert crude Koiku-tenolide into a pure product.
I was able to ship it for the first time. That is, conventional literature reports state that fractional distillation may be possible, but there is no description of the conditions. The present inventors have invented a method of preventing oxidation by applying the Cent type high vacuum distillation purification method, and packing and shipping pure coixenolide.

Furthermore, although there have been no reports regarding the purity test or quantitative method for coixenolide as a pure product, the present inventor has conducted elemental analysis, infrared absorption, and Gaff chromatography regarding coixenolide obtained through the above-mentioned purification. Testing for the first time,
He was the first to invent a quantitative method.

Example: A portion of silica gel was added to a solution of a portion of pressed pearl barley seed oil dissolved in a portion of petroleum ether using a patch method, and after stirring for 2 hours,
The residue obtained by distilling off the volatile components is dissolved in 3 parts of toluene and subjected to silica gel column separation. Main eluate 80
When the residue obtained by concentrating % is subjected to column separation again in the same manner, 85 parts of a yellowish yellowish color (oil) is obtained.

Elemental analysis value molecular weight [038■l7oO4] Calculated value Experimental value C77,2376,88 Summer 1 11,94.
11, 92mm chromatography column 8E80.8% Injection l Crystallinity 290°C Detector
250'fl carrier
Nitrogen gas speed 8
0-4/1 at/min cheer speed
The lQ m7 minute infrared absorption spectrum is as shown in the drawing.

Example & Same as Example 1 - The residue obtained from the first column treatment was first thoroughly removed from the residue at a bath temperature of 50° to 70°C for about 1 hour, and then Hg0.05~0-07 cod, temperature 65~? 8°C1 distillate slightly yellowish oil fi10.8
'Get 1 copy. The same elemental analysis value, gas chromatography value, and infrared absorption spectrum value as in Example 1 are shown.

Example 3 Example 1. And 1 stick of oil obtained in Example 2, 6,
A dilution series sample was prepared17, and quantitative analysis was performed using gas chromatography1 under the same conditions as in Example 1.The results showed a proportional area area at a retention time of 5 to 6 minutes, and the sounding line was a straight line. I was able to hit the mark.

4. Brief explanation of the drawing The drawing shows an infrared absorption spectrum.

Patent applicant: Yasuo Araki 113-

Claims (1)

[Claims] All f of pearl barley! [By using the pulverized product or the pressed oily substance thereof as raw material, extracting the components with organic solvent extraction, adsorption fractionation method, high vacuum distillation method, or a combination of both methods.] , a manufacturing method for shipping pure coixenolide and its quantitative assay method.